CN-122011306-A - Method for synthesizing phenolic resin from mixed phenol containing 2,4, 6-tricresyl

CN122011306ACN 122011306 ACN122011306 ACN 122011306ACN-122011306-A

Abstract

The invention belongs to the technical field of organic synthesis and separation, and particularly relates to a method for synthesizing phenolic resin from mixed phenol containing 2,4, 6-tricresyl. The invention provides a method for synthesizing phenolic resin by mixed phenol containing 2,4, 6-tricresyl, which comprises the steps of adding a first phenol component, a phenol material containing 2,4, 6-tricresyl, formaldehyde and a catalyst into a reactor, stirring, heating, carrying out thermal insulation reaction, sampling and analyzing that the p-ethyl phenol is less than or equal to 5%, heating, decompressing and dehydrating, distilling off unreacted 2,4, 6-tricresyl, p-ethyl phenol, water and the like, dehydrating to obtain phenolic resin, adding a catalyst into the distilled material, heating to react the unreacted p-ethyl phenol completely (when the formaldehyde in the distilled material is insufficient, adding a small amount of formaldehyde), adding a non-water-soluble solvent for extraction, layering, removing a water layer from a wastewater treatment workshop, and adding an oil layer into a rectifying tower for rectifying to obtain 99%2,4, 6-tricresyl.

Inventors

ZHAO JIAWEI
HAN XUE
SUN HUIQING
YAN CHUNPING
ZHAO YUAN
MENG DECHANG
QIN LIYING
SHI ZHIJIE
Kong Bihua
CHEN YIMING
WANG JING

Assignees

煤炭科学技术研究院有限公司

Dates

Publication Date: 20260512
Application Date: 20260211

Claims (10)

1. A method for synthesizing phenolic resin by mixed phenol containing 2,4, 6-tricresyl, which is characterized by comprising the following steps: (1) Adding a part of phenolic materials containing 2,4, 6-tricresyl, a part of aldehydes and a first catalyst into a polymerization reactor, stirring, heating to 60-105 ℃ to react for 1-6 hours, dropwise adding the remaining phenolic materials containing 2,4, 6-tricresyl and the remaining aldehydes to react for 1-4 hours, and keeping the temperature for 1-6 hours to sample and analyze that the content of p-ethylphenol is less than or equal to 5%, wherein the phenolic materials containing 2,4, 6-tricresyl comprise 10-60 wt% of m-ethylphenol, 10-90 wt% of 2,4, 6-tricresyl, 10-30 wt% of 3, 5-xylenol, 0-10 wt% of 2,4/2, 5-methylethylphenol and 0-10 wt% of 3, 4-xylenol; (2) Cooling to 60-80 ℃, starting vacuumizing and dehydrating, wherein the dehydrating temperature is 80-85 ℃ and the time is 2-5 hours, controlling the final pressure to be minus 0.075-minus 0.08Mpa, and observing the water level of the receiver at the same time, wherein the water level is more particularly constant within 20 minutes; (3) Gradually increasing the vacuum to-0.09 to-0.1 Mpa within 1-2 hours, simultaneously further heating and dehydrating, when the temperature of the materials in the kettle reaches 80-230 ℃ and no liquid is distilled, preserving the heat for 0.5-1 hour, stopping dehydrating, discharging the vacuum by using nitrogen, discharging the materials while the materials are hot under the protection of the nitrogen, and cooling to obtain the phenolic resin.
2. The method for synthesizing a phenolic resin from a mixed phenol containing 2,4, 6-tricresyl according to claim 1, wherein in the step (1), a first phenol component is added into a polymerization reactor, wherein the first phenol component comprises at least one of m-cresol, m-ethylphenol, m-isopropylphenol, m-propylphenol, 3, 5-xylenol, phenol or 3-ethyl-5-cresol, and the amount of the first phenol component is 0.1-200% of the mass of the phenolic material containing 2,4, 6-tricresyl; And/or in the step (1), the phenolic material containing 2,4, 6-tricresyl is obtained by rectifying crude phenol extracted from coal-burnt crude phenol, medium-low temperature coal gasification crude phenol or coal pyrolysis of phenol-containing coal tar.
3. The method for synthesizing a phenolic resin from a mixed phenol containing 2,4, 6-tricresyl according to claim 2, wherein in said step (1), said aldehydes include at least one of paraformaldehyde, formaldehyde or acetaldehyde; the dosage of the aldehydes is 0.8-2.5 times of the total molar weight of the first phenol component, the m-ethyl phenol, the 2, 5-methyl ethyl phenol, the 3, 5-xylenol and the 3, 4-xylenol.
4. The method for synthesizing a phenolic resin from a mixed phenol containing 2,4, 6-tricresyl according to claim 1, wherein in the step (1), a part of the phenolic material containing 2,4, 6-tricresyl is 0 to 100 wt% of the total amount of the phenolic material, and a part of the aldehyde is 0 to 100 wt% of the total amount of the aldehyde.
5. The method for synthesizing a phenolic resin from a mixed phenol containing 2,4, 6-tricresyl according to claim 1, wherein in the step (1), the first catalyst is an acidic catalyst, the acidic catalyst comprises at least one of oxalic acid, formic acid, phosphoric acid, hydrochloric acid, sulfamic acid or benzenesulfonic acid, and the amount of the first catalyst is 0.5-10 wt% of the total amount of phenolic materials.
6. The method for synthesizing the phenolic resin by using the mixed phenol containing 2,4, 6-tricresyl according to claim 1, wherein in the step (1), the first catalyst is an alkaline catalyst, the alkaline catalyst comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia water, and the dosage of the first catalyst is 0.5-10 wt% of the total phenolic material; The step (2) is to add glacial acetic acid or formic acid to neutralize until the pH value is 6-7, gradually opening vacuum to-0.07-0.1 MPa within 0.5-1 hour, starting dehydration, heating to continue dehydration when the dehydration speed is slow or the temperature is reduced to about 70-75 ℃, controlling the final temperature of liquid to be 70-90 ℃ until the water level is reduced to a required value, and sampling and analyzing the water content of the material to be less than or equal to 5%; And (3) adding ethylene glycol into a polymerization reactor, uniformly stirring, sampling, analyzing the moisture and the viscosity, stopping vacuumizing when the moisture is 2-5%, adding ethanol according to the requirements of different products to adjust the viscosity to 10-30 Pa.s, cooling to 50 ℃ after the viscosity reaches the requirements, and discharging, wherein the consumption of the ethylene glycol is 1-10% of the mass of the phenolic material raw material.
7. The method for synthesizing the phenolic resin by using the mixed phenol of 2,4, 6-tricresyl according to claim 5 or 6, which is characterized by further comprising the step (4) of adding a second catalyst and aldehydes into the distilled material, heating to 80-105 ℃ for reflux reaction for 1-3 hours, detecting that the p-ethyl phenol is less than or equal to 0.5% and is qualified, adding a water-insoluble solvent for extraction, stirring for 0.5-2 hours, standing for 0.5-1 hour for layering, heating a water layer to remove a small amount of solvent, then sending the water layer to a wastewater treatment workshop for treatment, washing the oil layer once by water, and layering to obtain an oil layer which is a solution of 2,4, 6-tricresyl.
8. The method for synthesizing a phenolic resin from a mixed phenol containing 2,4, 6-tricresyl according to claim 7, wherein the second catalyst is an acidic catalyst or a basic catalyst, the acidic catalyst comprises at least one of oxalic acid, formic acid, phosphoric acid or hydrochloric acid, the basic catalyst comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia water; The dosage of the second catalyst is 0.01-0.5 wt% of the total weight of phenolic material raw materials; The dosage of the aldehydes is 0-0.5 times of the total molar weight of the first phenol component, the m-ethyl phenol, the 2, 5-methyl ethyl phenol, the 3, 5-xylenol and the 3, 4-xylenol.
9. The method for synthesizing the phenolic resin from the mixed phenol containing the 2,4, 6-tricresyl, which is characterized in that the water-insoluble solvent comprises at least one of aromatic hydrocarbon, chlorinated alkane, ether, ketone or ester, and the dosage of the water-insoluble solvent is 0.5-2 times of the total weight of the phenolic material raw material; The water consumption in the oil layer washing process is 0.01-0.1 time of the weight of the water-insoluble solvent.
10. The method for synthesizing the phenolic resin by using the mixed phenol containing 2,4, 6-tricresyl according to claim 7, which is characterized by further comprising the steps of (5) adding the obtained solution of 2,4, 6-tricresyl into a distillation kettle with 5-30 trays, heating, distilling under normal pressure and then decompressing to remove solvent for application, transferring the materials in the distillation kettle into a high-efficiency rectifying kettle with the tray number of 100-250, rectifying to obtain 99% of 2,4, 6-tricresyl or crude 2,4, 6-tricresyl, and putting the kettle residues into a polymerization reactor for the next phenolic resin synthesis reaction; The pressure of reduced pressure distillation is-0.03 to-0.07 MPa, the reflux ratio (1-3) is 1, the pressure of rectification is-0.07 to-0.1 MPa, and the reflux ratio (5-25) is 1.

Description

Method for synthesizing phenolic resin from mixed phenol containing 2,4, 6-tricresyl Technical Field The invention belongs to the technical field of organic synthesis and separation, and particularly relates to a method for synthesizing phenolic resin from mixed phenol containing 2,4, 6-tricresyl. Background Phenolic resin is a synthetic resin formed by polycondensation of phenol and formaldehyde under the action of a catalyst, and has wide application in the fields of refractory materials, friction materials, packaging materials and the like due to the excellent performances of high temperature resistance, chemical resistance, bonding strength and the like. However, the raw material phenol is expensive, so that the production cost is high. Therefore, how to prepare phenolic resins using mixed powders containing 2,4, 6-tricresyl has received increasing attention from those skilled in the art. Disclosure of Invention The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, the examples of the present invention propose a method for synthesizing a phenolic resin from a mixed phenol containing 2,4, 6-tricresyl. The method for synthesizing the phenolic resin by the mixed phenol containing the 2,4, 6-tricresyl comprises the following steps: (1) Adding a part of phenolic materials containing 2,4, 6-tricresyl, a part of aldehydes and a first catalyst into a polymerization reactor, stirring, heating to 60-105 ℃ to react for 1-6 hours, dropwise adding the remaining phenolic materials containing 2,4, 6-tricresyl and the remaining aldehydes to react for 1-4 hours, and keeping the temperature for 1-6 hours to sample and analyze that the content of p-ethylphenol is less than or equal to 5%, wherein the phenolic materials containing 2,4, 6-tricresyl comprise 10-60 wt% of m-ethylphenol, 10-90 wt% of 2,4, 6-tricresyl, 10-30 wt% of 3, 5-xylenol, 0-10 wt% of 2,4/2, 5-methylethylphenol and 0-10 wt% of 3, 4-xylenol; (2) Cooling to 60-80 ℃, starting vacuumizing and dehydrating, wherein the dehydrating temperature is 80-85 ℃ and the time is 2-5 hours, controlling the final pressure to be minus 0.075-minus 0.08Mpa, and observing the water level of the receiver at the same time, wherein the water level is more particularly constant within 20 minutes; (3) Gradually increasing the vacuum to-0.09 to-0.1 Mpa within 1-2 hours, simultaneously further heating and dehydrating, when the temperature of the materials in the kettle reaches 80-230 ℃ and no liquid is distilled, preserving the heat for 0.5-1 hour, stopping dehydrating, discharging the vacuum by using nitrogen, discharging the materials while the materials are hot under the protection of the nitrogen, and cooling to obtain the phenolic resin. The method for synthesizing the phenolic resin by using the mixed phenol containing 2,4, 6-tricresyl has the advantages and technical effects that 1, the method of the embodiment of the invention utilizes the characteristic that 2,4, 6-tricresyl is rarely reacted with aldehyde, completely reacts m-ethyl phenol containing 2,4, 6-tricresyl, p-ethyl phenol, 3, 5-xylenol, 3, 4-xylenol and the like with formaldehyde, uses part of low-cost phenol materials containing 2,4, 6-tricresyl to replace phenol to produce phenolic resin, simultaneously produces 99%2,4, 6-tricresyl, has better economic benefit, simultaneously expands the application range and market scale of the phenol materials containing 2,4, 6-tricresyl, and 2, the method of the embodiment of the invention uses m-p-ethyl phenol containing 2,4, 6-tricresyl to replace phenol to produce phenolic resin, can effectively solve the problem of refining m-p-ethyl phenol containing 2,4, 6-tricresyl generated by 10-20 ten thousand tons of crude phenol generated by coal gasification, coal pyrolysis, coal liquefaction industry, reduces the production cost of the coal gasification industry and makes a good contribution to coal gasification industry and has a health development. In some embodiments, in the step (1), adding a first phenol component into the polymerization reactor, wherein the first phenol component comprises at least one of m-cresol, m-ethylphenol, m-isopropylphenol, m-propylphenol, 3, 5-xylenol, phenol or 3-ethyl-5-cresol, and the amount of the first phenol component is 0.1-200% of the mass of the phenolic material containing 2,4, 6-trimethylphenol; And/or in the step (1), the phenolic material containing 2,4, 6-tricresyl is obtained by rectifying crude phenol extracted from coal-burnt crude phenol, medium-low temperature coal gasification crude phenol or coal pyrolysis of phenol-containing coal tar. In some embodiments, in step (1), the aldehydes comprise at least one of paraformaldehyde, formaldehyde or acetaldehyde; the dosage of the aldehydes is 0.8-2.5 times of the total molar weight of the first phenol component, the m-ethyl phenol, the 2, 5-methyl ethyl phenol, the 3, 5-xylenol and the 3, 4-xylenol. In some embodime