A phenolic resin production process

Abstract

This application relates to the technical field of polymer materials, and specifically discloses a production process of phenolic resin. The production process of phenolic resin includes sequentially adding phenolic components, a catalyst, and water into a reactor. After stirring and dissolving, a formaldehyde solution is added for reaction to obtain a phenolic solution; a modifier and an acid solution are added to the phenolic solution and stirring reaction is continued to obtain phenolic resin; the above production process is obtained by adding a catalyst to phenol and aldehyde for reaction, then adding a modifier for mixing, and adding acid for curing; first, the catalyst promotes the condensation reaction of phenol and aldehyde to form a phenolic solution with macromolecules having a linear structure, and then after adding a modifier for mixing and modification, acid is added for curing to form a phenolic resin with a cross-linked network structure; the reaction conditions of this application are mild, the reaction process is controllable, the curing temperature is low, and the obtained phenolic resin has excellent mechanical properties such as strength, toughness, and wear resistance.

Description

Technical Field

[0001] This application relates to the technical field of polymer materials, and more specifically, to a production process of phenolic resin. Background Technique

[0002] Phenolic resin is a kind of resin obtained by the phenolic condensation reaction of phenolic organic compounds and other aldehyde organic compounds, among which the phenolic resin obtained by the condensation of phenol and formaldehyde is the most important. Phenolic resin has the advantages of low product price, easy processing and obtaining of raw materials, simple production process, high mechanical strength of products, low toxicity, heat resistance, flame retardancy, excellent electrical insulation performance, etc., and is widely used in various fields such as refractory materials, molding plastics, foam plastics, coatings, casting composite resins, semiconductor packaging materials, etc.

[0003] In actual production, it is not common for phenolic resin to be directly used as a material. The reason is that the phenolic hydroxyl group and methylene group in the structure of phenolic resin are easily oxidized by oxidizing substances, which affects its heat resistance, and it is brittle after curing. At the same time, the H2O molecules generated during the curing process will cause bubbles inside the cured resin, resulting in a decrease in the mechanical properties of the resin. Therefore, generally, phenolic resin needs to be modified before it can be applied to actual production.

[0004] In related technologies, inorganic fillers, rubber elastomers, thermoplastics, nanoparticles, etc. are often directly added to phenolic resin to improve its mechanical properties. The above modification methods are simple to operate. Although they can improve the mechanical properties of phenolic resin to a certain extent, due to the weak bonding between the filler and phenolic resin, while improving the mechanical properties of phenolic resin, they will also cause a decline in the excellent properties of phenolic resin itself. Based on the above statement, in order to obtain a high-performance phenolic resin that can be directly applied to actual production, this application proposes a production process of phenolic resin. Summary of the Invention

[0005] In order to solve the problem that the modification of phenolic resin in the prior art will cause a decline in the excellent properties of phenolic resin itself while improving the mechanical properties of phenolic resin, this application provides a production process of phenolic resin.

[0006] This application provides a production process of phenolic resin, adopting the following technical scheme:

[0007] A production process of phenolic resin includes the following production steps:

[0008] S1. Add phenolic components, catalyst and water to the reactor in sequence. After stirring and dissolving, add formaldehyde solution to react to obtain a phenolic solution;

[0009] S2. Add a modifier and an acid solution to the phenolic solution in step S1 and continue stirring and reacting to obtain phenolic resin.

[0010] By adopting the above technical solution, the present application discloses a phenolic resin production process, which is obtained by reacting phenol and aldehyde with a catalyst, then adding a modifier for mixing, and adding an acid for curing; firstly, the catalyst promotes the condensation reaction of phenol and aldehyde to form a phenolic solution with macromolecules having a linear structure, and then after adding a modifier for mixing and modification, adding an acid for curing to form a phenolic resin with a crosslinked network structure; the reaction conditions of the present application are mild, the reaction process is controllable, the curing temperature is low, and the mechanical properties such as strength, toughness, and wear resistance of the obtained phenolic resin are excellent.

[0011] Preferably, in the step S1, the mass ratio of the phenolic component to the formaldehyde solution is 1:1.9 - 2.4.

[0012] Preferably, the addition amount of the catalyst in the step S1 is 0.8 - 1.2% of the mass of the phenolic component.

[0013] Preferably, the addition amount of water in the step S1 is 1.1 - 1.3 times the mass of the phenolic component.

