CN102351653A - Method for purifying 2, 4-di-(1-phenylisopropyl) phenol with secondary recrystallization - Google Patents

Abstract

A method for purifying 2,4-dicumylphenol by secondary recrystallization relates to a method for purifying 2,4-dicumylphenol. The invention solves the problems of complex process, low yield and poor purity in the existing 2,4-dicumylphenol purification method. This method: dissolve the crude product of 2,4-dicumylphenol to be purified in petroleum ether, crystallize out after cooling, and dry the crystal to obtain a primary crystal; then dissolve the primary crystal in a mixture of methanol and water In the solvent, crystals precipitated after cooling, and after the crystals were dried, the pure product of 2,4-dicumylphenol was obtained. The purity of the pure product of 2,4-dicumylphenol was greater than 99%, and the extraction rate of the product was 70%- 85%; the purification method is simple and suitable for industrial production.

Description

Method for purifying 2,4-dicumylphenol by secondary recrystallization

technical field

The invention relates to a method for purifying 2,4-dicumylphenol. the

Background technique

2,4-dicumylphenol is an important fine chemical raw material, which can be used in the production of fine chemicals as ultraviolet absorbers, surfactants, agricultural emulsifiers, and fungicides for polycarbonate products. However, since 2,4-dicumylphenol is in the synthetic process, the reaction system inevitably contains 2-cumylphenol, 4-cumylphenol, 2,4,6-tricumylphenol and α-methyl Styrene oligomers make the purity of 2,4-dicumylphenol only 60% to 80%. The existing 2,4-dicumylphenol purification method is to use a solvent for multiple recrystallizations after vacuum distillation, that is, to collect the main fraction by vacuum distillation to obtain a crude product with a purity of 85% to 90%, and then use a The solvent is purified by multiple recrystallization methods. This purification method has complicated process and is difficult to remove complex and diverse by-products in the product, the yield is only 30%-60%, and the product purity is lower than 97%. the

Contents of the invention

The object of the present invention is to provide a method for purifying 2,4-dicumylphenol by secondary recrystallization in order to solve the problems of complex process, low yield and poor purity in the existing 2,4-dicumylphenol purification method. the

The present invention utilizes secondary recrystallization to purify 2, the method for 4-dicumylphenol is carried out according to the following steps: 1, sherwood oil recrystallization: press the ratio of 2,4-dicumylphenol crude product to be purified and sherwood oil to be 1g : 1.2mL～3mL take by weighing the crude product of 2,4-dicumylphenol and sherwood oil to be purified, add the crude product of 2,4-dicumylphenol to be purified in petroleum ether, after stirring and dissolving, cool to a temperature of 0℃～10℃ and keep it for 8h～12h, filter to obtain petroleum ether mother liquor and solid phase, rinse the solid phase with petroleum ether, and then put it in a vacuum of 0.085MPa～0.095MPa and a temperature of 40℃～60 Vacuum dry for 4h-6h under the condition of ℃ to obtain primary crystallization; 2. Methanol-water recrystallization: Measure methanol and water according to the volume ratio of methanol to water of 6-9:1 and mix them uniformly to obtain a methanol-water mixture Solvent, according to the ratio of the primary crystal crystal and the methanol-water mixed solvent is 1g: 1mL~3mL, weigh the primary crystal crystal obtained in step 1 and the methanol-water mixed solvent, stir and dissolve, and cool to a temperature of 0°C~10°C And keep it for 8h ~ 12h, filter, get the methanol-water mixed solvent mother liquor and solid phase, rinse the solid phase with methanol-water mixed solvent, and then put it in a vacuum of 0.085MPa ~ 0.095MPa and a temperature of 40℃ ~ Vacuum drying at 60°C for 4h to 8h to obtain pure 2,4-dicumylphenol. the

The 2,4-dicumylphenol crude product to be purified in step 1 of the present invention comprises 2,4-dicumylphenol, 2-cumylphenol, 4-cumylphenol, 2,4,6-tricumylphenol And α-methylstyrene polymer, the total content of impurities is less than 20%. The crystals obtained after recrystallization with petroleum ether contain 2,4-dicumylphenol, 2-cumylphenol and 4-cumylphenol, which are white needle-like crystals; recrystallization with methanol-water mixed solvent removes 2 - cumylphenol and 4-cumylphenol to obtain pure white needle-like crystal 2,4-dicumylphenol. Through two recrystallizations of step 1 and step 2, the pure product of 2,4-dicumylphenol with a mass purity greater than 99% by liquid chromatography can be obtained; after two recrystallizations, 2,4-dicumylphenol The proposing rate is 70%-85% (mass percentage). The purification process by two recrystallizations is obviously simplified and is suitable for industrial production. the

