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CN116731285B - Bisphenol A type epoxy resin and production process and production device thereof - Google Patents

Bisphenol A type epoxy resin and production process and production device thereof Download PDF

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Publication number
CN116731285B
CN116731285B CN202311006834.9A CN202311006834A CN116731285B CN 116731285 B CN116731285 B CN 116731285B CN 202311006834 A CN202311006834 A CN 202311006834A CN 116731285 B CN116731285 B CN 116731285B
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bisphenol
epoxy resin
water
ech
reaction kettle
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CN116731285A (en
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张亮
熊高虎
齐润崧
李陈洪
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Dongfang Feiyuan Shandong Electronic Materials Co ltd
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Dongfang Feiyuan Shandong Electronic Materials Co ltd
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention belongs to the technical field of preparation of bisphenol A epoxy resin, and particularly relates to bisphenol A epoxy resin, a production process thereof and a production device thereof. The production process of the bisphenol A epoxy resin comprises the following steps: mixing sodium hydroxide solution and water, adding bisphenol A, heating and stirring to obtain a system I; adding benzyl triethyl ammonium chloride into ECH, heating and stirring, and reacting to obtain a second system; adding the first system into the second system to obtain a third system; depressurizing, heating, steam bubbling and cooling the system III to recover ECH; adding toluene and water into the system III, stirring, standing and separating to obtain toluene resin; f. benzene removal: toluene resin is decompressed and heated, toluene is recovered, and water is added for rotary evaporation, so that bisphenol A type epoxy resin is obtained. The bisphenol A epoxy resin production process provided by the invention has the advantages of continuous reaction, low energy consumption, strong index controllability and narrow molecular weight distribution of the prepared bisphenol A epoxy resin, and also provides a production device.

Description

Bisphenol A type epoxy resin and production process and production device thereof
Technical Field
The invention belongs to the technical field of preparation of bisphenol A epoxy resin, and particularly relates to bisphenol A epoxy resin, a production process thereof and a production device thereof.
Background
Epoxy resin refers to a resin compound having at least two reactive epoxy groups in the molecule. The epoxy resin has the following advantages after curing: has strong adhesion to metal, chemical corrosion resistance, high mechanical strength and good electrical insulation. Epoxy resins can be cured over a fairly broad temperature range and have a small volume shrinkage upon curing. Bisphenol A type epoxy resin is a high molecular compound prepared by condensing bisphenol A, ECH (epichlorohydrin) under alkaline condition, washing with water, and refining with solvent. The epoxy resin has excellent chemical resistance, electric insulating performance and physical and mechanical performance, so that it may be used widely in adhesive, paint, glass fiber reinforced plastic, laminated board, electronic casting, encapsulating, etc.
The existing technology for synthesizing bisphenol A epoxy resin generally comprises the following 6 types: (1) one-step method: the principle is that bisphenol A and ECH are directly polycondensed in the presence of sodium hydroxide to generate bisphenol A type epoxy resin; (2) a two-step process: the principle is that bisphenol A and ECH firstly carry out etherification ring-opening reaction under the condition of a catalyst, and then sodium hydroxide solution is added to carry out ring-closing reaction to generate bisphenol A type epoxy resin; (3) solid alkaline method: the principle is that bisphenol A and ECH generate bisphenol A type epoxy resin under the action of solid alkali; (4) solvent method: the principle is based on a two-step method, and an alcohol solvent is added in the reaction process to improve the condition of poor contact of two phases; (5) azeotropic dehydration method: the principle is based on a one-step method, a reflux water diversion system is added, water is separated, ECH is refluxed, and hydrolysis of ECH is reduced; (6) sodium salt method: the principle is that bisphenol A sodium salt is directly mixed with ECH to directly produce bisphenol A epoxy resin in the presence of catalyst. But each method has drawbacks.
Such as a one-step process, with long reaction times; ECH consumption is high, and hydrolysis product glycerol affects product quality; excessive ECH consumption is easy to cause side reaction, and the content of the product unsaponifiable chlorine is increased. For example, the two-step method is difficult to remove the catalyst used for production in the system, the catalyst has an effect on the performance of the resin product, and the dosage of the catalyst needs to be strictly controlled. For example, the solid alkali method is characterized in that the solid alkali is easy to absorb water and agglomerate, and is difficult to store and measure; the solid alkali is easy to block the valve and is difficult to uniformly feed. Such as solvent processes, require additional rectification columns to separate ECH from solvent; alcohols and ECH react under alkaline conditions to form difficult to separate glycidyl ethers. Such as azeotropic dehydration, the consumption of ECH hydrolysis is greatly reduced compared to the one-step process, but some ECH is hydrolyzed to glycerol because the system is still strongly alkaline. For example, the sodium salt method has complex production process and long period; the sodium salt is easy to absorb moisture and agglomerate, is difficult to uniformly feed, and is easy to block a valve.
CN106554480a discloses a preparation method of bisphenol a epoxy resin, specifically, bisphenol a, epichlorohydrin and auxiliary agent benzyl triethyl ammonium chloride are stirred under the protection of nitrogen to be completely dissolved; then adding solid alkali into the mixture, and reacting at normal temperature to 60 ℃; filtering; standing for layering, removing the water layer, and then distilling under reduced pressure to obtain the product. The method is a solid alkali method, bisphenol A and ECH generate bisphenol A epoxy resin under the action of solid alkali, the solid alkali is easy to absorb water and agglomerate, a valve is blocked, uniform feeding is difficult, the feeding amount is difficult to accurately calculate, the raw material waste is serious, and the product purity is reduced.
In summary, the most serious problem in the production of bisphenol a epoxy resins by the prior art is that ECH is very easily hydrolyzed to generate glycerol during the reaction process, which increases raw material consumption. Although hydrolysis of ECH can be reduced by using a solid-alkali method and a sodium salt method, when solid feeding is used, the solid is easy to absorb water and agglomerate to block a valve, and even feeding is difficult, so that the performance index of a product is influenced. Therefore, a production process for reducing ECH hydrolysis, facilitating material feeding and uniform material mixing in the reaction process needs to be found.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, providing a bisphenol A epoxy resin production process, continuously carrying out reaction, reducing energy consumption, reducing ECH hydrolysis, facilitating feeding and uniformly mixing materials in the reaction process, and providing a bisphenol A epoxy resin production device with strong index controllability and narrow molecular weight distribution.
The invention relates to a production process of bisphenol A epoxy resin, which comprises the following steps:
a. preparation of a first system: mixing 40-50wt.% sodium hydroxide solution and water, heating in an anaerobic state, adding bisphenol A, maintaining the temperature, and stirring to obtain a first system;
b. preparing a second system: under the anaerobic state, adding benzyl triethyl ammonium chloride into ECH, heating and stirring, and reacting to obtain a second system;
c. the reaction: dropwise adding the first system into the second system under the conditions of 25KPa-30KPa and 70-80 ℃, controlling the dropwise adding time to be 2-6 h, and preserving heat for 30-60 min to obtain a third system;
d. recovery of ECH: reducing the pressure of the system three to 1KPa-5KPa, simultaneously heating to 120-130 ℃, then bubbling steam for 30-60 min, reducing the temperature to 70-80 ℃, and recovering normal pressure;
e. desalting: maintaining the third temperature of the system, adding toluene and water, stirring, standing and separating to obtain toluene resin;
f. benzene removal: and (3) decompressing and heating the toluene resin, recovering toluene, adding water, and performing rotary evaporation until no liquid is evaporated, thereby obtaining the bisphenol A type epoxy resin.
In the step a, the mass ratio of bisphenol A, sodium hydroxide solution and water is 1 (0.5-0.65) to 1-1.7. The sodium hydroxide solution concentration was 50wt.%.
Step a is heated to 60-80 ℃ and stirred for 10-40 min.
The addition amount of the benzyl triethyl ammonium chloride in the step b is 5-15 wt. per mill of bisphenol A in the step a.
And b, heating to 60-80 ℃ and stirring for 8-12 min.
The mass ratio of bisphenol A in the first system to ECH in the second system in the step c is 1 (0.85-2.85).
And e, maintaining the temperature of the system three at 70-80 ℃, adding toluene and water, stirring, wherein the mass ratio is (1.5-2), 2, stirring for 10-30 min at 500-700 rpm, standing, separating liquid, and removing the lower-layer brine to obtain the upper-layer toluene resin.
And f, reducing the pressure of the toluene resin to below 1KPa, heating to 130-150 ℃, maintaining for 1-3 h, recovering toluene, adding water accounting for 10-20% of the theoretical bisphenol A epoxy resin mass, and continuously performing rotary evaporation at 130-150 ℃ until no liquid is evaporated, thus obtaining the bisphenol A epoxy resin.
A bisphenol A epoxy resin is obtained by the production process of the bisphenol A epoxy resin.
The device for producing the bisphenol A type epoxy resin comprises: the device comprises a reaction kettle I, a reaction kettle II, a water separator, a water receiver, a condenser I, a condenser II and a pressure system, wherein the reaction kettle I is connected with the reaction kettle II; the water separator is connected with the reaction kettle II through an ECH return pipe; the first reaction kettle is connected with the first condenser, the outlet of the first condenser is divided into two paths, one path returns to the first reaction kettle, and the other path is connected with the pressure system; the pipeline of the condenser II connected with the pressure system is provided with a balance pipe I and a balance pipe II, the balance pipe I is connected with the water separator, and the balance pipe II is connected with the water receiver. The water separator is provided with a water separator water outlet, and the height of the water separator water outlet is 2-3cm higher than the highest point of the ECH return pipe. The first balance pipe is used for balancing the pressure of the water separator; the second balancing pipe is used for balancing the pressure of the water receiver. Reaction kettle I: the method is used for preparing a first system and has the functions of stirring, heating, vacuum, nitrogen sealing and the like. And (2) a reaction kettle II: the method is used for preparing, reacting, recycling ECH and desalting a second system, and has the functions of stirring, heating/cooling, steam bubbling, vacuum, nitrogen sealing and the like. A water separator: is used for separating water in a system and refluxing ECH in the reaction process. A water receiver: for the collection of water separated by the water separator. Condenser one: the water vapor is used for condensing and refluxing the first reaction kettle. And a second condenser: and the condensing device is used for condensing steam in the using process of the reaction kettle II. Pressure system: the system pressure was changed and balanced.
Specifically, the production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: mixing 40-50wt.% sodium hydroxide solution and pure water, processing into an anaerobic state in a first reaction kettle by vacuum nitrogen sealing, heating to 60-80deg.C under nitrogen introducing condition, adding bisphenol A, keeping the temperature and stirring for 10-40 min, and reacting to obtain a uniform first system; the mass ratio of bisphenol A, sodium hydroxide solution and water is 1 (0.5-0.65) (1-1.7); the reaction formula is:
。
b. preparing a second system: ECH is taken in a reaction kettle II, the reaction kettle II is treated into an anaerobic state by utilizing a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining nitrogen, heating is carried out to 60-80 ℃, 5-15 wt%o of benzyl triethyl ammonium chloride of bisphenol A is added into the reaction kettle II, and the reaction kettle II is subjected to heat preservation and stirring for 8-12 min to obtain a system II.
c. The reaction: stopping introducing nitrogen into the reaction kettle II, gradually dropwise adding the first system into the second system under the conditions of 25KPa-30KPa and 70-80 ℃, controlling the dropwise adding time to be 2-6 h, and preserving heat for 30-60 min to obtain a third system, controlling the reflux speed of ECH (ethylene glycol) to reflux to the reaction kettle II by adjusting the opening of a reflux port valve of a water separator during the reaction, ensuring that the quantity of ECH entering the water separator is consistent with the quantity of ECH refluxing to the reaction kettle II, and maintaining the height of an ECH layer in the water separator to be constant and not higher than the water separator water outlet at most; the mass ratio of bisphenol A in the first system to ECH in the second system is 1 (0.85-2.85).
d. Recovery of ECH (ECH): and (c) reducing the pressure of a system III of the reaction kettle II to 1KPa-5KPa, simultaneously heating to 120-130 ℃, recovering ECH which does not participate in the reaction kettle II, then removing ECH by steam bubbling for 30-60 min, reducing the temperature to 70-80 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b) by the recovered ECH.
e. Desalting: and maintaining the temperature of the system III of the reaction kettle II at 70-80 ℃, adding toluene and water into the reaction kettle II, stirring the mixture in a mass ratio of (1.5-2) to 2, stirring the mixture at 500-700 rpm for 10-30 min, standing the mixture, and separating the liquid to remove the lower-layer brine to obtain the toluene resin of the upper layer.
f. Benzene removal: reducing the pressure of toluene resin to below 1KPa, heating to 130-150 ℃, maintaining for 1-3 h, recovering toluene, then adding water accounting for 10-20% of the theoretical bisphenol A type epoxy resin mass, and continuously steaming at 130-150 ℃ until no liquid is distilled out, thus obtaining bisphenol A type epoxy resin.
The bisphenol A epoxy resin production process of the invention adopts a dropwise adding mode to dropwise add the system I into the system II, the moisture in the system I and ECH are quickly brought away by azeotropy under the condition of heating negative pressure, and as bisphenol A salt is used as a reactant, no alkali exists in the whole reaction system, and the alkalinity of the whole reaction system is lower than that of the two-step production process, thus greatly reducing the consumption generated by ECH hydrolysis in the production process. According to the bisphenol A epoxy resin production device, the water separator is introduced, so that ECH carried by the water can flow back to the reaction kettle to continue to react, and therefore, the reaction ratio of reactants can be better maintained by using the process, and the bisphenol A epoxy resin with controllable quality and narrow molecular weight distribution is produced. The bisphenol A type epoxy resin production process uses the aqueous solution of bisphenol A salt to be dripped into ECH for reaction, avoids the occurrence of valve blockage and uneven feeding caused by water absorption and agglomeration of the bisphenol A salt, and has controllable feeding speed.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bisphenol A epoxy resin production process has low ECH hydrolysis consumption.
(2) The bisphenol A epoxy resin production device adopts the water separator, reduces the feeding amount of ECH, maintains stable reactant proportion, and has narrow molecular weight distribution and controllable quality.
(3) Compared with the solid alkali method and the sodium salt method, the bisphenol A epoxy resin production process disclosed by the invention has the advantages that the conditions of valve blockage and uneven feeding are avoided during feeding, the feeding controllability is strong, and the reaction is continuous and uniform.
(4) The bisphenol A epoxy resin production process has strong adjustability, and the performance index of the epoxy value of the product is changed by changing the component composition, the reaction condition and the feeding rate of the first system.
Drawings
FIG. 1 is a schematic view of an apparatus for producing bisphenol A type epoxy resin according to the present invention.
In the figure: 1. a first reaction kettle; 2. a reaction kettle II; 3. a water separator; 4. a water receiver; 5. a first condenser; 6. a second condenser; 7. a pressure system; 8. a balance pipe I; 9. a balance pipe II; 10. ECH return pipe; 11. a water outlet of the water separator.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The raw material auxiliary agent and the like are all from normal commercial products.
The production device in the production process of bisphenol A epoxy resin is a production schematic diagram, and other existing operation structures normally used in the chemical process are not repeated, and the operation is conducted by taking the effect of the invention as a guide.
As shown in FIG. 1, the device for producing bisphenol A epoxy resin comprises a first reaction kettle 1, a second reaction kettle 2, a water separator 3, a water receiver 4, a first condenser 5, a second condenser 6 and a pressure system 7, wherein the first reaction kettle 1 is connected with the second reaction kettle 2, the second reaction kettle 2 is connected with the second condenser 6, the second condenser 6 is connected with the pressure system 7, the second condenser 6 is connected with the water separator 3, and the water separator 3 is connected with the water receiver 4; the water separator 3 is connected with the second reaction kettle 2 through an ECH return pipe 10; the reaction kettle I1 is connected with a condenser I5, the outlet of the condenser I5 is divided into two paths, one path returns to the reaction kettle I1, and the other path is connected with a pressure system 7; the pipeline of the condenser II 6 connected with the pressure system 7 is provided with a balance pipe I8 and a balance pipe II 9, the balance pipe I8 is connected with the water separator 3, and the balance pipe II 9 is connected with the water receiver 4. The water separator 3 is provided with a water separator water outlet 11, and the height delta h of the water separator water outlet 11 is 2-3cm higher than the highest point of the ECH return pipe 10. The balance pipe I8 is used for balancing the pressure of the water separator; the function of the balancing pipe two 9 is to balance the pressure of the water receiver. Reaction kettle I: the method is used for preparing a first system and has the functions of stirring, heating, vacuum, nitrogen sealing and the like. And (2) a reaction kettle II: the method is used for preparing, reacting, recycling ECH and desalting a second system, and has the functions of stirring, heating/cooling, steam bubbling, vacuum, nitrogen sealing and the like. A water separator: is used for separating water in a system and refluxing ECH in the reaction process. A water receiver: for the collection of water separated by the water separator. Condenser one: the water vapor is used for condensing and refluxing the first reaction kettle. And a second condenser: and the condensing device is used for condensing steam in the using process of the reaction kettle II. Pressure system: the system pressure was changed and balanced.
The following examples all adopt the above device for producing bisphenol a epoxy resin for production, and the reaction vessel 1, the reaction vessel 2, the water separator 3, the water receiver 4, the condenser 5, the condenser 6 and the pressure system 7 are devices in the prior art, and the internal structures are also conventional structures in the art, and the functions of the devices are achieved by the functions of the invention, so that the internal structures of the devices are not discussed.
Example 1
The production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: 100g of 50wt.% sodium hydroxide solution and 340g of pure water are mixed, the circulating water cooling of the condenser I5 is started in the reaction kettle I1, the condenser I is processed into an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, the temperature is heated to 80 ℃ under the condition of maintaining the nitrogen, 200g of bisphenol A is added, and the mixture is continuously kept at the temperature and stirred for 40min after the addition, so that a uniform system I is obtained.
b. Preparing a second system: 170g of ECH is taken in a second reaction kettle 2, the circulating water of a second condenser 6 is started for cooling, a pressure system 7 is utilized, the second reaction kettle 2 is treated into an anaerobic state in a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining the nitrogen, heating to 80 ℃, 1g of benzyl triethyl ammonium chloride is added, the temperature is kept and stirring is carried out for 8min, and a second system is obtained.
c. The reaction: stopping introducing nitrogen into the reaction kettle II 2, regulating the system pressure to 30KPa by using the pressure system 7, gradually dropwise adding the system I into the system II at 80 ℃, controlling the dropwise adding time to 2h, and preserving heat for 60min to obtain a system III, controlling the reflux speed of ECH to the reaction kettle II 2 by regulating the opening of a reflux port valve of the water separator 3 during the reaction, ensuring that the ECH amount entering the water separator 3 is consistent with the ECH amount of the reflux reaction kettle II 2, and maintaining the ECH layer height in the water separator 3 to be constant and not higher than the water outlet of the water separator 3 at most. During this time, water in the upper layer of the water separator 3 continuously flows from the water outlet of the water separator 3 into the water receiver 4 to be stored.
d. Recovery of ECH: and (c) reducing the pressure of a system III of the reaction kettle II 2 to 5KPa by utilizing a pressure system 7, simultaneously heating to 120 ℃, recovering ECH which does not participate in the reaction kettle II 2, then removing ECH by steam bubbling for 30min, reducing the temperature to 80 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b) by the recovered ECH.
e. Desalting: maintaining the temperature of the system III of the reaction kettle II 2 at 80 ℃, adding 500g of toluene and 500g of water into the reaction kettle II 2, stirring at 500rpm for 10min, standing and separating to remove the lower-layer brine, and obtaining the upper-layer toluene resin.
f. Benzene removal: the toluene resin was depressurized to 1KPa, heated to 150℃and maintained for 1 hour, toluene was recovered, then 100g of water was added, and the spin-evaporation was continued at 150℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Example 2
The production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: 108g of 50wt.% sodium hydroxide solution and 305g of pure water are mixed, the circulating water cooling of the condenser I5 is started in the reaction kettle I1, the reaction kettle I is treated into an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, the reaction kettle I is heated to 75 ℃ under the condition of maintaining the nitrogen, 200g of bisphenol A is added, and the reaction kettle I is continuously insulated and stirred for 33 minutes after the addition is completed, so that a uniform system I is obtained.
b. Preparing a second system: 270g of ECH is taken in a second reaction kettle 2, the circulating water of a second condenser 6 is started, a pressure system 7 is utilized, the second reaction kettle 2 is treated into an anaerobic state in a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining the nitrogen, heating to 75 ℃, 1.5g of benzyl triethyl ammonium chloride is added, the temperature is kept and stirring is carried out for 9min, and a second system is obtained.
c. The reaction: stopping introducing nitrogen into the reaction kettle II 2, regulating the pressure of the system to 29Kpa by using the pressure system 7, gradually dropwise adding the system I into the system II at 78 ℃, controlling the dropwise adding time to be 3h, and preserving heat for 53min to obtain a system III, controlling the reflux speed of ECH to reflux the reaction kettle II 2 by regulating the opening of a reflux port valve of the water separator 3 during the reaction, ensuring that the quantity of ECH entering the water separator 3 is consistent with the quantity of ECH refluxing the reaction kettle II 2, and maintaining the height of an ECH layer in the water separator 3 to be constant and not higher than the water outlet of the water separator 3 at most. During this time, water in the upper layer of the water separator 3 continuously flows from the water outlet of the water separator 3 into the water receiver 4 to be stored.
d. Recovery of ECH: and (c) reducing the pressure of a system III of the reaction kettle II 2 to 4KPa by utilizing a pressure system 7, simultaneously heating to 123 ℃, recovering ECH which does not participate in the reaction kettle II 2, then removing ECH by steam bubbling for 38min, reducing the temperature to 78 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b).
e. Desalting: maintaining the temperature of the system III of the reaction kettle II 2 at 78 ℃, adding 470g of toluene and 500g of water into the reaction kettle II 2, stirring, rotating at 550rpm, stirring for 15min, standing, separating liquid, and removing the lower layer of brine to obtain the upper layer of toluene resin.
f. Benzene removal: the toluene resin was depressurized to 1KPa, heated to 145℃and maintained for 1.5 hours, toluene was recovered, then 125g of water was added, and the spin-evaporation was continued at 145℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Example 3
The production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: 115g of 50wt.% sodium hydroxide solution and 270g of pure water are mixed, the circulating water cooling of the condenser I5 is started in the reaction kettle I1, the reaction kettle I is treated into an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, the reaction kettle I is heated to 70 ℃ under the condition of maintaining the nitrogen, 200g of bisphenol A is added, and the reaction kettle I is continuously insulated and stirred for 25min after the addition is completed, so that a uniform system I is obtained.
b. Preparing a second system: 370g of ECH is taken in a second reaction kettle 2, the circulating water of a second condenser 6 is started, a pressure system 7 is utilized, the second reaction kettle 2 is treated into an anaerobic state in a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining the nitrogen, heating to 70 ℃, 2g of benzyl triethyl ammonium chloride is added, the temperature is kept and stirring is carried out for 10min, and a second system is obtained.
c. The reaction: stopping introducing nitrogen into the reaction kettle II 2, regulating the pressure of the system to 27Kpa by using the pressure system 7, gradually dropwise adding the system I into the system II at the temperature of 75 ℃, controlling the dropwise adding time to be 4h, and preserving heat for 45min to obtain a system III, controlling the reflux speed of ECH to reflux to the reaction kettle II 2 by regulating the opening of a reflux port valve of the water separator 3 during the reaction, ensuring that the quantity of ECH entering the water separator 3 is consistent with the quantity of ECH refluxing to the reaction kettle II 2, and maintaining the height of an ECH layer in the water separator 3 to be constant and not higher than the water outlet of the water separator 3 at most. During this time, water in the upper layer of the water separator 3 continuously flows from the water outlet of the water separator 3 into the water receiver 4 to be stored.
d. Recovery of ECH: and (c) reducing the pressure of a system III of the reaction kettle II 2 to 3KPa by utilizing a pressure system 7, simultaneously heating to 125 ℃, recovering ECH which does not participate in the reaction kettle II 2, then bubbling steam for 45min to remove ECH, reducing the temperature to 75 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b).
e. Desalting: maintaining the temperature of the system III of the reaction kettle II 2 at 75 ℃, adding 440g of toluene and 500g of water into the reaction kettle II 2, stirring at 600rpm for 20min, standing and separating to remove the lower-layer brine, and obtaining the upper-layer toluene resin.
f. Benzene removal: the toluene resin was depressurized to 0.8KPa, heated to 140℃and maintained for 2 hours, toluene was recovered, then 150g of water was added, and the spin-evaporation was continued at 140℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Example 4
The production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: 123g of 50wt.% sodium hydroxide solution and 235g of pure water are mixed, the circulating water cooling of the condenser I5 is started in the reaction kettle I1, the reaction kettle I is treated into an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, the reaction kettle I is heated to 65 ℃ under the condition of maintaining the nitrogen, 200g of bisphenol A is added, and the reaction kettle I is continuously insulated and stirred for 18min after the addition is completed, so that a uniform system I is obtained.
b. Preparing a second system: 470g of ECH is taken in a second reaction kettle 2, the circulating water of a second condenser 6 is started, a pressure system 7 is utilized, the second reaction kettle 2 is treated into an anaerobic state in a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining the nitrogen, heating to 65 ℃, 2.5g of benzyl triethyl ammonium chloride is added, the temperature is kept and stirring is carried out for 11min, and a second system is obtained.
c. The reaction: stopping introducing nitrogen into the reaction kettle II 2, regulating the pressure of the system to 26Kpa by using a pressure system 7, gradually dropwise adding the system I into the system II at 73 ℃, controlling the dropwise adding time to 5h, and preserving heat for 38min to obtain a system III, controlling the reflux speed of ECH to reflux the reaction kettle II 2 by regulating the opening of a reflux port valve of the water separator 3 during the reaction, ensuring that the quantity of ECH entering the water separator 3 is consistent with the quantity of ECH refluxing to the reaction kettle II 2, and maintaining the height of an ECH layer in the water separator 3 constant and the highest value is not higher than a water outlet of the water separator 3. During this time, water in the upper layer of the water separator 3 continuously flows from the water outlet of the water separator 3 into the water receiver 4 to be stored.
d. Recovery of ECH: and (c) reducing the pressure of a system III of the reaction kettle II 2 to 2KPa by utilizing a pressure system 7, simultaneously heating to 128 ℃, recovering ECH which does not participate in the reaction kettle II 2, then removing ECH by steam bubbling for 53min, reducing the temperature to 73 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b) by the recovered ECH.
e. Desalting: maintaining the temperature of the system III of the reaction kettle II 2 at 73 ℃, adding 410g of toluene and 500g of water into the reaction kettle II 2, stirring at 650rpm for 25min, standing and separating to remove the lower-layer brine, and obtaining the upper-layer toluene resin.
f. Benzene removal: the toluene resin was depressurized to 1KPa, heated to 135℃and maintained for 2.5 hours, toluene was recovered, then 175g of water was added, and the spin-evaporation was continued at 135℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Example 5
The production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: 130g of 50wt.% sodium hydroxide solution and 200g of pure water are mixed, the circulating water cooling of the condenser I5 is started in the reaction kettle I1, the reaction kettle I is treated into an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, the reaction kettle I is heated to 60 ℃ under the condition of maintaining the nitrogen, 200g of bisphenol A is added, and the reaction kettle I is continuously insulated and stirred for 10min after the addition is completed, so that a uniform system I is obtained.
b. Preparing a second system: 570g of ECH is taken in a second reaction kettle 2, circulating water cooling of a second condenser 6 is started, the second reaction kettle 2 is treated into an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining nitrogen, heating to 60 ℃, 3g of benzyl triethyl ammonium chloride is added, heat preservation and stirring are carried out for 12min, and a second system is obtained.
c. The reaction: stopping introducing nitrogen into the reaction kettle II 2, regulating the pressure of the system to 25Kpa by using a pressure system 7, gradually dropwise adding the system I into the system II at 70 ℃, controlling the dropwise adding time to be 6h, and preserving the heat for 30min to obtain a system III, controlling the reflux speed of ECH to reflux to the reaction kettle II 2 by regulating the opening of a reflux port valve of the water separator 3 during the reaction, ensuring that the quantity of ECH entering the water separator 3 is consistent with the quantity of ECH refluxing to the reaction kettle II 2, and maintaining the height of an ECH layer in the water separator 3 to be constant and not higher than the water outlet of the water separator 3 at most. During this time, water in the upper layer of the water separator 3 continuously flows from the water outlet of the water separator 3 into the water receiver 4 to be stored.
d. Recovery of ECH: and (c) reducing the pressure of a system III of the reaction kettle II 2 to 1KPa by utilizing a pressure system 7, simultaneously heating to 130 ℃, recovering ECH which does not participate in the reaction kettle II 2, then removing ECH by steam bubbling for 60min, reducing the temperature to 70 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b) by the recovered ECH.
e. Desalting: maintaining the temperature of the system III of the reaction kettle II 2 at 70 ℃, adding 375g of toluene and 510g of water into the reaction kettle II 2, stirring at 700rpm for 30min, standing for separating liquid, and removing the lower-layer brine to obtain the upper-layer toluene resin.
f. Benzene removal: the toluene resin was depressurized to 1KPa, heated to 130℃and maintained for 3 hours, toluene was recovered, then 200g of water was added, and the spin-evaporation was continued at 130℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Example 6
The production process of the bisphenol A epoxy resin comprises the following steps:
a. preparation of a first system: 144g of 40wt.% sodium hydroxide solution and 270g of pure water are mixed, the circulating water cooling of the condenser I5 is started in the reaction kettle I1, the condenser I is treated to be in an anaerobic state by using a pressure system 7 in a vacuum nitrogen sealing mode, the temperature is heated to 70 ℃ under the condition of maintaining the nitrogen, 200g of bisphenol A is added, and the mixture is kept warm and stirred for 25min after the addition is finished, so that a uniform system I is obtained.
b. Preparing a second system: 370g of ECH is taken in a second reaction kettle 2, the circulating water of a second condenser 6 is started, a pressure system 7 is utilized, the second reaction kettle 2 is treated into an anaerobic state in a vacuum nitrogen sealing mode, stirring is started under the condition of maintaining the nitrogen, heating to 70 ℃, 2g of benzyl triethyl ammonium chloride is added, the temperature is kept and stirring is carried out for 10min, and a second system is obtained.
c. The reaction: stopping introducing nitrogen into the reaction kettle II 2, regulating the pressure of the system to 27Kpa by using the pressure system 7, gradually dripping the system I into the system II at 75 ℃, after the dripping is finished for 4 hours, preserving heat for 45 minutes to obtain a system III, controlling the reflux speed of ECH to the reaction kettle II 2 by regulating the opening of a reflux port valve of the water separator 3 during the reaction, ensuring that the quantity of ECH entering the water separator 3 is consistent with the quantity of ECH refluxing the reaction kettle II 2, and maintaining the height of an ECH layer in the water separator 3 constant and the highest value is not higher than the water outlet of the water separator 3. During this time, water in the upper layer of the water separator 3 continuously flows from the water outlet of the water separator 3 into the water receiver 4 to be stored.
d. Recovery of ECH: and (c) reducing the pressure of a system III of the reaction kettle II 2 to 3KPa by utilizing a pressure system 7, simultaneously heating to 125 ℃, recovering ECH which does not participate in the reaction kettle II 2, then bubbling steam for 45min to remove ECH, reducing the temperature to 75 ℃, breaking vacuum by nitrogen, recovering normal pressure, and continuously participating in the step (b).
e. Desalting: maintaining the temperature of the system III of the reaction kettle II 2 at 75 ℃, adding 440g of toluene and 500g of water into the reaction kettle II 2, stirring at 600rpm for 20min, standing and separating to remove the lower-layer brine, and obtaining the upper-layer toluene resin.
f. Benzene removal: the toluene resin was depressurized to 0.8KPa, heated to 140℃and maintained for 2 hours, toluene was recovered, then 150g of water was added, and the spin-evaporation was continued at 140℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Comparative example 1
A preparation method of bisphenol A epoxy resin comprises the following steps:
200g of bisphenol A and 650g of ECH are added into a reaction kettle II, the mixture is treated to be in an anaerobic state by a vacuum nitrogen sealing mode, and the temperature is raised to 45 ℃ and stirred until the bisphenol A is completely dissolved. Heating to 70 ℃, and adding 3g of benzyl triethyl ammonium chloride to react for 2.5h. The pressure was reduced to 5KPa, 150 parts of sodium hydroxide solution was added dropwise to the flask over 3 hours, and the flask was kept at a temperature for 30 minutes after the completion of the dropwise addition.
Reducing the pressure to 1KPa, heating to 130 ℃ at the same time, removing ECH which does not participate in the reaction, then bubbling steam for 60min to remove ECH, reducing the temperature to 70 ℃, and breaking vacuum with nitrogen to restore normal pressure. The reaction system was maintained at 70℃and 375g of toluene and 500g of water were added thereto and stirred at 700rpm for 30 minutes, followed by standing and liquid separation to remove brine, thereby obtaining toluene resin. The toluene resin was depressurized to 1KPa, heated to 130℃and maintained for 3 hours, toluene was recovered, then 200g of water was added, and the spin-evaporation was continued at 150℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Comparative example 2
A preparation method of bisphenol A epoxy resin comprises the following steps:
200g of bisphenol A and 680g of ECH are added into a reaction kettle II, the mixture is treated to be in an anaerobic state by a vacuum nitrogen sealing mode, the temperature is raised to 45 ℃ and the mixture is stirred until the bisphenol A is completely dissolved, and 3g of benzyl triethyl ammonium chloride and 1g of 50wt.% sodium hydroxide solution are added for reaction for 80min. Reduced pressure to 23KPa, warmed to 70℃and 115g of 50wt.% sodium hydroxide solution were added dropwise to the flask over 2 h. Then, 30g of 50wt.% sodium hydroxide solution was added dropwise to the flask over 1.5 hours, and the flask was incubated for 30 minutes after the completion of the dropwise addition.
Reducing the pressure to 1KPa, heating to 130 ℃ at the same time, removing ECH which does not participate in the reaction, then bubbling steam for 60min to remove ECH, reducing the temperature to 70 ℃, and breaking vacuum with nitrogen to restore normal pressure. The reaction system was maintained at 70℃and 375g of toluene and 500g of water were added thereto and stirred at 700rpm for 30 minutes, followed by standing and liquid separation to remove brine, thereby obtaining toluene resin. The toluene resin was depressurized to 1KPa, heated to 130℃and maintained for 3 hours, toluene was recovered, then 200g of water was added, and the spin-evaporation was continued at 150℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Comparative example 3
A preparation method of bisphenol A epoxy resin comprises the following steps:
200g of bisphenol A and 820g of ECH are added into a reaction kettle II, the mixture is treated to be in an anaerobic state by a vacuum nitrogen sealing mode, the temperature is raised to 80 ℃ and stirred until the bisphenol A is completely dissolved, and 1g of benzyl triethyl ammonium chloride is added. The pressure was reduced to 30KPa, 100g of 50wt.% sodium hydroxide solution was added dropwise to the flask over 2 hours, and the flask was incubated for 30 minutes after the addition was completed.
Reducing the pressure to 5KPa, heating to 120 ℃ at the same time, removing ECH which does not participate in the reaction, then bubbling steam for 30min to remove ECH, reducing the temperature to 80 ℃, breaking vacuum by nitrogen and recovering normal pressure. Maintaining the temperature of the system at 80 ℃, adding 500g of toluene and 500g of water, stirring at 500rpm for 10min, standing, separating liquid, and removing salt water to obtain toluene resin. The toluene resin is decompressed to 1KPa, heated to 150 ℃, maintained for 1h, toluene is recovered, 100 parts of water is added, and the spin evaporation is continued at 150 ℃ until no liquid is evaporated, thus obtaining bisphenol A type epoxy resin.
Comparative example 4
A preparation method of bisphenol A epoxy resin comprises the following steps:
200g of bisphenol A and 450g of ECH are added into a reaction kettle II, the mixture is treated to be in an anaerobic state by a vacuum nitrogen sealing mode, and the temperature is raised to 40 ℃ and the mixture is stirred until the bisphenol A is completely dissolved. Heating to 60 ℃, and adding 2g of benzyl triethyl ammonium chloride to react for 1h. Reduced pressure to 20KPa, and 120g of 50wt.% sodium hydroxide solution was added dropwise to the flask over 4 hours, and the flask was incubated for 30 minutes after the addition was completed.
Reducing the pressure to 3KPa, heating to 125 ℃, removing ECH which does not participate in the reaction, then bubbling steam for 45min to remove ECH, reducing the temperature to 75 ℃, breaking vacuum by nitrogen, and recovering normal pressure. Maintaining the system temperature at 75deg.C, adding 440g toluene and 500g water, stirring at 600rpm for 20min, standing, and separating to remove salt water to obtain toluene resin. The toluene resin was depressurized to 1KPa, heated to 140℃and maintained for 2 hours, toluene was recovered, then 150g of water was added, and the spin-evaporation was continued at 150℃until no liquid was distilled off, to obtain bisphenol A type epoxy resin.
Comparative example 5
A preparation method of bisphenol A epoxy resin comprises the following steps:
200g of bisphenol A and 170g of epichlorohydrin are added into a reaction kettle II 2, 1g of benzyl triethyl ammonium chloride is added, and the mixture is stirred under the protection of nitrogen to be completely dissolved; 50g of solid sodium hydroxide was added to the second reactor 2, and reacted at 60℃for 6 hours. The solid matter formed in the reaction system was filtered, and then the mother liquor after filtration was allowed to stand for delamination, and the aqueous layer was removed. Unreacted epichlorohydrin is removed under reduced pressure distillation to obtain an epoxy resin.
The epoxy value, the hydrolysis chlorine, and the viscosity were measured according to examples 1 to 6 and comparative examples 1 to 5 above, and the consumption of ECH was calculated for each of the examples and comparative examples to produce 1kg of resin, the results of which are shown in Table 1, and the molecular weight distribution of bisphenol A type epoxy resin was measured, and the results of which are shown in Table 2.
TABLE 1 bisphenol A type epoxy resin index and ECH consumption
TABLE 2 bisphenol A type epoxy resin molecular weight distribution results
According to the data of the examples 1-6 and the tables, the epoxy resin products with different epoxy values can be produced by simply changing the reaction proportion and the reaction parameters, and the operation is simple and convenient.
As is clear from comparative examples 1 and 3, examples 1 and 5, and examples 3 and 4, the epoxy resins produced by the present invention have narrower molecular weight distribution, lower viscosity under the same epoxy value, and more excellent product properties.
As can be seen from the comparison of comparative examples 1 and 3, the comparison of examples 3 and 4, and the comparison of examples 5 and 1 and 2, the consumption of the bisphenol a type epoxy resin ECH produced using the present invention is lower because: the bisphenol A is firstly used to react with the sodium hydroxide solution, so that a large amount of sodium hydroxide solution is consumed, the whole reaction system is slightly alkaline, and the hydrolysis of ECH is reduced; the bisphenol A sodium salt solution is dripped into the ECH for reaction in a dripping way, so that the feeding amount of the ECH is not required to be excessive, the hydrolysis of the ECH during the recovery of the ECH by reducing the pressure and the temperature rise is reduced, and the consumption is lower.

Claims (8)

1. A production process of bisphenol A epoxy resin is characterized in that: the method comprises the following steps:
a. preparation of a first system: mixing 40-50wt.% sodium hydroxide solution and water, heating to 60-80deg.C under anaerobic condition, adding bisphenol A, stirring for 10-40 min, and reacting to obtain a first system;
the mass ratio of bisphenol A, sodium hydroxide solution and water is 1 (0.5-0.65) (1-1.7);
b. preparing a second system: under the anaerobic state, adding benzyl triethyl ammonium chloride into ECH, heating and stirring, and reacting to obtain a second system;
c. the reaction: dropwise adding the first system into the second system under the conditions of 25KPa-30KPa and 70-80 ℃, controlling the dropwise adding time to be 2-6 h, and preserving heat for 30-60 min to obtain a third system;
d. recovery of ECH: reducing the pressure of the system three to 1KPa-5KPa, simultaneously heating to 120-130 ℃, then bubbling steam for 30-60 min, reducing the temperature to 70-80 ℃, and recovering normal pressure;
e. desalting: maintaining the third temperature of the system, adding toluene and water, stirring, standing and separating to obtain toluene resin;
f. benzene removal: and (3) decompressing and heating the toluene resin, recovering toluene, adding water, and performing rotary evaporation until no liquid is evaporated, thereby obtaining the bisphenol A type epoxy resin.
2. The process for producing bisphenol a type epoxy resin according to claim 1, wherein: the addition amount of the benzyl triethyl ammonium chloride in the step b is 5-15 wt. per mill of bisphenol A in the step a.
3. The process for producing bisphenol a type epoxy resin according to claim 1, wherein: and b, heating to 60-80 ℃ and stirring for 8-12 min.
4. The process for producing bisphenol a type epoxy resin according to claim 1, wherein: the mass ratio of bisphenol A in the first system to ECH in the second system in the step c is 1 (0.85-2.85).
5. The process for producing bisphenol a type epoxy resin according to claim 1, wherein: and e, maintaining the temperature of the system three at 70-80 ℃, adding toluene and water with the mass ratio of (1.5-2) 2, stirring for 10-30 min at the rotation speed of 500-700 rpm, standing for separating liquid, and removing the lower-layer brine to obtain the upper-layer toluene resin.
6. The process for producing bisphenol a type epoxy resin according to claim 1, wherein: and f, reducing the pressure of the toluene resin to below 1KPa, heating to 130-150 ℃, maintaining for 1-3 h, recovering toluene, adding water accounting for 10-20% of the theoretical bisphenol A epoxy resin mass, and continuously performing rotary evaporation at 130-150 ℃ until no liquid is evaporated, thus obtaining the bisphenol A epoxy resin.
7. A bisphenol A type epoxy resin is characterized in that: is obtained by the process for producing bisphenol A type epoxy resin according to any one of claims 1 to 6.
8. An apparatus for producing bisphenol a type epoxy resin as claimed in claim 7, wherein: the device comprises a first reaction kettle (1), a second reaction kettle (2), a water separator (3), a water receiver (4), a first condenser (5), a second condenser (6) and a pressure system (7), wherein the first reaction kettle (1) is connected with the second reaction kettle (2), the second reaction kettle (2) is connected with the second condenser (6), the second condenser (6) is connected with the pressure system (7), the second condenser (6) is connected with the water separator (3), and the water separator (3) is connected with the water receiver (4); the water separator (3) is connected with the second reaction kettle (2) through an ECH return pipe (10); the reaction kettle I (1) is connected with the condenser I (5), the outlet of the condenser I (5) is divided into two paths, one path returns to the reaction kettle I (1), and the other path is connected with the pressure system (7); a first balance pipe (8) and a second balance pipe (9) are arranged on a pipeline connected with the pressure system (7) of the condenser II (6), the first balance pipe (8) is connected with the water separator (3), and the second balance pipe (9) is connected with the water receiver (4).
CN202311006834.9A 2023-08-11 2023-08-11 Bisphenol A type epoxy resin and production process and production device thereof Active CN116731285B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2801227A (en) * 1953-10-19 1957-07-30 Shell Dev Process for manufacture of glycidyl ethers of polyhydric phenols
US6001873A (en) * 1996-12-31 1999-12-14 Chang Chun Plastics Co., Ltd. Process for preparing a high purity epoxy resin
CN206345815U (en) * 2016-11-22 2017-07-21 张瑞丽 A kind of bisphenol A type epoxy resin production system
CN114456353A (en) * 2022-03-18 2022-05-10 安徽善孚新材料科技股份有限公司 Preparation method of bisphenol A epoxy resin with low toluene residue

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2801227A (en) * 1953-10-19 1957-07-30 Shell Dev Process for manufacture of glycidyl ethers of polyhydric phenols
US6001873A (en) * 1996-12-31 1999-12-14 Chang Chun Plastics Co., Ltd. Process for preparing a high purity epoxy resin
CN206345815U (en) * 2016-11-22 2017-07-21 张瑞丽 A kind of bisphenol A type epoxy resin production system
CN114456353A (en) * 2022-03-18 2022-05-10 安徽善孚新材料科技股份有限公司 Preparation method of bisphenol A epoxy resin with low toluene residue

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