[0014] By adopting the above technical solution, the present application can effectively ensure the smooth occurrence of the reaction by controlling the phenol - aldehyde ratio and the addition amount of the catalyst, improve the curing crosslinking degree of the phenolic resin, and further improve its mechanical properties.

[0015] Preferably, the phenolic component in the step S1 is a compound of phenol, cetylphenol, and 2,6 - dimethylphenol with a mass ratio of 5.5:3:1.5.

[0016] By adopting the above technical solution, the present application selects phenol, cetylphenol, and 2,6 - dimethylphenol together as the phenolic component, which has good reaction stability and high curing crosslinking degree when used for producing phenolic resin, and the obtained phenolic resin has higher strength.

[0017] Preferably, the catalyst includes modified silica, barium chloride, and lanthanum chloride.

[0018] Preferably, the catalyst is prepared by the following method:

[0019] Take tetraethoxysilane, n - octyltriethoxysilane, and boron trifluoride and add them to an ethanol solution with a mass fraction of 30% in sequence. After stirring and dispersing, add ammonia water until the pH is 9, neutralize and precipitate, and centrifuge and dry to obtain a mixture;

[0020] Mix the mixture, barium chloride, lanthanum chloride, and cetyltrimethylammonium chloride evenly by grinding, then calcine at a temperature of 480 - 520 °C for 2 - 5 h, and grind after cooling to obtain the catalyst.

[0021] Preferably, the mass ratio of the tetraethoxysilane, n-octyltriethoxysilane, boron trifluoride and ethanol solution is 1.2-1.4:0.1-0.2:0.4-0.5:3-5.

[0022] Preferably, the mass ratio of the mixture, barium chloride, lanthanum chloride and cetyltrimethylammonium chloride is 1:0.2-0.3:0.05-0.1:0.1-0.3.

[0023] By adopting the above technical solution, the present application uses tetraethoxysilane, n-octyltriethoxysilane and boron trifluoride to jointly prepare modified silica, and then adds barium chloride and lanthanum chloride to grind and calcine to obtain a catalyst with a high specific surface area and multiple active sites. The catalyst of the present application has high catalytic activity, good catalytic selectivity and good catalytic stability, can ensure the smooth progress of the catalytic reaction, reduce or avoid the foaming of the reaction solution, and thus ensure the thermal stability and mechanical properties of the finally prepared phenolic resin.

[0024] Preferably, the mass ratio of the phenolic solution, modifier and acid solution in step S2 is 1-2:0.4-0.5:0.1.

[0025] Preferably, the modifier in step S2 comprises a compounded bisphenol A and hydroxyl-terminated polybutadiene with a mass ratio of 1:1.5-2.

[0026] By adopting the above technical solution, the present application uses the compounded bisphenol A and hydroxyl-terminated polybutadiene as the modifier together, and blends the prepared phenolic solution with the modifier. On the one hand, it is beneficial to improve the heat resistance of the prepared phenolic resin. On the other hand, the properties such as plasticity, flexibility and strength of the obtained phenolic resin have been greatly improved.

[0027] Preferably, the compounded bisphenol A comprises bisphenol A and diallyl bisphenol A with a mass ratio of 1:0.3-0.5.

[0028] By adopting the above technical solution, the present application adds the compounded bisphenol A to the phenolic solution, introduces bisphenol A into the molecular structure, and improves the heat resistance and toughness of the phenolic resin. By compounding and modifying with bisphenol A and diallyl bisphenol A, the heat resistance and toughness can be further improved.

[0029] Preferably, the acid solution is prepared by compounding 3.2 mol / L glacial acetic acid and 4-dodecylbenzenesulfonic acid according to a mass ratio of 1:1.

[0030] By adopting the above technical solution, the present application prepares the acid solution by compounding 3.2 mol / L glacial acetic acid and 4-dodecylbenzenesulfonic acid. Its addition amount is small, it can accelerate the curing of the phenolic resin under mild reaction conditions, the curing temperature is low, and at the same time it can effectively avoid the generation of bubbles during the curing process, and ensure the mechanical properties of the prepared phenolic resin.

[0031] In summary, the present application has the following beneficial effects:

[0032] The present application is obtained by reacting phenol and formaldehyde with a catalyst, adding a modifier for mixing, and then curing with an acid. First, the catalyst promotes the condensation reaction of phenol and formaldehyde to form a phenolic aldehyde solution with a linear macromolecular structure. Then, after adding a modifier for mixing and modification, an acid is added for curing to form a cross-linked network structure of phenolic resin. The reaction conditions of the present application are mild, the reaction process is controllable, the curing temperature is low, and the mechanical properties such as strength, toughness, and wear resistance of the obtained phenolic resin are excellent.

