CN111302934B - Preparation and separation method of 6-hydroxyhexyl acrylate - Google Patents
Preparation and separation method of 6-hydroxyhexyl acrylate Download PDFInfo
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Abstract
The invention provides a preparation and separation method of 6-hydroxyhexyl acrylate, which comprises the following steps: mixing acrylic acid, 1, 6-hexanediol, a copper salt polymerization inhibitor and a catalyst, heating to 105-110 ℃ for reaction to obtain a reaction solution containing acrylic acid-6-hydroxyhexyl ester, 1, 6-hexanediol and 1, 6-hexanediol diacrylate; adding water into the reaction solution to form a water phase A, and extracting by taking aliphatic alkane as an extracting agent to obtain a water phase B; distilling the water phase B under reduced pressure to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate; feeding the mixture from the bottom of the rectifying tower, feeding the mixture of the ionic liquid and the copper salt polymerization inhibitor from a tower plate at the upper part of the rectifying tower, and feeding the tower bottom liquid into a short-path evaporator for distillation to obtain the 6-hydroxyhexyl acrylate product. The invention can obtain the acrylic acid-6-hydroxyhexyl ester with the yield of 94-96 percent and the purity of more than 99 percent.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a preparation and separation method of 6-hydroxyhexyl acrylate.
Background
Acrylic acid-6-hydroxyhexyl ester belongs to novel acrylic acid hydroxy esters, and the market of the product is blank at present. 6-hydroxyhexyl acrylate is predominantly para-4-hydroxybutyl acrylate (4-HBA). Compared with 4-HBA, the method has the following advantages: (1) the carbon chain of the acrylic acid-6-hydroxyhexyl ester is longer, and the viscosity of the resin prepared by the acrylic acid-6-hydroxyhexyl ester can be further reduced, so that a high-solid low-viscosity product is obtained; (2) the balance between hardness and softness is better realized, and the problem of the traditional acrylate is solved; (3) the chain segment connected with the hydroxyl has larger flexibility, so that the steric hindrance of the alcoholic hydroxyl is reduced, and the hydroxyl has larger activity and higher reactivity, so that the curing speed of the synthesized hydroxyl acrylic resin is obviously improved, and the drying speed and the hardness building speed are very high; (4) the prepared paint film has good appearance, good scratch resistance and wear resistance, and is very suitable for automotive OEM coating and repair coating, so that the paint film has good application prospect.
The reaction solution of 6-hydroxyhexyl acrylate mainly comprises excessive 1, 6-hexanediol, byproduct 1, 6-hexanediol diacrylate and product 6-hydroxyhexyl acrylate, however, the product 6-hydroxyhexyl acrylate is difficult to separate from the reaction solution for the following reasons: on one hand, the 1, 6-hexanediol is greatly excessive and has strong water solubility, so that the water consumption is large in the process of removing the 1, 6-hexanediol by extraction, the loss of the product of the hydroxyhexyl acrylate is increased, and the yield is low; on the other hand, because the boiling points of the product 6-hydroxyhexyl acrylate and the byproduct 1, 6-hexanediol diacrylate are close to each other, and two vinyl groups are contained at two ends of the 1, 6-hexanediol diacrylate, the 1, 6-hexanediol diacrylate is easy to polymerize at high temperature, the separation of the two is not realized through conventional vacuum rectification, and the 1, 6-hexanediol diacrylate is polymerized and crosslinked at high temperature for a long time, so that the impurities in the product 6-hydroxyhexyl acrylate are further increased, and the yield and the purity of the product hydroxyhexyl acrylate are lower.
Therefore, the preparation and separation method of the acrylic acid-6-hydroxyhexyl ester with high yield and high purity is of great significance.
Disclosure of Invention
Therefore, the invention aims to provide a preparation and separation method of 6-hydroxyhexyl acrylate with high yield and high purity.
The invention is realized by the following technical scheme:
the invention provides a preparation and separation method of 6-hydroxyhexyl acrylate, which comprises the following steps:
(1) respectively adding acrylic acid, 1, 6-hexanediol, a copper salt polymerization inhibitor and a catalyst into a reaction container, stirring, heating to 105-110 ℃ for reaction (for example, reacting for 0.5-1.5h) to obtain a reaction solution containing acrylic acid-6-hydroxyhexyl ester, 1, 6-hexanediol and 1, 6-hexanediol diacrylate;
(2) adding water into the reaction liquid to form a water phase A, taking aliphatic alkane as an extracting agent, and extracting (preferably, performing multistage continuous countercurrent centrifugal extraction) to separate 1, 6-hexanediol diacrylate in the reaction liquid to obtain a raffinate water phase B; through the steps, the aim is to remove 1, 6-hexanediol diacrylate in the reaction liquid;
(3) removing water from the raffinate water phase B through reduced pressure distillation to obtain a mixture containing 1, 6-hexanediol and acrylic acid-6-hydroxyhexyl ester; preferably, the reduced pressure distillation is carried out at 80-90 ℃ under the condition of 10-20 kPa (A);
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate in the step (3) from the bottom of a rectifying tower, feeding the mixture of the ionic liquid and the copper salt polymerization inhibitor from a tower plate at the upper part of the rectifying tower, preferably 3-6 tower plates, rectifying to obtain the 1, 6-hexanediol (namely tower top liquid) from the top of the tower, and feeding the tower bottom liquid of the rectifying tower into a short-path evaporator for distillation to obtain the 6-hydroxyhexyl acrylate product.
The structural formula of the acrylic acid-6-hydroxyhexyl ester is shown as follows:
preferably, in the method for preparing and separating 6-hydroxyhexyl acrylate of the present invention, in step (4), the ionic liquid is a mixture of 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate; wherein the mass ratio of the 1-octyl-3-methylimidazole hexafluorophosphate to the 1-hexyl-3-methylimidazole trifluoromethanesulfonate is preferably 2: 8-6.5: 3.5, and more preferably 3: 7-6.2: 3.8.
Preferably, in the preparation and separation method of 6-hydroxyhexyl acrylate, in the step (4), the mass ratio of the ionic liquid to the copper salt polymerization inhibitor is 100: 1-100: 6, and preferably 100: 3-100: 4;
preferably, in the step (4), the mass ratio of the ionic liquid to the mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 8-1: 15, and preferably 1: 10-1: 12.
Preferably, in the method for preparing and separating 6-hydroxyhexyl acrylate, in the step (4), the number of the plates of the rectifying tower is 28-30;
preferably, in the step (4), the rectification conditions of the 1, 6-hexanediol in the rectification tower are 95-100 ℃ and 0.2-0.25 kPa (A).
Preferably, in the above method for preparing and separating 6-hydroxyhexyl acrylate of the present invention, in step (1) and step (4), the copper salt polymerization inhibitor is copper N, N-dibutyldithiocarbamate;
preferably, in the step (1), the amount of the copper salt polymerization inhibitor is 0.5-2 wt%, preferably 1-1.5 wt% of the amount of the acrylic acid.
Preferably, in the above method for preparing and separating 6-hydroxyhexyl acrylate of the present invention, in step (1), the catalyst is at least one selected from the group consisting of p-toluenesulfonic acid, phosphoric acid and methanesulfonic acid; preferably, the amount of the catalyst is 0.5wt% to 5wt%, more preferably 2 to 3.5wt% of the amount of the acrylic acid;
preferably, the molar ratio of the acrylic acid to the 1, 6-hexanediol is 1: 1.8-1: 2.2, preferably 1: 2;
preferably, the aliphatic alkane is selected from at least one of cyclohexane, n-hexane, n-heptane and n-octane, more preferably from cyclohexane.
Preferably, in the method for preparing and separating 6-hydroxyhexyl acrylate, in the step (2), the mass ratio of the water to the reaction liquid is 1: 2.5-1: 3.5, and preferably 1: 2.75-1: 3.25; too little water is not beneficial to forming larger polarity difference between the water phase A and the aliphatic alkane, and too much water increases the energy consumption of the subsequent reduced pressure distillation for removing water.
Preferably, the mass ratio of the aliphatic alkane to the water phase A is 1: 2-1: 4, preferably 1: 2.5-1: 3.5;
preferably, the theoretical number N of the multistage continuous countercurrent centrifugal extraction is 9-11.
The multistage continuous countercurrent centrifugal extraction equipment is well known by the technical personnel in the field and is formed by connecting centrifugal extractors in series in a certain number of stages, the flowing mode of a light phase and a heavy phase is countercurrent, the diameter of a rotary drum of the centrifugal extractor is 50mm, the rotating speed is 560-700 rpm, and the extraction operating temperature is 10-35 ℃; in some embodiments, the mass flow ratio of the light phase to the heavy phase during extraction is 1:2.5 to 3.5. The two phases enter a centrifugal extractor and are dispersed into small liquid drops through a rotary drum rotating at a high speed at the bottom to realize full mixing, the mixed liquid and the rotary drum realize the separation of light phase and heavy phase by means of density difference under the centrifugal force generated by high-speed rotation, the equipment has small volume, large handling capacity and high automation degree, and is very suitable for industrial continuous production.
Preferably, in the preparation and separation method of 6-hydroxyhexyl acrylate, in the step (4), the refrigerant in the built-in condenser of the short-path evaporator is 30-60 wt% of ethylene glycol aqueous solution, and the cooling temperature of the built-in condenser of the short-path evaporator is 0-8 ℃;
preferably, the operation temperature of the short-path evaporator is 110-120 ℃, and the operation pressure is 0.06-0.1 kPa (A).
In the present invention, kPa (A) represents the unit of absolute pressure.
Preferably, in the above method for preparing and separating 6-hydroxyhexyl acrylate of the present invention, the bottom liquid obtained after distillation by the short-path evaporator contains ionic liquid and copper salt polymerization inhibitor, and the mixture is recycled to the rectification column for reuse.
Preferably, in the above method for preparing and separating 6-hydroxyhexyl acrylate of the present invention, the purity of 6-hydroxyhexyl acrylate in the 6-hydroxyhexyl acrylate product (which is a light phase component) is more than 99%.
The technical scheme provided by the invention has the following beneficial effects:
(1) the preparation and separation method of the acrylic acid-6-hydroxyhexyl ester adopts a direct esterification process to obtain good conversion rate; in the preferred scheme, the higher conversion rate of the acrylic acid-6-hydroxyhexyl ester (the conversion rate is more than 75 percent) can be obtained by optimizing reaction parameters such as reaction temperature, reaction time, the mixture ratio of all raw materials and the like;
(2) an ionic liquid mixed copper salt polymerization inhibitor is fed from a tower plate at the upper part of a rectifying tower, so that the relative volatility of 1, 6-hexanediol in a mixed system of rectified materials 1, 6-hexanediol and 6-hydroxyhexyl acrylate is changed, the effective separation of the 1, 6-hexanediol is realized, and the difficulty of subsequent separation and purification is reduced; in the preferred scheme, the preferred compound ionic liquid is adopted, so that the separation effect can be improved, and the serious polymerization of a copper salt polymerization inhibitor in the tower is avoided; the invention can realize higher yield of the 6-hydroxyhexyl acrylate (the yield reaches 94-96%) and higher purity (the purity is more than 99%) by distilling the bottom liquid of the rectifying tower in a short-path evaporator.
(3) According to the preparation and separation method of the 6-hydroxyhexyl acrylate, after the esterification reaction is finished, the 1, 6-hexanediol diacrylate is removed through extraction, particularly by adopting a continuous countercurrent centrifugal extraction device, and the aliphatic alkane is used as an extractant, so that the extraction effect is good; in the preferred scheme, the operation parameters of the separation process, the mass ratio of water to the reaction liquid, the mass ratio of the heavy phase to the light phase and the like are optimized, so that the extraction efficiency in the whole process is high, and the dosage of the solvent is small.
(4) According to the preparation and separation method of the 6-hydroxyhexyl acrylate, the polymerization inhibitor can be effectively distributed in a rectification system by utilizing the intersolubility of the ionic liquid and the copper salt polymerization inhibitor, and the problem of serious polymerization of the copper salt polymerization inhibitor in a tower is solved.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples and comparative examples of the present invention, each raw material was a commercially available product.
The component analysis methods referred to in the examples employed gas chromatography, column types: DB-5(30 × 0.25), carrier gas velocity: 1mL/min, sample size: 0.2. mu.l, temperature program: the initial temperature is 80 ℃ and is kept for 10min, the heating rate is 2 ℃/min, and the final temperature is 160 ℃.
Example 1
The preparation and separation method of 6-hydroxyhexyl acrylate of the embodiment comprises the following steps:
(1) 106.2kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.36kg of copper N, N-dibutyldithiocarbamate and 0.72kg of p-toluenesulfonic acid are put into a 250L reaction kettle, stirred and heated to 105 ℃ for reaction for 1.5h to obtain a reaction solution. Wherein, the reaction solution mainly comprises the following main components in percentage by weight: 47.6 wt% of 1, 6-hexanediol, 42.2 wt% of 6-hydroxyhexyl acrylate, 6.3 wt% of 1, 6-hexanediol diacrylate, 82.8% of selectivity to 6-hydroxyhexyl acrylate, and 78.1% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 2.75; removing 1, 6-hexanediol diacrylate in the reaction liquid by 9-grade continuous countercurrent centrifugal extraction by taking cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of a 9-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1:2.5, the extraction temperature is 20 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 90 ℃ under the condition of 18kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the plates of the rectifying tower is 28; then compounding 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate according to the mass ratio of 3:7 to obtain ionic liquid, feeding a mixture of the ionic liquid and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate from a 3 rd tray of a rectifying tower, wherein the mass ratio of the ionic liquid to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100:3, and the mass ratio of the ionic liquid to a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 10; rectifying to obtain 1, 6-hexanediol as the top liquid, wherein the rectification conditions of the 1, 6-hexanediol at the top of the tower are 95 ℃ and 0.2kPa (A); pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein a built-in condenser of the short-path evaporator is filled with 30 wt% of ethylene glycol aqueous solution, the cooling temperature is 0 ℃, the operating conditions of the evaporator are 110 ℃ and 0.06kPa (A), and the acrylic acid-6-hydroxyhexyl ester product is obtained by distillation, wherein the purity of the acrylic acid-6-hydroxyhexyl ester is 99.6%, and the yield is 96.1%.
Carrying out high-resolution mass spectrometry on the prepared 6-hydroxyhexyl acrylate, wherein the mass spectrometry is HRMS-ESI: m/z: 173.1066([ M + H)] + Calculated values: 173.1102) with a molecular weight consistent with 6-hydroxyhexyl acrylate.
Example 2
The preparation and separation method of 6-hydroxyhexyl acrylate of the embodiment comprises the following steps:
(1) 129.8kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.54kg of copper N, N-dibutyldithiocarbamate and 1.26kg of phosphoric acid are put into a 250L reaction kettle, stirred and heated to 110 ℃ for reaction for 0.5h to obtain a reaction solution. Wherein, the reaction solution mainly comprises the following main components in percentage by weight: 48.6 wt% of 1, 6-hexanediol, 41.1 wt% of 6-hydroxyhexyl acrylate, 5.2 wt% of 1, 6-hexanediol diacrylate, 84.2% of 6-hydroxyhexyl acrylate selectivity and 79.3% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 3.25; removing 1, 6-hexanediol diacrylate in the reaction liquid by 11-stage continuous countercurrent centrifugal extraction by using cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of an 11-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1:3.5, the extraction temperature is 30 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 80 ℃ and under the condition of 10kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the tower plates of the rectifying tower is 30; then compounding 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate according to the mass ratio of 2:8 to obtain ionic liquid, feeding a mixture of the ionic liquid and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate from a 6 th tower plate of a rectifying tower, wherein the mass ratio of the ionic liquid to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100:4, and the mass ratio of the ionic liquid to a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 12; rectifying to obtain 1, 6-hexanediol as the top liquid, wherein the rectification conditions of the 1, 6-hexanediol at the top of the tower are 100 ℃ and 0.25kPa (A); pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein 50 wt% of ethylene glycol aqueous solution is filled in a built-in condenser of the short-path evaporator, the cooling temperature is 8 ℃, the operation conditions of the evaporator are 120 ℃ and 0.1kPa (A), and the acrylic acid-6-hydroxyhexyl ester product is obtained by distillation, wherein the purity of the acrylic acid-6-hydroxyhexyl ester is 99.2%, and the yield is 94.1%.
Carrying out high-resolution mass spectrometry on the prepared 6-hydroxyhexyl acrylate, wherein the mass spectrometry is HRMS-ESI: m/z: 173.1066([ M + H)] + Calculated values: 173.1102) with a molecular weight consistent with 6-hydroxyhexyl acrylate.
Example 3
The preparation and separation method of 6-hydroxyhexyl acrylate of the embodiment comprises the following steps:
(1) 115kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.42kg of copper N, N-dibutyldithiocarbamate and 1.1kg of methanesulfonic acid were put into a 250L reaction kettle, and the temperature was raised to 108 ℃ by stirring to react for 1 hour, thereby obtaining a reaction solution. Wherein, the reaction solution mainly comprises the following main components in percentage by weight: 47.9 wt% of 1, 6-hexanediol, 41.6 wt% of acrylic acid-6-hydroxyhexyl ester, 5.8 wt% of 1, 6-hexanediol diacrylate, 83.2% of selectivity to acrylic acid-6-hydroxyhexyl ester, and 78.7% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 3; removing 1, 6-hexanediol diacrylate in the reaction liquid by 10-grade continuous countercurrent centrifugal extraction by using cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of a 10-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1:3, the extraction temperature is 25 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 85 ℃ and 14kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the plates of the rectifying tower is 29; then compounding 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate according to the mass ratio of 6.5:3.5 to obtain ionic liquid, feeding a mixture of the ionic liquid and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate from a 4 th tray of a rectifying tower, wherein the mass ratio of the ionic liquid to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100: 3.5, and the mass ratio of the ionic liquid to a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 11; rectifying to obtain 1, 6-hexanediol as the top liquid, wherein the rectification conditions of the 1, 6-hexanediol at the top of the tower are 98 ℃ and 0.23kPa (A); pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein a built-in condenser of the short-path evaporator is filled with 60wt% of ethylene glycol aqueous solution, the cooling temperature is 3 ℃, the operation conditions of the evaporator are 115 ℃ and 0.08kPa (A), and the acrylic acid-6-hydroxyhexyl ester product is obtained by distillation, wherein the purity of the acrylic acid-6-hydroxyhexyl ester is 99.1%, and the yield is 95.2%.
Carrying out high-resolution mass spectrometry on the prepared 6-hydroxyhexyl acrylate, wherein the mass spectrometry is HRMS-ESI: m/z: 173.1066([ M + H)] + Calculated values: 173.1102) with a molecular weight consistent with 6-hydroxyhexyl acrylate.
Example 4
The preparation and separation method of 6-hydroxyhexyl acrylate of the embodiment comprises the following steps:
(1) 115kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.42kg of copper N, N-dibutyldithiocarbamate and 1.1kg of methanesulfonic acid were put into a 250L reaction kettle, and the temperature was raised to 108 ℃ by stirring to react for 1 hour, thereby obtaining a reaction solution. Wherein, the reaction solution mainly comprises the following main components in percentage by weight: 47.9 wt% of 1, 6-hexanediol, 41.6 wt% of acrylic acid-6-hydroxyhexyl ester, 5.8 wt% of 1, 6-hexanediol diacrylate, 83.2% of selectivity to acrylic acid-6-hydroxyhexyl ester, and 78.7% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 3; removing 1, 6-hexanediol diacrylate in the reaction liquid by 10-grade continuous countercurrent centrifugal extraction by using cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of a 10-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1:3, the extraction temperature is 25 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 85 ℃ and 14kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the plates of the rectifying tower is 29; then compounding 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate according to the mass ratio of 6.2:3.8 to obtain ionic liquid, feeding a mixture of the ionic liquid and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate from a 4 th tray of a rectifying tower, wherein the mass ratio of the ionic liquid to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100:4, and the mass ratio of the ionic liquid to a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 11; rectifying to obtain 1, 6-hexanediol as the top liquid, wherein the rectification conditions of the 1, 6-hexanediol at the top of the tower are 98 ℃ and 0.23kPa (A); pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein a built-in condenser of the short-path evaporator is filled with 60wt% of ethylene glycol aqueous solution, the cooling temperature is 3 ℃, the operation conditions of the evaporator are 115 ℃ and 0.08kPa (A), and the acrylic acid-6-hydroxyhexyl ester product is obtained by distillation, wherein the purity of the acrylic acid-6-hydroxyhexyl ester is 99.5%, and the yield is 95.6%.
Carrying out high-resolution mass spectrometry on the prepared 6-hydroxyhexyl acrylate, wherein the mass spectrometry is HRMS-ESI: m/z: 173.1066([ M + H)] + Calculated values: 173.1102) with a molecular weight consistent with 6-hydroxyhexyl acrylate.
Example 5
The preparation and separation method of 6-hydroxyhexyl acrylate of the embodiment comprises the following steps:
(1) 115kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.42kg of copper N, N-dibutyldithiocarbamate and 1.1kg of methanesulfonic acid were put into a 250L reaction kettle, and the temperature was raised to 108 ℃ by stirring to react for 1 hour, thereby obtaining a reaction solution. Wherein, the reaction solution mainly comprises the following main components in percentage by weight: 47.9 wt% of 1, 6-hexanediol, 41.6 wt% of acrylic acid-6-hydroxyhexyl ester, 5.8 wt% of 1, 6-hexanediol diacrylate, 83.2% of selectivity to acrylic acid-6-hydroxyhexyl ester, and 78.7% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 3; removing 1, 6-hexanediol diacrylate in the reaction liquid by 10-grade continuous countercurrent centrifugal extraction by using cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of an 11-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1: 3.4, the extraction temperature is 25 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 85 ℃ and 14kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the plates of the rectifying tower is 29; then compounding 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate according to the mass ratio of 5.5: 4.5 to obtain ionic liquid, feeding a mixture of the ionic liquid and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate from a 4 th tray of a rectifying tower, wherein the mass ratio of the ionic liquid to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100:4, and the mass ratio of the ionic liquid to a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 11; rectifying to obtain 1, 6-hexanediol as the top liquid, wherein the rectification conditions of the 1, 6-hexanediol at the top of the tower are 98 ℃ and 0.23kPa (A); pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein a built-in condenser of the short-path evaporator is a 60wt% ethylene glycol aqueous solution, the cooling temperature is 3 ℃, the operating conditions of the evaporator are 115 ℃ and 0.08kPa (A), and the obtained heavy component is a mixture of a compound ionic liquid and copper salt polymerization inhibitor N, N-dibutyl dithiocarbamate; pumping the heavy component into a fourth tower plate of the rectifying tower for recycling by a pump, wherein the mass ratio of the heavy component to a mixture of 1, 6-hexanediol and 6-hydroxyhexyl acrylate entering the bottom of the rectifying tower is 1: 11; the light component obtained by the short-path evaporator is an acrylic acid-6-hydroxyhexyl ester product, wherein the purity of the acrylic acid-6-hydroxyhexyl ester is 99.4 percent, the yield is 95.1 percent,
carrying out high-resolution mass spectrometry on the prepared 6-hydroxyhexyl acrylate, wherein the mass ratio of HRMS-ESI: m/z: 173.1066([ M + H)] + Calculated values: 173.1102) with a molecular weight consistent with 6-hydroxyhexyl acrylate.
Example 6
The preparation and separation method of 6-hydroxyhexyl acrylate of the embodiment comprises the following steps:
(1) 115kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.42kg of copper N, N-dibutyldithiocarbamate and 1.1kg of methanesulfonic acid were put into a 250L reaction kettle, and the temperature was raised to 108 ℃ by stirring to react for 1 hour, thereby obtaining a reaction solution. Wherein, the reaction liquid mainly comprises the following components in percentage by weight: 47.9 wt% of 1, 6-hexanediol, 41.6 wt% of acrylic acid-6-hydroxyhexyl ester, 5.8 wt% of 1, 6-hexanediol diacrylate, 83.2% of selectivity to acrylic acid-6-hydroxyhexyl ester, and 78.7% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 3; removing 1, 6-hexanediol diacrylate in the reaction liquid by 10-grade continuous countercurrent centrifugal extraction by using cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of a 10-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1:3, the extraction temperature is 25 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 80 ℃ and under the condition of 10kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the plates of the rectifying tower is 29; then feeding a mixture of ionic liquid 1-octyl-3-methylimidazole hexafluorophosphate and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate from a 4 th tower plate of a rectifying tower, wherein the mass ratio of the ionic liquid to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100: 3.5, and the mass ratio of the ionic liquid to the mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 11; rectifying to obtain 1, 6-hexanediol as the top liquid, wherein the rectification conditions of the 1, 6-hexanediol at the top of the tower are 98 ℃ and 0.23kPa (A); pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein the cooling temperature of a built-in condenser of the short-path evaporator is 3 ℃, the operation conditions of the evaporator are 115 ℃ and 0.08kPa (A), and obtaining the 6-hydroxyhexyl acrylate product by distillation, wherein the purity of the 6-hydroxyhexyl acrylate is 84.5 percent, and the yield is 82.4 percent.
Comparative example
The preparation and separation method of 6-hydroxyhexyl acrylate of the comparative example comprises the following steps:
(1) 115kg of 1, 6-hexanediol, 36kg of acrylic acid, 0.42kg of copper N, N-dibutyldithiocarbamate and 1.1kg of methanesulfonic acid were put into a 250L reaction kettle, and the temperature was raised to 108 ℃ by stirring to react for 1 hour, thereby obtaining a reaction solution. Wherein, the reaction solution mainly comprises the following main components in percentage by weight: 47.9 wt% of 1, 6-hexanediol, 41.6 wt% of acrylic acid-6-hydroxyhexyl ester, 5.8 wt% of 1, 6-hexanediol diacrylate, 83.2% of selectivity to acrylic acid-6-hydroxyhexyl ester, and 78.7% of conversion.
(2) Adding water into the reaction liquid obtained in the step (1) to form a water phase A, wherein the mass ratio of the water to the reaction liquid is 1: 3; removing 1, 6-hexanediol diacrylate in the reaction liquid by 10-grade continuous countercurrent centrifugal extraction by using cyclohexane as an extracting agent; in the extraction process, the water phase A enters from a heavy phase inlet of a 10-stage continuous countercurrent centrifugal extraction device, cyclohexane enters from a light phase inlet, the mass flow ratio of the light phase to the heavy phase is 1:3, the extraction temperature is 25 ℃, and the extracted water phase B is obtained after extraction;
(3) removing water from the raffinate water phase B by reduced pressure distillation at 85 ℃ and 14kPa (A) to obtain a mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate obtained in the step (3) from the bottom of a rectifying tower through a pump, wherein the number of the plates of the rectifying tower is 29; then, a mixture of acrylic acid-6-hydroxyhexyl ester with the purity of 99.4 percent and copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is taken as polymerization inhibition spray liquid to be fed from a 4 th tower plate of a rectifying tower, the mass ratio of the acrylic acid-6-hydroxyhexyl ester to the copper salt polymerization inhibitor copper N, N-dibutyl dithiocarbamate is 100:4, and the mass ratio of the acrylic acid-6-hydroxyhexyl ester at the tower top to the mixture containing 1, 6-hexanediol and acrylic acid-6-hydroxyhexyl ester is 1: 11; rectifying to obtain a light component product at the top of the tower, wherein the rectification conditions of the light component at the top of the tower are 98 ℃ and 0.23kPa (A), and the main components comprise 61.2 wt% of 1, 6-hexanediol and 38.1 wt% of acrylic acid-6-hydroxyhexyl ester; pumping the tower bottom liquid into a short-path evaporator by a pump for distillation, wherein the cooling temperature of a built-in condenser of the short-path evaporator is 3 ℃, the operating conditions of the evaporator are 115 ℃ and 0.08kPa (A), and the main components of the light components obtained by the short-path distillation are 58.6 wt% of 1, 6-hexanediol and 40.9 wt% of 6-hydroxyhexyl acrylate, so that the purification of the 6-hydroxyhexyl acrylate cannot be realized.
Compared with the examples 1-6, the comparative example does not use the ionic liquid, normal polymerization inhibition spraying is carried out at the top of the rectifying tower, the volatility of the two components in the mixed system of the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate in the rectifying process is similar, separation cannot be realized, the light component obtained by the final scraper evaporator is a mixture, and the purity of the 6-hydroxyhexyl acrylate is only 40.9%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (20)
1. A preparation and separation method of 6-hydroxyhexyl acrylate is characterized by comprising the following steps:
(1) adding acrylic acid, 1, 6-hexanediol, a copper salt polymerization inhibitor and a catalyst into a reaction container, heating to 105-110 ℃ for reaction to obtain a reaction solution containing acrylic acid-6-hydroxyhexyl ester, 1, 6-hexanediol and 1, 6-hexanediol diacrylate;
(2) adding water into the reaction liquid to form a water phase A, taking aliphatic alkane as an extracting agent, and extracting to separate 1, 6-hexanediol diacrylate in the reaction liquid to obtain a raffinate water phase B;
(3) removing water from the raffinate water phase B through reduced pressure distillation to obtain a mixture containing 1, 6-hexanediol and acrylic acid-6-hydroxyhexyl ester;
(4) feeding the mixture containing the 1, 6-hexanediol and the 6-hydroxyhexyl acrylate in the step (3) from the bottom of a rectifying tower, feeding the mixture of the ionic liquid and the copper salt polymerization inhibitor from a tower plate positioned at the upper part in the rectifying tower, obtaining the 1, 6-hexanediol from the top of the rectifying tower through rectification, and feeding the bottom liquid of the rectifying tower into a short-path evaporator for distillation to obtain the 6-hydroxyhexyl acrylate product;
wherein the ionic liquid is 1-octyl-3-methylimidazole hexafluorophosphate or a mixture of 1-octyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methylimidazole trifluoromethanesulfonate.
2. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 1, wherein in step (1), the temperature is raised to 105-110 ℃ for reaction for 0.5-1.5 h.
3. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 1 wherein in step (2) the extraction is a multi-stage continuous countercurrent centrifugal extraction.
4. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 1, wherein in step (3), the reduced pressure distillation is performed at 80-90 ℃ under 10-20 kPaA.
5. The process for preparing and separating 6-hydroxyhexyl acrylate according to claim 1 wherein in step (4), the mixture of ionic liquid and copper salt polymerization inhibitor is fed from 3 rd to 6 th trays in the rectification column.
6. The method for preparing and separating 6-hydroxyhexyl acrylate according to any of claims 1-5, wherein in step (4), the mass ratio of 1-octyl-3-methylimidazole hexafluorophosphate to 1-hexyl-3-methylimidazole trifluoromethanesulfonate is 2:8 to 6.5: 3.5.
7. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 6, wherein in step (4), the mass ratio of 1-octyl-3-methylimidazole hexafluorophosphate to 1-hexyl-3-methylimidazole trifluoromethanesulfonate is 3:7 to 6.2: 3.8.
8. The method for preparing and separating 6-hydroxyhexyl acrylate according to any one of claims 1-5, wherein in step (4), the mass ratio of the ionic liquid to the copper salt polymerization inhibitor is 100: 1-100: 6;
and/or in the step (4), the mass ratio of the ionic liquid to the mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 8-1: 15.
9. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 8, wherein in step (4), the mass ratio of the ionic liquid to the copper salt polymerization inhibitor is 100: 3-100: 4;
and/or in the step (4), the mass ratio of the ionic liquid to the mixture containing 1, 6-hexanediol and 6-hydroxyhexyl acrylate is 1: 10-1: 12.
10. The method for preparing and separating 6-hydroxyhexyl acrylate according to any of claims 1-5, wherein in step (4), the number of plates of the rectification column is 28-30;
and/or in the rectifying tower, the rectifying conditions of the 1, 6-hexanediol are 95-100 ℃ and 0.2-0.25 kPaA.
11. The process for producing and isolating 6-hydroxyhexyl acrylate according to any of claims 1-5, wherein in step (1) and step (4), the copper salt inhibitor is copper N, N-dibutyldithiocarbamate;
in the step (1), the dosage of the copper salt polymerization inhibitor is 0.5-2 wt% of that of the acrylic acid.
12. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 11, wherein in step (1), the amount of the copper salt polymerization inhibitor is 1 to 1.5wt% of the amount of acrylic acid.
13. The process for producing and isolating 6-hydroxyhexyl acrylate according to any of claims 1-5 wherein in step (1) the catalyst is selected from at least one of p-toluenesulfonic acid, phosphoric acid and methanesulfonic acid; in the step (1), the amount of the catalyst is 0.5-5 wt% of that of the acrylic acid;
and/or in the step (1), the molar ratio of the acrylic acid to the 1, 6-hexanediol is 1: 1.8-1: 2.2;
and/or, in the step (2), the aliphatic alkane is selected from at least one of cyclohexane, normal hexane, normal heptane and normal octane.
14. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 13, wherein in step (1), the amount of the catalyst is 2-3.5 wt% of the amount of acrylic acid;
and/or, in step (1), the molar ratio of the acrylic acid to the 1, 6-hexanediol is 1: 2;
and/or, in the step (2), the aliphatic alkane is selected from cyclohexane.
15. The method for producing and separating 6-hydroxyhexyl acrylate according to any one of claims 1 to 5, wherein in step (2), the mass ratio of the water to the reaction solution is 1:2.5 to 1: 3.5; and/or the presence of a gas in the gas,
in the step (2), the mass ratio of the aliphatic alkane to the water phase A is 1: 2-1: 4.
16. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 15, wherein in step (2), the mass ratio of the water to the reaction solution is 1:2.75 to 1: 3.25; and/or the presence of a gas in the gas,
in the step (2), the mass ratio of the aliphatic alkane to the water phase A is 1: 2.5-1: 3.5.
17. The method for preparing and separating 6-hydroxyhexyl acrylate according to claim 3, wherein the number of theoretical stages N of the multistage continuous countercurrent centrifugal extraction is 9-11.
18. The method for preparing and separating 6-hydroxyhexyl acrylate according to any one of claims 1 to 5, wherein in step (4), the refrigerant in the built-in condenser of the short-path evaporator is 30-60 wt% of ethylene glycol aqueous solution, and the cooling temperature of the built-in condenser of the short-path evaporator is 0-8 ℃;
and/or the operating temperature of the short-path evaporator is 110-120 ℃, and the operating pressure is 0.06-0.1 kPaA.
19. The method for preparing and separating 6-hydroxyhexyl acrylate according to any of claims 1-5, wherein the purity of 6-hydroxyhexyl acrylate in the 6-hydroxyhexyl acrylate product obtained by the short path evaporator distillation is > 99%.
20. The preparation and separation method according to any one of claims 1 to 5, wherein after the distillation in the short-path evaporator, the mixture containing the ionic liquid and the copper salt polymerization inhibitor obtained at the bottom of the tower is recycled to the rectifying tower in the step (4).
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