Detailed ways

Specific embodiment one: this embodiment utilizes secondary recrystallization to purify 2, the method for 4-dicumylphenol is carried out according to the following steps: 1, sherwood oil recrystallization: press 2,4-dicumylphenol crude product to be purified and The ratio of petroleum ether is 1g: 1.2mL～3mL. Weigh the crude 2,4-dicumylphenol to be purified and petroleum ether, add the crude 2,4-dicumylphenol to be purified into petroleum ether, stir to dissolve Afterwards, cool to a temperature of 0°C to 10°C and keep it for 8h to 12h, filter to obtain petroleum ether mother liquor and solid phase, rinse the solid phase with petroleum ether, and then place it in a vacuum of 0.085MPa to 0.095MPa, Vacuum drying at a temperature of 40°C to 60°C for 4h to 6h to obtain primary crystals; 2. Methanol-water recrystallization: measure methanol and water according to the volume ratio of methanol to water of 6 to 9:1 and mix well , to obtain methanol-water mixed solvent, and then according to the ratio of primary crystal crystal and methanol-water mixed solvent is 1g: 1mL～3mL, weigh the primary crystal crystal obtained in step 1 and methanol-water mixed solvent, after stirring and dissolving, cool to temperature Keep it at 0℃～10℃ for 8h～12h, filter to obtain the methanol-water mixed solvent mother liquor and solid phase, rinse the solid phase with methanol-water mixed solvent, and then put it in a vacuum of 0.085MPa～0.095MPa 1. Vacuum drying at a temperature of 40° C. to 60° C. for 4 hours to 8 hours to obtain pure 2,4-dicumylphenol. the

The purpose of washing the solid phase with sherwood oil in step 1 is to wash away the impurities attached to the surface of the solid phase with sherwood oil;

The purpose of rinsing the solid phase with a methanol-water mixed solvent in step 2 is to wash away the impurities attached to the surface of the solid phase with a methanol-water mixed solvent. the

The crude 2,4-dicumylphenol to be purified in step 1 of this embodiment includes 2,4-dicumylphenol, 2-cumylphenol, 4-cumylphenol, 2,4,6-tricumylphenol A polymer of phenol and α-methylstyrene with a total impurity content of less than 20%. The crystals obtained after recrystallization with petroleum ether contain 2,4-dicumylphenol, 2-cumylphenol and 4-cumylphenol, which are white needle-like crystals; recrystallization with methanol-water mixed solvent removes 2 - cumylphenol and 4-cumylphenol to obtain pure white needle-like crystal 2,4-dicumylphenol. Through two recrystallizations of step 1 and step 2, the pure product of 2,4-dicumylphenol with a mass purity greater than 99% by liquid chromatography can be obtained; after two recrystallizations, 2,4-dicumylphenol The proposing rate is 70%-85% (mass percentage). The purification process by two recrystallizations is obviously simplified and is suitable for industrial production. the

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the ratio of crude 2,4-dicumylphenol to be purified to petroleum ether in step 1 is 1 g: 1.5 mL to 2.8 mL. Others are the same as in the first embodiment.

Embodiment 3: This embodiment differs from Embodiment 1 in that the ratio of crude 2,4-dicumylphenol to be purified to petroleum ether in step 1 is 1 g: 2.0 mL. Others are the same as in the first embodiment. the

Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that: in step 1, the cooling temperature is 2°C to 8°C, and the cooling time is 8.5h to 11.5h. Others are the same as those in the first to third specific embodiments. the

Embodiment 5: This embodiment is different from Embodiment 1 to Embodiment 3 in that: in step 1, the cooling temperature is 5° C., and the cooling time is 10 h. Others are the same as those in the first to third specific embodiments. the

Specific embodiment six: the difference between this embodiment and one of the specific embodiments one to five is: the vacuum degree of vacuum drying in step 1 is 0.087MPa～0.093MPa, the temperature is 43°C～57°C, and the drying time is 4.5h～ 5.5h. Others are the same as one of the specific embodiments 1 to 5. the

Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 5 in that: in step 1, the vacuum degree of vacuum drying is 0.090 MPa, the temperature is 50° C., and the drying time is 5 hours. Others are the same as one of the specific embodiments 1 to 5. the

Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that in step 2, the volume ratio of methanol to water is 6.3 to 8.7: 1 to measure methanol and water and mix them uniformly to obtain methanol-water mixture solvent. Others are the same as one of the specific embodiments 1 to 7. the

Embodiment 9: This embodiment differs from Embodiment 1 to Embodiment 7 in that: in step 2, methanol and water are measured at a volume ratio of methanol to water of 7.5:1 and mixed uniformly to obtain a methanol-water mixed solvent. Others are the same as one of the specific embodiments 1 to 7. the

Embodiment 10: This embodiment differs from Embodiment 1 to Embodiment 9 in that the ratio of the primary crystallization crystal to the methanol-water mixed solvent in step 2 is 1 g: 1.5 mL to 2.5 mL. Others are the same as one of the specific embodiments 1 to 9. the

Embodiment 11: This embodiment is different from Embodiment 1 to Embodiment 9 in that the ratio of the primary crystallization crystal to the methanol-water mixed solvent in step 2 is 1 g: 2.0 mL. Others are the same as one of the specific embodiments 1 to 9. the

Embodiment 12: This embodiment is different from Embodiments 1 to 11 in that: in step 2, the cooling temperature is 2°C-8°C, and the cooling time is 8.5h-11.5h. Others are the same as those of the specific embodiments 1 to 11. the

Embodiment 13: This embodiment is different from Embodiments 1 to 11 in that: in step 2, the cooling temperature is 5° C., and the cooling time is 10 h. Others are the same as those of the specific embodiments 1 to 11. the

Embodiment 14: The difference between this embodiment and Embodiment 1 to 13 is that the degree of vacuum drying in step 2 is 0.087MPa-0.093MPa, the temperature is 42°C-58°C, and the drying time is 4.2h ~7.5h. Others are the same as those of the first to thirteenth specific embodiments. the

Embodiment 15: This embodiment differs from Embodiment 1 to Embodiment 13 in that: the vacuum degree of vacuum drying in step 2 is 0.090 MPa, the temperature is 50° C., and the drying time is 6 hours. Others are the same as those in the first to thirteenth specific embodiments. the

Specific Embodiment Sixteen: In this embodiment, the method for purifying 2,4-dicumylphenol by recrystallization is carried out according to the following steps: 1. Petroleum ether recrystallization: Weigh 300 g of 2,4 to be purified with a mass purity of 86%. - Crude dicumylphenol and 450mL petroleum ether, add the crude 2,4-dicumylphenol to be purified into petroleum ether, stir and dissolve, cool to 3°C and keep for 10h, filter to obtain petroleum ether mother liquor and solid phase, after the solid phase is filtered out, rinse twice with petroleum ether, and then be placed in a vacuum oven with a vacuum of 0.090MPa and a temperature of 45°C for 4 hours to obtain 220g of primary crystals; Methanol-water recrystallization: Measure 250mL of methanol and 40mL of distilled water, mix well to obtain a methanol-water mixed solvent, add 220g of primary crystals obtained in step 1 into the methanol-water mixed solvent, stir and dissolve, then cool to a temperature of 3°C And kept for 10h, filtered to obtain methanol-water mixed solvent mother liquor and solid phase, the solid phase was rinsed twice with a mixed solvent with a volume ratio of methanol and water of 7:1, and then placed in a vacuum of 0.090MPa, Dry in a vacuum oven at a temperature of 50° C. for 5 hours to obtain 206 g of pure 2,4-dicumylphenol. the

In this embodiment, the primary crystal in step 1 is detected by high performance liquid chromatography, wherein the mass content of 2,4-dicumylphenol is 95.2%; the pure product of 2,4-dicumylphenol obtained in step 2 is obtained by high performance liquid chromatography Phase chromatography detection shows that its mass purity is 99.20%, and the pure 2,4-dicumylphenol obtained in step 2 accounts for 79.8% of the mass of the crude 2,4-dicumylphenol to be purified. the