[0033] The present application uses tetraethoxysilane, n-octyltriethoxysilane, and boron trifluoride to jointly prepare modified silica, and then adds barium chloride and lanthanum chloride for co-grinding and calcination to obtain a catalyst with a high specific surface area and multiple active sites. The catalyst of the present application has high catalytic activity, good catalytic selectivity, and good catalytic stability, can ensure the smooth progress of the catalytic reaction, reduce or avoid the foaming of the reaction solution, and thus ensure the thermal stability and mechanical properties of the finally prepared phenolic resin.

[0034] The present application uses a compound of bisphenol A and hydroxyl-terminated polybutadiene as a modifier, and blends the prepared phenolic aldehyde solution with the modifier. On the one hand, it is beneficial to improve the heat resistance of the prepared phenolic resin. On the other hand, the properties such as plasticity, flexibility, and strength of the obtained phenolic resin have been greatly improved. Detailed implementation manners

[0035] The following further elaborates on the present application with reference to examples.

[0036] Preparation Examples 1-3 and Comparative Examples 1-3 provide the preparation methods of the catalyst.

[0037] Preparation Example 1

[0038] The catalyst is prepared by the following method:

[0039] Weigh the raw materials tetraethoxysilane, n-octyltriethoxysilane, boron trifluoride, and an ethanol solution with a mass fraction of 25% according to the mass ratio of 1.2:0.1:0.4:3 for standby;

[0040] Add tetraethoxysilane, n-octyltriethoxysilane, and boron trifluoride to the ethanol solution with a mass fraction of 25% in sequence. Under the conditions of a temperature of 60 °C and a rotation speed of 260 r / min, stir and disperse for 8 min, then add 7.5 mol / L ammonia water until the pH is 9 for neutralization precipitation. After centrifuging at a rotation speed of 12000 rpm for 12 min, place it in a vacuum drying oven and dry it at a temperature of 80 °C for 1 h to obtain a mixture;

[0041] Weigh the raw material mixture, barium chloride, lanthanum chloride, and cetyltrimethylammonium chloride according to the mass ratio of 1:0.2:0.05:0.1, mix and grind them, control the grinding pressure at 0.10 MPa and the grinding temperature at 65 °C. After grinding and mixing for 2 h, calcine at 480 °C for 4 h, and then grind after cooling to obtain a catalyst with a particle size of 0.1 μm.

[0042] Preparation Example 2

[0043] The catalyst is prepared by the following method:

[0044] Weigh the raw materials tetraethoxysilane, n-octyltriethoxysilane, boron trifluoride, and an ethanol solution with a mass fraction of 30% according to the mass ratio of 1.4:0.2:0.4:4 for standby;

[0045] Add tetraethoxysilane, n-octyltriethoxysilane, and boron trifluoride to the ethanol solution with a mass fraction of 30% in sequence. Under the conditions of a temperature of 65 °C and a rotation speed of 250 r / min, stir and disperse for 10 min, then add 7.8 mol / L ammonia water until the pH reaches 9 to neutralize the precipitate. After centrifuging at 15000 rpm for 10 min, place it in a vacuum drying oven and dry at 85 °C for 0.8 h to obtain a mixture;

[0046] Weigh the raw material mixture, barium chloride, lanthanum chloride, and cetyltrimethylammonium chloride according to the mass ratio of 1:0.2:0.1:0.2, mix and grind them, control the grinding pressure at 0.12 MPa and the grinding temperature at 60 °C. After grinding and mixing for 1.5 h, calcine at 500 °C for 3 h, and then grind after cooling to obtain a catalyst with a particle size of 1 μm.

[0047] Preparation Example 3

[0048] The catalyst is prepared by the following method:

[0049] Weigh the raw materials tetraethoxysilane, n-octyltriethoxysilane, boron trifluoride, and an ethanol solution with a mass fraction of 35% according to the mass ratio of 1.4:0.2:0.5:5 for standby;

[0050] Add tetraethoxysilane, n-octyltriethoxysilane, and boron trifluoride to the ethanol solution with a mass fraction of 35% in sequence. Under the conditions of a temperature of 70 °C and a rotation speed of 240 r / min, stir and disperse for 12 min, then add 8.0 mol / L ammonia water until the pH reaches 9 to neutralize the precipitate. After centrifuging at 18000 rpm for 8 min, place it in a vacuum drying oven and dry at 90 °C for 0.5 h to obtain a mixture;

[0051] Weigh the raw material mixture, barium chloride, lanthanum chloride and cetyltrimethylammonium chloride according to the mass ratio of 1:0.3:0.1:0.3, mix and grind them. Control the grinding pressure at 0.15 MPa and the grinding temperature at 55 °C. After grinding and mixing for 1 h, calcine at 520 °C for 2 h. After cooling, grind to obtain a catalyst with a particle size of 10 μm.

