WO2018209735A1 - 一种丙烯酸酯的低温液相制备方法 - Google Patents

一种丙烯酸酯的低温液相制备方法 Download PDF

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WO2018209735A1
WO2018209735A1 PCT/CN2017/086897 CN2017086897W WO2018209735A1 WO 2018209735 A1 WO2018209735 A1 WO 2018209735A1 CN 2017086897 W CN2017086897 W CN 2017086897W WO 2018209735 A1 WO2018209735 A1 WO 2018209735A1
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acetate
low
acrylate
reactor
reaction
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PCT/CN2017/086897
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French (fr)
Chinese (zh)
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李春山
王刚
李增喜
杨丹
陈洪楠
张锁江
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中国科学院过程工程研究所
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

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  • the invention relates to the technical field of acrylates, and in particular to a method for preparing a low temperature liquid phase of an acrylate.
  • Acrylate is an important organic chemical raw material and commonly used polymerization monomer. It is used in the preparation of coatings, resins and plastics. It is a vinyl monomer with very fast polymerization rate and the simplest unsaturated carboxylic acid ester. Pure acrylate is a colorless, transparent liquid with a pungent odor. Acrylate plays a very important role in the field of fine chemicals. By the late 1970s, copolymers produced with acrylates were often used as flocculants, thickeners, dispersants, and the like.
  • Acrylates can also be copolymerized with other functional monomers such as styrene or acrylonitrile to produce polymers for a variety of industrial applications, such as oilfield auxiliaries, daily chemical detergents, water treatment agents, and superabsorbent resins.
  • Polymer materials synthesized by acrylate have excellent physical and chemical properties such as copolymerization, esterification, miscibility, and functionalization. They can be widely used in pharmaceuticals, coatings, plastics, chemical fiber, leather, building materials, textiles, water treatment, and adhesives. Mixtures and oil exploration and many other fields. At present, China has become one of the world's largest markets for acrylate demand.
  • the conventional preparation of acrylate mainly includes the preparation of acrylic acid and the subsequent esterification process. Since the industrial production of acrylic acid in the 1930s, the process has undergone the cyanide process, the high pressure Repe method, the ketene method, the acrylonitrile hydrolysis method, and the propylene oxidation method. The first four processes have been eliminated due to their technical and economic reasons.
  • the propylene oxidation process was developed in the 1960s and consists mainly of a one-step process and a two-step process. Since the 1980s, acrylic acid has been prepared by a two-step oxidation of propylene. However, with the depletion of petroleum resources and the soaring international oil prices, the production cost of acrylates has also increased significantly.
  • the object of the present invention is to provide a low-temperature liquid phase preparation method of acrylate, which has high yield and good selectivity.
  • a low-temperature liquid phase preparation method of acrylate comprises the steps of: adding acetic acid ester, a formaldehyde source, an organic amine, a solvent and an in-situ catalyst to a reactor according to a ratio, stirring and mixing, and catalyzing in situ After the reaction, an acrylate was prepared.
  • the preparation method of the invention is a low-temperature liquid phase method, and the depolymerization of polyoxymethylene, the activation of formaldehyde, the activation of acetate and the aldol condensation reaction are simultaneously carried out under low temperature liquid phase conditions, the process operation is simple, the reaction conditions are mild, and the cost is low.
  • the preparation method comprises the steps of: adding acetate, formaldehyde source, organic amine, solvent and in-situ catalyst to the reactor according to the ratio, after in situ catalytic reaction Prepare an acrylate.
  • reaction mechanism for preparing acrylate by the low temperature liquid phase method used in the present invention is as follows:
  • the molar ratio of the acetate to the formaldehyde source is 1-3, and the concentration of the formaldehyde source in terms of a monomer (ie, a single formaldehyde molecule) in the solvent is 0.2 to 0.25 mol/L.
  • the molar ratio of the organic amine to the acetate is from 1 to 1.5, and the molar ratio of the in situ catalyst to the acetate is from 1 to 1.5.
  • the molar ratio of the acetate to the formaldehyde source is 1-3, for example, the molar ratio of the acetate to the formaldehyde source is 1:1, 1.5:1, 2:1, 2.5:1. 3:1; the concentration of the formaldehyde source in the solvent is 0.2 mol / L, 0.21 mol / L, 0.22 mol / L, 0.23 mol / L, 0.24 mol / L, 0.25 mol / L; The molar ratio of the organic amine to the acetate is 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1; the molar ratio of the in situ catalyst to the acetate is 1 1: 1.11, 1.2:1, 1.3:1, 1.4:1, 1.5:1.
  • the reactor is a batch reactor; preferably, the batch reactor is replaced by nitrogen.
  • the batch reactor is a batch jacketed stirred tank or a jacketed slurry bed reactor.
  • the stirring speed is 350 to 500r/min, for example, the stirring speed is 350r/min, 360r/min, 370r/min, 380r/min, 390r/min, 400r/min, 410r/min, 420r.
  • reaction temperature of the in-situ catalytic reaction is 10 to 25 ° C,
  • the reaction temperature is 10 ° C, 11 ° C, 12 ° C, 13 ° C, 14 ° C, 15 ° C, 16 ° C, 17 ° C, 18 ° C, 19 ° C, 20 ° C, 21 ° C, 22 ° C, 23 ° C, 24 ° C, 25 °C
  • reaction pressure is 1 atm
  • reaction time is 1.5-3.5h, for example, reaction time is 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h 2.6h, 2.7h, 2.8h, 2.9h, 3h, 3.1h, 3.2h, 3.3h, 3.4h
  • the acetate is selected from one or a mixture of at least two of methyl acetate, ethyl acetate and propyl acetate.
  • the acetate is methyl acetate and the acetate is acetic acid.
  • An ester the acetate being propyl acetate, the acetate being a mixture of methyl acetate and ethyl acetate, the acetate being a mixture of methyl acetate and propyl acetate, the acetate being ethyl acetate and A mixture of propyl acetate, which is a mixture of methyl acetate, ethyl acetate and propyl acetate.
  • the formaldehyde source is selected from one or a mixture of at least two of formaldehyde gas, trioxane, and paraformaldehyde.
  • the formaldehyde source is formaldehyde gas
  • the formaldehyde source is trioxane.
  • the source of formaldehyde is paraformaldehyde
  • the source of formaldehyde is a mixture of formaldehyde gas and paraformaldehyde
  • the source of formaldehyde is a mixture of formaldehyde gas and paraformaldehyde
  • the source of formaldehyde is paraformaldehyde and paraformaldehyde.
  • Polyformaldehyde is a low molecular weight polymer with a polymerization degree n of 8-100. Its product is a white powder or granular solid, insoluble in ethanol, ether and acetone, soluble in dilute alkali and dilute acid, and soluble in 100.
  • paraformaldehyde has the characteristics of storage, transportation and convenient use compared with formaldehyde aqueous solution. It is widely used in the production of automotive high-grade paints and resins. Medicine, etc.
  • the organic amine is selected from the group consisting of diisopropylethylamine and/or triethylamine.
  • the solvent is a polar or weakly polar organic solvent; preferably, the organic solvent is selected from the group consisting of dichloromethane and/or 1,2-dichloroethane.
  • the in-situ catalyst is one or a mixture of at least two of a silicone reagent, an organoboron reagent, and an ammonium trifluoromethanesulfonate ionic liquid;
  • the in situ catalyst is a silicone reagent
  • the in situ catalyst is an organoboron reagent
  • the in situ catalyst is an ammonium trifluoromethanesulfonate ionic liquid
  • the in situ catalyst is a mixture of a silicone reagent and an organoboron reagent
  • the in situ catalyst is a silicone reagent and a mixture of ammonium trifluoromethanesulfonate ionic liquids
  • the in situ catalyst being a mixture of an organoboron reagent and an ammonium fluorosulfonate ionic liquid
  • the in situ catalyst being a silicone reagent, an organoboron reagent, and a trifluorocarbon
  • the organoboron reagent is selected from the group consisting of dibutyl boron triflate, diethyl boron trifluoromethanesulfonate, diphenyl boron trifluoromethanesulfonate or a mixture of at least two; for example
  • the organoboron reagent is dibutylboron trifluoromethanesulfonate, the organoboron reagent is diethyl boron trifluoromethanesulfonate, and the organoboron reagent is diphenylboron trifluoromethanesulfonate.
  • the organic boron reagent is a mixture of dibutylboron trifluoromethanesulfonate and diethyl boron trifluoromethanesulfonate, and the organoboron reagent is dibutylboron trifluoromethanesulfonate and diphenylboron trifluoromethanesulfonate.
  • the organoboron reagent is a mixture of diethyl boron trifluoromethanesulfonate and diphenylboron trifluoromethanesulfonate
  • the organic boron reagent is dibutylboron trifluoromethanesulfonate, trifluoromethanesulfonic acid
  • diethyl boron and diphenyl boron triflate are examples of diethyl boron and diphenyl boron triflate.
  • the silicone reagent is selected from the group consisting of trimethylsilyl triflate and/or silyl tert-butyldimethyltrifluoromethanesulfonate.
  • ammonium trifluoromethanesulfonate ionic liquid is selected from the group consisting of diisopropylethylamine triflate and/or triethylamine triflate.
  • the low-temperature liquid phase preparation method of the acrylate of the present invention comprises the following steps:
  • step 3 The organic amine is added to the mixture of step 2) to prepare a mixture, the molar ratio of the organic amine to the acetate is 1 to 1.5;
  • step 4) adding the mixture of the step 3) to a batch reactor after nitrogen replacement, slowly adding the in-situ catalyst under stirring, the molar ratio of the in-situ catalyst to the acetate is from 1 to 1.5, The stirring speed is 350-500 r/min, the control reaction temperature is 10-25 ° C, the reaction pressure is 1 atm, the reaction time is 1.5-3.5 h, and after the in-situ catalytic reaction, the acrylate is prepared.
  • the low-temperature liquid phase preparation method of the acrylate of the present invention has a high yield of acrylate, and the yield is 51.3% or more and up to 90.7%.
  • the low-temperature liquid phase preparation method of the acrylate of the present invention has high selectivity for preparing acrylate, and the selectivity is 58.6% or more, and the highest is 94.4%.
  • the invention adopts low-temperature liquid phase method to prepare acrylate, the operation process is simple, the condition is mild, the reaction temperature is low, and the temperature can be completed under the condition of 10-25 ° C, and the depolymerization of polyoxymethylene is realized under the condition of low temperature liquid phase.
  • the activation of formaldehyde, the activation of acetate and the aldol condensation reaction are carried out simultaneously, and the cost and energy consumption are low, which is advantageous for industrial applications.
  • FIG. 1 is a schematic view showing the process of a low-temperature liquid phase preparation method of an acrylate according to the present invention
  • the present invention has carried out a series of experiments by changing the reaction conditions and the reaction raw materials while keeping the low-temperature liquid phase process unchanged, and the specific implementation is as follows.
  • the yield and selectivity of the acrylate were determined by GC-MS analysis using a HP-5 capillary column and cyclohexane as an internal standard.
  • the acrylic acid of the present invention was used.
  • the process of the low temperature liquid phase preparation method of the ester is as follows: first, the nitrogen inlet 5 and the exhaust port 7 of the reactor are opened, and the air in the reactor is replaced with nitrogen.
  • Preparation of methyl acrylate by methyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to methyl acetate, diisopropylethylamine and dibutylboron trifluoride is 1:3:3:3, formaldehyde ( The concentration of the monomer in the dichloromethane is 0.21 mol/L, and the prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled to 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 350 r/min. , The reaction time was 2 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of methyl acrylate were 90.7% and 91.8%.
  • Methyl acrylate and formaldehyde were used to prepare methyl acrylate: first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to methyl acetate, diisopropylethylamine and dibutylboron trifluoride is 1:2:3:3, formaldehyde ( The concentration of the monomer in the dichloromethane is 0.23 mol/L, and the prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 15 ° C, the reaction pressure is 1 atm, and the stirring speed is 400 r/min. The reaction time was 1.5 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of methyl acrylate were 86.4% and 92.5%.
  • Methyl acrylate and paraformaldehyde were used to prepare methyl acrylate: first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then, using 1,2-dichloroethane as a solvent, the molar ratio of formaldehyde (by monomer) to methyl acetate, diisopropylethylamine and dibutylboron trifluoride is 1:3:3: 3, the concentration of formaldehyde (in terms of monomer) in 1,2-dichloroethane is 0.22 mol / L, the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 25 ° C, the reaction The pressure was 1 atm, the stirring speed was 430 r/min, and the reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of methyl acrylate were 73.4% and 90.2%.
  • Preparation of ethyl acrylate by ethyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to ethyl acetate, diisopropylethylamine and dibutylboron trifluoride is 1:3:3:3, formaldehyde ( The concentration of the monomer in the dichloromethane is 0.21 mol/L, and the above prepared solution is injected through the material.
  • the reaction temperature is controlled at 20 ° C
  • the reaction pressure is 1 atm
  • the stirring speed is 410r / min
  • the reaction time is 2h
  • the material is taken out through the material discharge port
  • the yield and selectivity of ethyl acrylate are 85.6% and 86.9%.
  • Isobutyl acrylate was prepared from isobutyl acetate and paraformaldehyde: first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to isobutyl acetate, diisopropylethylamine and dibutylboron trifluoride is 1:3:3:3, formaldehyde ( The concentration of the monomer in dichloromethane was 0.21 mol/L, and the above prepared solution was injected into the reactor through the material inlet to control the reaction temperature to 20 ° C, the reaction pressure was 1 atm, and the stirring speed was 460 r / Min, the reaction time was 2 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of isobutyl acrylate were 81.8% and 83.2%.
  • the concentration of formaldehyde (in terms of monomer) in dichloromethane is 0.21 mol/L, and the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 16 ° C, the reaction pressure is 1 atm, and the stirring speed is 470r/min, the reaction time was 2h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of cyclohexyl acrylate were 76.4% and 78.7%.
  • methyl acrylate by methyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to methyl acetate, diisopropylethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, formaldehyde
  • the concentration (in terms of monomer) in dichloromethane is 0.24 mol/L, and the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 480 r. /min, the reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of methyl acrylate were 80.8% and 94.4%.
  • Preparation of methyl acrylate by methyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to methyl acetate, triethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, formaldehyde (in single The concentration in the dichloromethane is 0.24 mol/L, and the prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 480 r/min. The reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of methyl acrylate were 72.9% and 90.5%.
  • