Preparation method of bis-hydroxyethyl bisphenol A ether

Abstract

The invention discloses a preparation method of bis-hydroxyethyl bisphenol A ether, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: adding bisphenol A, a mixed acetate catalyst and a solvent into a reaction kettle, starting stirring, replacing nitrogen, heating to a reaction temperature, starting to introduce ethylene oxide, keeping the temperature after the ethylene oxide is added, and continuously reacting until the pressure is not reduced any more to obtain bisphenol A; cooling to a desolventizing temperature, desolventizing until no solvent is discharged, cooling, degassing, and discharging to obtain the bis (hydroxyethyl) bisphenol A ether, wherein the mixed acetate catalyst is prepared from calcium acetate, magnesium acetate and barium acetate; the solvent is methyl cyclohexane. According to the preparation method, the specific mixed acetate is adopted as the catalyst, methyl cyclohexane is adopted as the solvent, the excellent catalytic effect is achieved, the prepared bis-hydroxyethyl bisphenol A ether is high in content, low in hydroxyl value and light in color, and the solvent is small in toxicity and easy to recycle.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing bishydroxyethyl bisphenol A ether. Background Art

[0002] Bis(hydroxyethyl)bisphenol A ether is an important dihydroxy compound. The benzene ring skeleton in its unique molecular structure can enhance the rigidity of the molecular chain, so that the material has excellent mechanical strength and wear resistance during use; at the same time, the polyether chain segment has high internal rotation freedom and good flexibility, which gives the material excellent plasticity and toughness. These excellent physical and chemical properties make bis(hydroxyethyl)bisphenol A ether not only a synthetic monomer for organic materials such as resins, coatings, adhesives, and glass fiber sizing agents, but also a modifier and additive for polymer chains, making it widely used in many fields such as automobile manufacturing, textiles, aviation, petrochemicals, construction, and transportation.

[0003] At present, the existing bishydroxyethyl bisphenol A polyether usually has a solvent dissolution method and a high-temperature melting method. Among them, the solvent dissolution method needs to be desorbed from the solvent, and the process is complicated and the production cost is greatly increased. Moreover, most of the solvents are toxic and have a great impact on the environment. Although the high-temperature melting method has well overcome the problems of complicated processes and great impact on the environment in the solvent dissolution method, due to the melting point of bisphenol A being about 158°C, the temperature of the heating medium must reach at least 160°C to melt bisphenol A without heating the solvent, and the melted bisphenol A is very easy to undergo isomerization and decomposition reactions under the action of high temperature and strong base catalysts, which increases the number of by-products and the hydroxyl value of the obtained product is high. At the same time, the product obtained by strong base catalysis at high temperature has a darker color and high chroma, which greatly affects the product quality. Some preparation processes use alkylamines as catalysts, but still cannot solve the problem of the darker color of the product, and it is difficult to meet the product requirements of high quality and high performance. At the same time, the process of removing the catalyst is relatively complicated, with high energy consumption and high cost. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing bishydroxyethyl bisphenol A ether. The preparation method adopts a specific mixed acetate as a catalyst and methylcyclohexane as a solvent, which not only has an excellent catalytic effect, but also makes the prepared bishydroxyethyl bisphenol A ether have a high content, a low hydroxyl value, and a light color, and the solvent has low toxicity and is easy to recycle.

[0005] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0006] A preparation method of bishydroxyethyl bisphenol A ether is as follows: bisphenol A, a mixed acetate catalyst and a solvent are added to a reaction kettle, stirring is started and nitrogen is replaced, ethylene oxide is introduced after the temperature is raised to the reaction temperature, the temperature is maintained after the ethylene oxide is added, and the reaction is continued until the pressure no longer decreases, the temperature is lowered to the desolvation temperature, and the desolvation is carried out until no solvent is left, and the material is discharged after the temperature is lowered and degassing to obtain the bishydroxyethyl bisphenol A ether;

[0007] Wherein, the mixed acetate catalyst is composed of calcium acetate, magnesium acetate and barium acetate; and the solvent is methylcyclohexane.

[0008] As a preferred embodiment of the present invention, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.5-1.

[0009] As a preferred embodiment of the present invention, the amount of the mixed acetate catalyst is 0.1% to 1% of the sum of the mass of bisphenol A and ethylene oxide.

[0010] Further preferably, the amount of the mixed acetate catalyst used is 0.4% of the sum of the mass of bisphenol A and ethylene oxide.