[0052] Comparative Preparation Example 1

[0053] Comparative Preparation Example 1 is the same as Preparation Example 1, except that: in the catalyst preparation process, boron trifluoride is replaced with an equal mass of ethanol solution. The specific preparation method is as follows:

[0054] Weigh the raw materials tetraethoxysilane, n-octyltriethoxysilane and a 25% ethanol solution by mass ratio of 1.2:0.1:3.4 for standby;

[0055] Add tetraethoxysilane and n-octyltriethoxysilane to the 25% ethanol solution in sequence. Under the conditions of a temperature of 60 °C and a rotation speed of 260 r / min, stir and disperse for 8 min, then add 7.5 mol / L ammonia water until the pH reaches 9 to neutralize the precipitate. After centrifuging at 12000 rpm for 12 min, place it in a vacuum drying oven and dry at 80 °C for 1 h to obtain a mixture;

[0056] Weigh the raw material mixture, barium chloride, lanthanum chloride and cetyltrimethylammonium chloride according to the mass ratio of 1:0.2:0.05:0.1, mix and grind them. Control the grinding pressure at 0.10 MPa and the grinding temperature at 65 °C. After grinding and mixing for 2 h, calcine at 480 °C for 4 h. After cooling, grind to obtain a catalyst with a particle size of 0.1 μm.

[0057] Comparative Preparation Example 2

[0058] Comparative Preparation Example 2 is the same as Preparation Example 1, except that: in the catalyst preparation process, lanthanum chloride is replaced with an equal mass of barium chloride. The specific preparation method is as follows:

[0059] Weigh the raw materials tetraethoxysilane, n-octyltriethoxysilane, boron trifluoride and a 25% ethanol solution by mass ratio of 1.2:0.1:0.4:3 for standby;

[0060] Add tetraethoxysilane, n-octyltriethoxysilane and boron trifluoride to the 25% ethanol solution in sequence. Under the conditions of a temperature of 60 °C and a rotation speed of 260 r / min, stir and disperse for 8 min, then add 7.5 mol / L ammonia water until the pH reaches 9 to neutralize the precipitate. After centrifuging at 12000 rpm for 12 min, place it in a vacuum drying oven and dry at 80 °C for 1 h to obtain a mixture;

[0061] Weigh the raw material mixture, barium chloride, and cetyltrimethylammonium chloride according to a mass ratio of 1:0.25:0.1, mix and grind them. Control the grinding pressure at 0.10 MPa and the grinding temperature at 65 °C. After grinding and mixing for 2 h, calcine at a temperature of 480 °C for 4 h. After cooling, grind to obtain a catalyst with a particle size of 0.1 μm.

[0062] Comparative Preparation Example 3

[0063] Comparative Preparation Example 3 is the same as Preparation Example 1, except that: in the catalyst preparation process, barium chloride is replaced with lanthanum chloride in equal mass. The specific preparation method is as follows:

[0064] Weigh tetraethoxysilane, n-octyltriethoxysilane, boron trifluoride, and an ethanol solution with a mass fraction of 25% according to a mass ratio of 1.2:0.1:0.4:3 for standby;

[0065] Add tetraethoxysilane, n-octyltriethoxysilane, and boron trifluoride to the ethanol solution with a mass fraction of 25% in sequence. Under the conditions of a temperature of 60 °C and a rotation speed of 260 r / min, stir and disperse for 8 min, then add 7.5 mol / L ammonia water until the pH is 9 for neutralization precipitation. After centrifuging at a rotation speed of 12000 rpm for 12 min, place it in a vacuum drying oven and dry at a temperature of 80 °C for 1 h to obtain a mixture;

[0066] Weigh the raw material mixture, lanthanum chloride, and cetyltrimethylammonium chloride according to a mass ratio of 1:0.25:0.1, mix and grind them. Control the grinding pressure at 0.10 MPa and the grinding temperature at 65 °C. After grinding and mixing for 2 h, calcine at a temperature of 480 °C for 4 h. After cooling, grind to obtain a catalyst with a particle size of 0.1 μm.