Embodiment 17: In this embodiment, the method for purifying 2,4-dicumylphenol by recrystallization is carried out in the following steps: 1. Petroleum ether recrystallization: take 300 g of 2,4-dicumylphenol to be purified with a purity of 91% (mass). , crude 4-dicumylphenol and 400mL petroleum ether, add the crude 2,4-dicumylphenol to be purified into petroleum ether, stir and dissolve, cool to 2°C and keep for 10h, filter to obtain petroleum Ether mother liquor and solid phase, the solid phase was washed twice with petroleum ether, and then placed in a vacuum oven with a vacuum degree of 0.090MPa and a temperature of 45°C for 5 hours to obtain 251g of primary crystals; 2. Methanol-water recrystallization: Measure 300mL of methanol and 40mL of distilled water, mix them evenly, add 251g of primary crystals obtained in step 1 into the mixed solvent of methanol-water, stir and dissolve, cool to 2°C and keep for 10h. Filter to obtain the methanol water solvent mother liquor and the solid phase, and after the solid phase is filtered out, use 50mL of methanol and water with a volume ratio of 7:1 to rinse twice with a mixed solvent, then place it in a vacuum of 0.090MPa and a temperature of Dry in a vacuum oven at 50° C. for 5 hours to obtain 215 g of pure 2,4-dicumylphenol. the

In this embodiment, the primary crystals in step 1 are detected by high performance liquid chromatography, wherein the mass content of 2,4-dicumylphenol is 96.3%; Phase chromatography detection shows that its mass purity is 99.4%, and the pure 2,4-dicumylphenol obtained in step 2 accounts for 78.8% of the mass of the crude 2,4-dicumylphenol to be purified. the

Embodiment 18: In this embodiment, the method for purifying 2 by recrystallization, 4-dicumylphenol is carried out in the following steps: 1. Petroleum ether recrystallization: take 500g of 2 to be purified with a purity of 92% (mass). , crude 4-dicumylphenol and 650mL petroleum ether, add the crude 2,4-dicumylphenol to be purified into petroleum ether, stir and dissolve, cool to 2°C and keep for 10h, filter to obtain petroleum Ether mother liquor and solid phase, the solid phase was rinsed twice with petroleum ether, and then placed in a vacuum oven with a vacuum of 0.090 MPa and a temperature of 45°C for 4 hours to obtain 379 g of primary crystals; 2. Methanol -Water recrystallization: Measure 450mL of methanol and 50mL of water, mix evenly, add 379g of primary crystals obtained in step 1 into the mixed solvent of methanol-water, stir and dissolve, cool to 2°C and keep for 10h, Filter to obtain the methanol water solvent mother liquor and solid phase, rinse the solid phase twice with 100mL of a mixed solvent with a volume ratio of methanol and water of 7:1, and dry in vacuum at a vacuum of 0.090MPa and a temperature of 50°C After drying in the oven for 6 hours, 340 g of pure 2,4-dicumylphenol was obtained. the

In this embodiment, the primary crystal in step 1 is detected by high performance liquid chromatography, wherein the mass content of 2,4-dicumylphenol is 97.4%; the pure product of 2,4-dicumylphenol obtained in step 2 is obtained by high performance liquid chromatography According to phase chromatography detection, its mass purity is 99.5%, and the pure 2,4-dicumylphenol obtained in step 2 accounts for 73.9% of the mass of the crude 2,4-dicumylphenol to be purified. the

Nineteenth specific embodiment: In this embodiment, the method for purifying 2,4-dicumylphenol by recrystallization is carried out according to the following steps: 1. Petroleum ether recrystallization: take 300 g of 2,4-dicumylphenol to be purified with a purity of 94% (mass). , crude 4-dicumylphenol and 360mL petroleum ether, add the crude 2,4-dicumylphenol to be purified into petroleum ether, stir and dissolve, cool to 1°C and keep for 10h, filter to obtain petroleum Ether mother liquor and solid phase, the solid phase was rinsed twice with petroleum ether, and then placed in a vacuum oven with a vacuum of 0.090 MPa and a temperature of 50°C for 5 hours to obtain 289 g of primary crystals; 2. Methanol -Water recrystallization: Measure 350mL of methanol and 30mL of water, mix well, add 289g of primary crystals obtained in step 1 into the mixed solvent of methanol-water, stir and dissolve, cool to 1°C and keep for 10h, Filter to obtain the methanol water solvent mother liquor and solid phase, rinse the solid phase twice with 100mL of a mixed solvent with a volume ratio of methanol and water of 7:1, and dry in vacuum at a vacuum of 0.090MPa and a temperature of 50°C After drying in the oven for 6 hours, 237 g of pure 2,4-dicumylphenol was obtained. the