[0011] As a preferred embodiment of the present invention, the amount of methylcyclohexane added is 30% to 100% of the mass of bisphenol A, preferably 50%.

[0012] As a preferred embodiment of the present invention, the reaction temperature is 100-150° C. and the reaction pressure is lower than 0.50 MPa.

[0013] Further preferably, the reaction temperature is 123±2° C. and the reaction pressure is lower than 0.35 MPa.

[0014] As a preferred embodiment of the present invention, the desolvation temperature is 90-110°C, preferably 100-105°C.

[0015] As a preferred embodiment of the present invention, the cooling is performed by cooling to 85° C. and then degassing.

[0016] The content of the bishydroxyethyl bisphenol A ether prepared by the preparation method of the invention is ≥97%, the hydroxyl value is 325-385 mgKOH / g, and the color (Pt-Co) is ≤35.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. The present invention adopts a mixed acetate catalyst composed of calcium acetate, magnesium acetate and barium acetate. The longer chain of acetate group makes it have excellent catalytic properties. At the same time, calcium acetate, magnesium acetate and barium acetate are all alkaline earth metal compound catalysts with divalent metal ions, which can form complexes with oxygen atoms in two polyether molecules at the same time. Due to the large steric hindrance, the interaction between the metal and the oxygen atoms of the polyether is weakened, thereby delaying the reaction rate of the epoxy monomer and the phenoloxy anion. The catalyst is used to produce a product with a narrow relative molecular weight distribution and a low small molecule free alcohol content, so that the content of the prepared bishydroxyethyl bisphenol A ether is ≥97%, the hydroxyl value is 325-385 mgKOH / g, the color (Pt-Co) is ≤35, and the color is lighter. Compared with other conventional single-component alkaline earth metal catalysts, the product prepared under the action of the catalyst has better color and higher bishydroxyethyl bisphenol A ether content.

[0019] 2. The preparation method of the present invention uses methylcyclohexane as a solvent, which is not only highly stable and has a low melting point, but also has low toxicity and is easy to recycle compared to other conventional solvents.

[0020] In summary, the preparation method of the present invention not only has excellent catalytic effect, but also makes the prepared bishydroxyethyl bisphenol A ether have high content, low hydroxyl value and light color, simple process and easy industrial implementation, and the prepared product has high quality and stable quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a product image of bishydroxyethyl bisphenol A ether prepared in Example 2 of the present invention;

[0022] Figure 2 This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 1 of the present invention;

[0023] Figure 3 This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 2 of the present invention;

[0024] Figure 4 This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 3 of the present invention;

[0025] Figure 5 This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 4 of the present invention;

[0026] Figure 6 This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 5 of the present invention;

[0027] Figure 7 This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 6 of the present invention;

[0028] Figure 8This is a product picture of bishydroxyethyl bisphenol A ether prepared in Comparative Example 7 of the present invention;

[0029] Fig. 9 This is a physical picture of the product of bishydroxyethyl bisphenol A ether prepared in Comparative Example 8 of the present invention. DETAILED DESCRIPTION

[0030] The preparation method of bishydroxyethyl bisphenol A ether provided by the present invention is as follows: bisphenol A, a mixed acetate catalyst composed of calcium acetate, magnesium acetate and barium acetate and a solvent methylcyclohexane are added into a reaction kettle, stirring is started and nitrogen is replaced, ethylene oxide is introduced after the temperature is raised to a reaction temperature of 100-150° C., the reaction pressure in the reaction process is controlled to be lower than 0.50Mpa, the temperature is maintained after the ethylene oxide is added and the reaction is continued until the pressure no longer decreases, the temperature is lowered to a desolvation temperature of 90-110° C., desolvation is carried out until no solvent is discharged, the temperature is lowered to 85° C., degassing is carried out for 30 minutes and then the material is discharged to obtain bishydroxyethyl bisphenol A ether.

[0031] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0032] Example 1

[0033] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0034] In a reactor, 1000 g of bisphenol A, 4.26 g of a mixed acetate catalyst (0.3% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 110° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C., and the solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0035] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bishydroxyethyl bisphenol A ether was 97.0%, the residual methyl cyclohexane was 283 ppm, the product color (Pt-Co) was 15.3, and the hydroxyl value was 381.5 mgKOH / g determined by chemical method.

[0036] Example 2

[0037] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0038] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 100° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C. The solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0039] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 99.2%, the residual amount of methylcyclohexane was 303 ppm, the product color (Pt-Co) was 14.5 ( Figure 1 ), the hydroxyl value was determined to be 356.8 mgKOH / g by chemical method.