[0067] Examples 1-5 provide a phenolic resin production process, which is described below taking Example 1 as an example.

[0068] Example 1

[0069] A phenolic resin production process specifically includes the following production steps:

[0070] S1. Add the phenolic component, catalyst, and water to the reactor in sequence, heat up to 65 °C, stir and dissolve at a rotation speed of 550 r / min for 20 min, then keep the conditions unchanged and add the formaldehyde solution to react for 3 h to obtain a phenolic solution;

[0071] Among them, the phenolic component is a compound of phenol, hexadecylphenol, and 2,6-dimethylphenol with a mass ratio of 5.5:3:1.5;

[0072] The catalyst is prepared from Preparation Example 1;

[0073] The mass fraction of the formaldehyde solution is 37%;

[0074] The mass ratio of the phenolic component to the formaldehyde solution is 1:1.9;

[0075] The addition amount of the catalyst is 0.8% of the mass of the phenolic component;

[0076] The addition amount of water is 1.1 times the mass of the phenolic component;

[0077] S2. Keep the rotation speed unchanged, continue to heat the phenolic aldehyde solution to 80 °C, add the modifier and react for 2 h, then cool down to 20 °C, add the acid solution and continue to stir for 20 min, and then keep warm and cure for 0.5 h to obtain the phenolic resin;

[0078] Among them, the mass ratio of the phenolic aldehyde solution, the modifier and the acid solution is 1:0.4:0.1;

[0079] The modifier includes compound bisphenol A and hydroxyl-terminated polybutadiene with a mass ratio of 1:1.5;

[0080] The compound bisphenol A includes bisphenol A and diallyl bisphenol A with a mass ratio of 1:0.3;

[0081] The acid solution is prepared by compounding 3.2 mol / L glacial acetic acid and 4-dodecylbenzenesulfonic acid in a mass ratio of 1:1.

[0082] Examples 2-3 are the same as Example 1, except that: the production raw material ratio / process parameters are different, as shown in Table 1 specifically.

[0083] Table 2:

[0084]

[0085]

[0086] Example 4

[0087] Example 4 is the same as Example 1, except that: the catalyst is prepared from Preparation Example 2.

[0088] Example 5

[0089] Example 5 is the same as Example 1, except that: the catalyst is prepared from Preparation Example 3.

[0090] In order to verify the performance of the phenolic resin obtained by the production of Examples 1-5 of the present application, the applicant set Comparative Examples 1-12, among which:

[0091] Comparative Example 1 is the same as Example 1, except that: the catalyst is prepared from Comparative Preparation Example 1.

[0092] Comparative Example 2 was the same as Example 1, except that: the catalyst was prepared from Comparative Preparation Example 2.

[0093] Comparative Example 3 was the same as Example 1, except that: the catalyst was prepared from Comparative Preparation Example 3.

[0094] Comparative Example 4 was the same as Example 1, except that: the total amount of phenolic components remained unchanged, and a mixture of phenol, cetylphenol and 2,6-dimethylphenol with a mass ratio of 8:1:1 was used.

[0095] Comparative Example 5 was the same as Example 1, except that: the total amount of phenolic components remained unchanged, and a mixture of phenol and cetylphenol with a mass ratio of 7:3 was used.

[0096] Comparative Example 6 was the same as Example 1, except that: the total amount of phenolic components remained unchanged, and only a mixture of phenol and 2,6-dimethylphenol with a mass ratio of 8.5:1.5 was used.

[0097] Comparative Example 7 was the same as Example 1, except that: the modifier included a mixture of bisphenol A and hydroxyl-terminated polybutadiene with a mass ratio of 1:1.

[0098] Comparative Example 8 was the same as Example 1, except that: the modifier included bisphenol A and hydroxyl-terminated polybutadiene with a mass ratio of 1:1.5.

[0099] Comparative Example 9 was the same as Example 1, except that: the modifier included diallyl bisphenol A and hydroxyl-terminated polybutadiene with a mass ratio of 1:1.5.

[0100] Comparative Example 10 was the same as Example 1, except that: the acid solution was prepared by mixing 3.2 mol / L phosphoric acid and 4-dodecylbenzenesulfonic acid in a mass ratio of 1:1.

[0101] Comparative Example 11 was the same as Example 1, except that: the acid solution was 3.2 mol / L glacial acetic acid.

[0102] Comparative Example 12 was the same as Example 1, except that: the acid solution was 4-dodecylbenzenesulfonic acid.

[0103] The properties of the phenolic resins obtained in Examples 1-5 and Comparative Examples 1-12 of the present application were measured respectively, and the specific test methods were as follows:

[0104] Thermal stability test:

[0105] Thermogravimetric analysis (TG) was carried out using a synchronous thermal analyzer (instrument model: STA449F5), and the test indexes are as follows: test temperature range: 200 - 1000 °C; heating rate: 30 K / min; test atmosphere: inert atmosphere N2, flow rate: 50 mL / min; mechanical property test: tensile strength and impact strength were detected according to the standard of GB / T2567 - 2008.

[0106] The test results are shown in Table 2 below:

[0107]

[0108]

[0109] It can be seen from the results shown in Table 2 above that the comprehensive performance of the phenolic resins obtained in Examples 1 - 5 of this application is far superior to that of Comparative Examples 1 - 12.

[0110] It can be seen from Example 1 and Comparative Examples 1 - 3 that in this application, tetraethoxysilane, n - octyltriethoxysilane and boron trifluoride are used together to prepare modified silica, and then barium chloride and lanthanum chloride are added and co - ground and then calcined to obtain a catalyst, which is used in the catalytic reaction of phenolic resin, and can ensure the thermal stability and mechanical properties of the finally prepared phenolic resin.

[0111] It can be seen from Example 1 and Comparative Examples 4 - 6 that in this application, phenol, hexadecylphenol and 2,6 - dimethylphenol are selected together as phenolic components, which are used in the production of phenolic resin, and have the characteristics of good reaction stability and high curing cross - linking degree, and the prepared phenolic resin has higher strength.

[0112] It can be seen from Example 1 and Comparative Examples 7 - 9 that in this application, compounded bisphenol A and hydroxyl - terminated polybutadiene are used together as modifiers, which is beneficial to improving the heat resistance and mechanical properties of the prepared phenolic resin; the compound modification of bisphenol A and diallylbisphenol A has a synergistic effect, and can further improve its heat resistance and mechanical properties.

[0113] It can be seen from Example 1 and Comparative Examples 10 - 12 that in this application, an acid solution is prepared by compounding glacial acetic acid and 4 - dodecylbenzenesulfonic acid, and the two have a synergistic effect, and can ensure the mechanical properties of the prepared phenolic resin.

[0114] This specific embodiment is only an explanation of this application, and it does not limit this application. After reading this specification, those skilled in the art can make modifications that do not contribute creatively to this embodiment as needed, but as long as they are within the scope of the claims of this application, they are protected by the patent law.

Claims

1. A phenolic resin production process, characterized in that, It includes the following production steps: S1. Add phenolic components, catalyst and water into a reactor in sequence. After stirring and dissolving, add formaldehyde solution for reaction to obtain phenolic aldehyde solution; S2. Add modifier and acid solution into the phenolic aldehyde solution in step S1 and continue stirring for reaction to obtain phenolic resin; In step S2, the modifier includes a compound of bisphenol A and hydroxyl-terminated polybutadiene with a mass ratio of 1:1.5 - 2; In step S1, the mass ratio of phenolic components to formaldehyde solution is 1:1.9 - 2.4; In step S1, the addition amount of catalyst is 0.8 - 1.2% of the mass of phenolic components; In step S1, the addition amount of water is 1.1 - 1.3 times the mass of phenolic components; The phenolic components in step S1 are a compound of phenol, cetylphenol and 2,6 - dimethylphenol with a mass ratio of 5.5:3:1.5; The catalyst includes modified silica, barium chloride and lanthanum chloride; The catalyst is prepared by the following method: Take tetraethoxysilane, n - octyltriethoxysilane and boron trifluoride and add them into an ethanol solution with a mass fraction of 30% in sequence. After stirring and dispersing, add ammonia water until the pH is 9, neutralize and precipitate, then centrifuge and dry to obtain a mixture; Mix and grind the mixture, barium chloride, lanthanum chloride and cetyltrimethylammonium chloride evenly, then calcine at a temperature of 480 - 520°C for 2 - 5 h, and grind after cooling to obtain the catalyst; In step S2, the mass ratio of phenolic aldehyde solution, modifier and acid solution is 1 - 2:0.4 - 0.5:0.1; The compound bisphenol A includes bisphenol A and diallylbisphenol A with a mass ratio of 1:0.3 - 0.5; The acid solution is prepared by compounding 3.2 mol / L glacial acetic acid and 4 - dodecylbenzenesulfonic acid according to a mass ratio of 1:1.

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