In this embodiment, the primary crystal in step 1 is detected by high-performance liquid chromatography, wherein the mass content of 2,4-dicumylphenol is 97.1%; the pure product of 2,4-dicumylphenol obtained in step 2 is obtained by high-performance liquid chromatography According to phase chromatography detection, its mass purity is 99.4%, and the pure 2,4-dicumylphenol obtained in step 2 accounts for 84.0% of the mass of the crude 2,4-dicumylphenol to be purified. the

Claims (8)

1. utilize secondary recrystallization to purify 2; The method of 4-di-(1-phenylisopropyl) phenol; It is characterized in that utilizing secondary recrystallization to purify 2; The method of 4-di-(1-phenylisopropyl) phenol is carried out according to the following steps: one; Sherwood oil recrystallization: by to be purified 2; The ratio of 4-di-(1-phenylisopropyl) phenol crude product and sherwood oil is that 1g: 1.2mL～3mL takes by weighing to be purified 2; 4-di-(1-phenylisopropyl) phenol crude product and sherwood oil; With to be purified 2; 4-di-(1-phenylisopropyl) phenol crude product joins in the sherwood oil; After the stirring and dissolving; To be cooled to temperature be 0 ℃～10 ℃ and keep 8h～12h; Filter, obtain sherwood oil mother liquor and solid formation, solid formation sherwood oil drip washing; Being placed on vacuum tightness then is 0.085MPa～0.095MPa; Temperature is vacuum-drying 4h～6h under 40 ℃～60 ℃ the condition, obtains the primary crystallization crystal; Two; The methanol-water recrystallization: by the volume ratio of methyl alcohol and water is to measure first alcohol and water and mix at 6～9: 1; Obtain the methanol-water mixed solvent; Ratio by primary crystallization crystal and methanol-water mixed solvent is that 1g: 1mL～3mL takes by weighing primary crystallization crystal and the methanol-water mixed solvent that step 1 obtains again; After the stirring and dissolving; To be cooled to temperature be 0 ℃～10 ℃ and keep 8h～12h; Filter; Obtain methanol-water mixed solvent mother liquor and solid formation; With solid formation with the drip washing of methanol-water mixed solvent; Being placed on vacuum tightness then is 0.085MPa～0.095MPa; Temperature is vacuum-drying 4h～8h under 40 ℃～60 ℃ the condition; Obtain 2, the pure article of 4-di-(1-phenylisopropyl) phenol.

2. the secondary recrystallization that utilizes according to claim 1 purifies 2, and the method for 4-di-(1-phenylisopropyl) phenol is characterized in that in the step 1 to be purified 2, and 4-di-(1-phenylisopropyl) phenol crude product is 1g: 1.5mL～2.8mL with the ratio of sherwood oil.

3. the secondary recrystallization that utilizes according to claim 1 and 2 purifies 2, and the method for 4-di-(1-phenylisopropyl) phenol is characterized in that in the step 1 that cooling temperature is that 2 ℃～8 ℃, cooling time are 8.5h～11.5h.

4. the secondary recrystallization that utilizes according to claim 1 and 2 purifies 2, the method for 4-di-(1-phenylisopropyl) phenol, it is characterized in that vacuum drying vacuum tightness in the step 1 be 0.087MPa～0.093MPa, temperature be 43 ℃～57 ℃, be 4.5h～5.5h time of drying.

5. the secondary recrystallization that utilizes according to claim 1 and 2 purifies 2, and the method for 4-di-(1-phenylisopropyl) phenol is characterized in that in the step 2 that volume ratio by methyl alcohol and water is to measure first alcohol and water and mix at 6.3～8.7: 1, obtains the methanol-water mixed solvent.

6. the secondary recrystallization that utilizes according to claim 1 and 2 purifies 2, and the method for 4-di-(1-phenylisopropyl) phenol is characterized in that the ratio of primary crystallization crystal and methanol-water mixed solvent is 1g: 1.5mL～2.5mL in the step 2.

7. the secondary recrystallization that utilizes according to claim 1 and 2 purifies 2, and the method for 4-di-(1-phenylisopropyl) phenol is characterized in that in the step 2 that cooling temperature is that 2 ℃～8 ℃, cooling time are 8.5h～11.5h.

8. the secondary recrystallization that utilizes according to claim 1 and 2 purifies 2, and the method for 4-di-(1-phenylisopropyl) phenol is characterized in that in the step 2 that vacuum drying vacuum tightness is that 0.087MPa～0.093MPa, temperature are that 42 ℃～58 ℃, time of drying are 4.2h～7.5h.