[0040] Example 3

[0041] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0042] In a reactor, 1000 g of bisphenol A, 7.10 g of a mixed acetate catalyst (0.5% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 121° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C., and the solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. for degassing for 30 minutes, and the finished product is obtained after the material is discharged.

[0043] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bishydroxyethyl bisphenol A ether was 99.3%, the residual methyl cyclohexane was 287 ppm, the product color (Pt-Co) was 29.7, and the hydroxyl value was 355.1 mgKOH / g determined by chemical method.

[0044] Example 4

[0045] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0046] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, the temperature is raised to 110° C., and 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 110±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C. The solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0047] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bishydroxyethyl bisphenol A ether was 97.2%, the residual methyl cyclohexane was 293 ppm, the product color (Pt-Co) was 16.1, and the hydroxyl value was 383.1 mgKOH / g determined by chemical method.

[0048] Example 5

[0049] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0050] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after heating to 110° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 140±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is reduced to 120° C., and the solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is reduced to 85° C. and degassing is carried out for 30 minutes, and the finished product is obtained after the material is discharged.

[0051] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bishydroxyethyl bisphenol A ether was 98.6%, the residual amount of methyl cyclohexane was 311 ppm, the product color (Pt-Co) was 34.1, and the hydroxyl value determined by chemical method was 357.2 mgKOH / g.

[0052] Example 6

[0053] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0054] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.5) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 100° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C. The solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0055] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bishydroxyethyl bisphenol A ether was 99.0%, the residual methyl cyclohexane was 308 ppm, the product color (Pt-Co) was 31.2, and the hydroxyl value was 357.8 mgKOH / g determined by chemical method.

[0056] Example 7

[0057] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0058] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:1) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 100° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C. The solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0059] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bishydroxyethyl bisphenol A ether was 98.2%, the residual methyl cyclohexane was 300 ppm, the product color (Pt-Co) was 16.5, and the hydroxyl value was 376.8 mgKOH / g determined by chemical method.

[0060] Comparative Example 1

[0061] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0062] Into a reactor, 1000 g of bisphenol A, 5.68 g of KOH (0.4% of the sum of the mass of bisphenol A and ethylene oxide) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, the temperature is raised to 110° C., and 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the temperature is lowered to 105° C. and then desolventizing is carried out, and the desolventizing temperature is controlled at 100-105° C. until no solvent comes out, and then the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0063] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 97.2%, the residual amount of methylcyclohexane was 331 ppm, the product color (Pt-Co) was 61.4 ( Figure 2 ), the hydroxyl value was determined to be 360.1 mgKOH / g by chemical method.

[0064] Comparative Example 2

[0065] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0066] Into a reactor, 1000 g of bisphenol A, 5.68 g of triethylamine (0.4% of the sum of the mass of bisphenol A and ethylene oxide) and 500 g of methylcyclohexane were added in sequence. After stirring, nitrogen was replaced three times. Under the condition of vacuum degree ≥-0.098 MPa, the temperature was raised to 110° C., and 420 g of ethylene oxide was continuously introduced. The reaction temperature was controlled at 123±2° C. and the pressure in the reactor was ≤0.35 MPa. After the addition was completed, the temperature was maintained and the reaction was continued until the system pressure in the reactor no longer decreased. After the temperature was reduced to 105° C., desolventization was carried out. The desolventization temperature was controlled at 100-105° C. until no solvent came out. The temperature was reduced to 85° C. and degassed for 30 minutes. The finished product was obtained after the material was discharged.

[0067] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 99.0%, the residual amount of methylcyclohexane was 299 ppm, the product color (Pt-Co) was 41.6 ( Figure 3 ), the hydroxyl value was determined to be 355.1 mgKOH / g by chemical method.

[0068] Comparative Example 3

[0069] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0070] Into a reactor, 1000 g of bisphenol A, 5.68 g of calcium acetate (0.4% of the sum of the mass of bisphenol A and ethylene oxide) and 500 g of methylcyclohexane were sequentially added, stirring was started and nitrogen was replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, the temperature was raised to 110° C., and 420 g of ethylene oxide was continuously introduced, and the reaction temperature was controlled at 123±2° C., and the pressure in the reactor was ≤0.35 MPa. After the addition was completed, the temperature was maintained and the reaction was continued until the system pressure in the reactor no longer decreased. After the temperature was lowered to 105° C., desolventization was carried out, and the desolventization temperature was controlled at 100-105° C. until no solvent came out, the temperature was lowered to 85° C. and degassed for 30 minutes, and the finished product was obtained after the material was discharged.

[0071] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 98.9%, the residual amount of methylcyclohexane was 325 ppm, the product color (Pt-Co) was 43.6 ( Figure 4 ), the hydroxyl value was determined to be 356.1 mgKOH / g by chemical method.

[0072] Comparative Example 4

[0073] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0074] Into a reactor, 1000 g of bisphenol A, 5.68 g of magnesium acetate (0.4% of the sum of the mass of bisphenol A and ethylene oxide) and 500 g of methylcyclohexane were sequentially added. After stirring, nitrogen was replaced three times. Under the condition of vacuum degree ≥-0.098 MPa, the temperature was raised to 110° C., and 420 g of ethylene oxide was continuously introduced. The reaction temperature was controlled at 123±2° C. and the pressure in the reactor was ≤0.35 MPa. After the addition was completed, the temperature was maintained and the reaction was continued until the pressure in the reactor stopped decreasing. After the temperature was lowered to 105° C., desolventization was carried out. The desolventization temperature was controlled at 100-105° C. until no solvent came out. The temperature was lowered to 85° C. and degassed for 30 minutes. The finished product was obtained after the material was discharged.

[0075] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 90.3%, the residual amount of methylcyclohexane was 300 ppm, the product color (Pt-Co) was 21.3 ( Figure 5 ), and the hydroxyl value was determined by chemical method to be 400.3 mgKOH / g.

[0076] Comparative Example 5

[0077] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0078] Into a reactor, 1000 g of bisphenol A, 5.68 g of barium acetate (0.4% of the sum of the mass of bisphenol A and ethylene oxide) and 500 g of methylcyclohexane were sequentially added, stirring was started and nitrogen was replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, the temperature was raised to 110° C., and 420 g of ethylene oxide was continuously introduced, the reaction temperature was controlled at 123±2° C., and the pressure in the reactor was ≤0.35 MPa. After the addition was completed, the temperature was maintained and the reaction was continued until the system pressure in the reactor no longer decreased, and the temperature was lowered to 105° C. and then the solvent was removed. The solvent removal temperature was controlled at 100-105° C. until no solvent came out, the temperature was lowered to 85° C. and degassed for 30 minutes, and the finished product was obtained after the material was discharged.

[0079] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 97.3%, the residual amount of methylcyclohexane was 302 ppm, the product color (Pt-Co) was 29.1 ( Figure 6 ), the hydroxyl value was determined to be 360.5 mgKOH / g by chemical method.

[0080] Comparative Example 6

[0081] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0082] Into a reactor, 1000 g of bisphenol A, 5.68 g of calcium carbonate (0.4% of the sum of the mass of bisphenol A and ethylene oxide) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, the temperature is raised to 110° C., and 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 105° C. The solvent removal temperature is controlled at 100-105° C. until no solvent comes out, the temperature is lowered to 85° C. and degassed for 30 minutes, and the finished product is obtained after the material is discharged.

[0083] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 97.5%, the residual amount of methylcyclohexane was 299 ppm, the product color (Pt-Co) was 45.3 ( Figure 7 ), the hydroxyl value was determined to be 358.9 mgKOH / g by chemical method.

[0084] Comparative Example 7

[0085] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0086] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 110° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and the solvent is removed after the temperature is lowered to 85° C. The solvent removal temperature is controlled at 75-85° C. until no solvent comes out, the temperature is lowered to 85° C. for degassing for 30 minutes, and the finished product is obtained after the material is discharged.

[0087] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 97.9%, the residual amount of methylcyclohexane was 925 ppm, the product color (Pt-Co) was 16.7 ( Figure 8 ), the hydroxyl value was determined to be 354.8 mgKOH / g by chemical method.

[0088] Comparative Example 8

[0089] A preparation method of bishydroxyethyl bisphenol A ether is as follows:

[0090] In a reactor, 1000 g of bisphenol A, 5.68 g of a mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500 g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, and under the condition of vacuum degree ≥-0.098 MPa, after the temperature is raised to 110° C., 420 g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2° C., and the pressure in the reactor is ≤0.35 MPa. After the addition is completed, the temperature is maintained and the reaction is continued until the system pressure in the reactor no longer decreases, and desolventizing is carried out, and the desolventizing temperature is controlled at 120-125° C. until no solvent comes out, the temperature is lowered to 85° C. for degassing for 30 minutes, and the finished product is obtained after discharging.

[0091] The obtained product was subjected to liquid chromatography and gas chromatography analysis, and the results were as follows: the content of bis(hydroxyethyl)bisphenol A ether was 98.3%, the residual amount of methylcyclohexane was 291 ppm, the product color (Pt-Co) was 32.2 ( Fig. 9 ), and the hydroxyl value was determined to be 359.3 mgKOH / g by chemical method.

[0092] The reaction conditions and product performance index data of Examples 1 to 7 and Comparative Examples 1 to 8 are summarized, and the results are shown in Table 1.

[0093] Table 1 Statistics of product performance indicators obtained under different implementation conditions

[0094]

[0095]

[0096] Note: In the above table, A represents the catalyst mixed acetate catalyst, B represents the catalyst KOH, C represents the catalyst triethylamine, D represents the catalyst calcium acetate, E represents the catalyst magnesium acetate, F represents the catalyst barium acetate, and G represents the catalyst calcium carbonate.

[0097] As can be seen from Table 1, by comparing Examples 1-3, it can be concluded that when other conditions remain unchanged and only the amount of catalyst is considered, if the amount of catalyst is less than 0.4%, the reaction is incomplete due to the lack of catalyst, so that the hydroxyl value of the obtained product is too large, and the content of bishydroxyethyl bisphenol A ether is low, close to the index limit; if the amount of catalyst is higher than 0.4%, the color of the bishydroxyethyl bisphenol A ether of the product is darker.

[0098] Comparing Examples 2, 4 and 5, it can be concluded that when other conditions remain unchanged and only the reaction temperature is considered, the reaction temperature is 123±2°C (Example 2) which is the best. If the reaction temperature is lower than 123°C (Example 4), the reaction is incomplete, resulting in a large hydroxyl value of the product and a low content of bis(hydroxyethyl)bisphenol A ether. If the reaction temperature is higher than 123°C (Example 5), although the hydroxyl value and the content of bis(hydroxyethyl)bisphenol A ether are both better, the product color is darker.

[0099] By comparing Examples 2, 6 and 7, it can be concluded that when other conditions remain unchanged and only the component ratio in the catalyst is considered, the mass ratio of calcium acetate, magnesium acetate and barium acetate is 1:1:0.7, and although the indicators under the ratios of Examples 6 and 7 meet the standards, they are not as good as the product indicators under the ratio of Example 2.

[0100] By comparing Example 2, Comparative Example 7 and Comparative Example 8, it can be concluded that when other conditions remain unchanged and only the desolvation temperature is considered, the desolvation temperature of 100-105°C (Example 2) is the best. If the desolvation temperature is lower than 100-105°C (Example 6), the desolvation is incomplete, resulting in a high residual methylcyclohexane in the product. If the desolvation temperature is higher than 100-105°C (Example 7), although the residual methylcyclohexane is low, the product color is darker.

[0101] In summary, the optimal reaction conditions of the preparation method of the present invention are: the mass of the solvent methylcyclohexane is 50% of the mass of bisphenol A; the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7; the amount of the mixed acetate catalyst is 0.4% of the sum of the mass of bisphenol A and ethylene oxide; the reaction temperature is 123±2°C, the reaction pressure is less than 0.35MP; and the desolvation temperature is 100-105°C.

[0102] Comparing Comparative Examples 1 and 2 with Example 2, it can be seen that under the optimal reaction conditions, when only the type of catalyst is considered, although the hydroxyl value of the commonly used catalyst can meet the index, the color of the obtained product is darker, which shows that the mixed acetate catalyst used in the present invention has the advantage of improving the color of the product. Comparing Comparative Examples 3, 4, 5, and 6 with Example 2, it can be seen that under the optimal reaction conditions, the mixed acetate catalyst used in the present invention is compared with the conventional single-component alkaline earth metal catalyst, and the product obtained by the mixed acetate catalyst of the present invention is better in various indicators, proving that the catalyst of the present invention can make the content of bishydroxyethyl bisphenol A ether high, the hydroxyl value low, and the color light.

[0103] Example 8

[0104] This embodiment is intended to examine the repeatability of a solvent. The specific steps of a method for preparing bis(hydroxyethyl)bisphenol A ether are as follows:

[0105] In the reactor, 1000g of bisphenol A, 5.68g of mixed acetate catalyst (0.4% of the sum of the mass of bisphenol A and ethylene oxide, the mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.7) and 500g of methylcyclohexane are sequentially added, stirring is started and nitrogen is replaced three times, under the condition of vacuum degree ≥-0.098Mpa, after heating to 110°C, 420g of ethylene oxide is continuously introduced, the reaction temperature is controlled at 123±2°C, the pressure in the reactor is ≤0.35Mpa, and after adding, the temperature is maintained and the reaction is continued until the pressure in the reactor system no longer decreases, the temperature is cooled to 105°C and then the solvent is removed, the solvent removal temperature is controlled at 100-105°C, until no solvent comes out, the temperature is cooled to 85°C and degassed for 30min, and the finished product is obtained after the material is discharged. Subsequently, the catalyst obtained by filtration recovery is used to repeat the experiment, and if the mass of the recovered solvent is ≤300g, additional solvent is added to make its mass reach 500g.

[0106] The bis(hydroxyethyl)bisphenol A ether obtained in each embodiment 8 was subjected to liquid chromatography analysis and gas chromatography analysis. The results are shown in Table 2.

[0107] Table 2 Product performance index data obtained by repeated experiments in Example 8

[0108] Use times Color(Pt-Co) Bis(hydroxyethyl)bisphenol A ether(%) Hydroxyl value (mgKOH / g) 1 13.1 99.1 358.1 5 13.4 99.1 356.8 10 14.3 99.0 358.2 20 15.2 99.2 356.7. 40 15.3 98.9 357.5

[0109] The data shown in Table 2 show that after the methylcyclohexane solvent used in the present invention is recycled and reused 40 times, a bishydroxyethyl bisphenol A ether product with a bishydroxyethyl bisphenol A ether content of ≥98%, a color of ≤30, and a hydroxyl value of about 345 to 365 mgKOH / g can still be obtained, which shows that the preparation method of the present invention not only has an excellent catalytic effect, so that the prepared bishydroxyethyl bisphenol A ether has a high content, a low hydroxyl value, and a light color, but also has a simple process, is easy to implement industrially, and the prepared product has high quality and stable quality.

[0110] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. A method for preparing bishydroxyethyl bisphenol A ether, characterized in that: Add bisphenol A, a mixed acetate catalyst and a solvent into a reaction kettle, start stirring and replace nitrogen, heat to the reaction temperature and start introducing ethylene oxide, maintain the temperature and continue the reaction until the pressure no longer decreases after the addition of ethylene oxide, cool to the desolvation temperature and then remove the solvent until no solvent comes out, cool and degas and then discharge to obtain the bishydroxyethyl bisphenol A ether; Wherein, the mixed acetate catalyst is composed of calcium acetate, magnesium acetate and barium acetate; and the solvent is methylcyclohexane.

2. The method for preparing bis(hydroxyethyl) bisphenol A ether according to claim 1, wherein: The mass ratio of calcium acetate, magnesium acetate and barium acetate in the mixed acetate catalyst is 1:1:0.5-1.

3. The method for preparing bishydroxyethyl bisphenol A ether according to claim 1 or 2, characterized in that: The dosage of the mixed acetate catalyst is 0.1% to 1% of the sum of the mass of bisphenol A and ethylene oxide.

4. The method for preparing bishydroxyethyl bisphenol A ether according to claim 3, wherein: The dosage of the mixed acetate catalyst is 0.4% of the sum of the mass of bisphenol A and ethylene oxide.

5. The method for preparing bis(hydroxyethyl)bisphenol A ether according to claim 1 or 2, characterized in that: The amount of methylcyclohexane added is 30% to 100% of the mass of bisphenol A, preferably 50%.

6. The method for preparing bishydroxyethyl bisphenol A ether according to claim 1 or 2, characterized in that: The reaction temperature is 100-150° C. and the reaction pressure is lower than 0.50 MPa.

7. The method for preparing bishydroxyethyl bisphenol A ether according to claim 6, characterized in that: The reaction temperature is 123±2° C. and the reaction pressure is lower than 0.35 MPa.

8. The method for preparing bis(hydroxyethyl) bisphenol A ether according to claim 1 or 2, characterized in that: The desolvation temperature is 90-110°C, preferably 100-105°C.

9. The method for preparing bishydroxyethyl bisphenol A ether according to claim 5, characterized in that: The cooling is to cool to 85° C. and then degas.

10. The method for preparing bishydroxyethyl bisphenol A ether according to claim 1 or 2, characterized in that: The content of the bishydroxyethyl bisphenol A ether is ≥97%, the hydroxyl value is 325-385 mgKOH / g, and the color (Pt-Co) is ≤35.

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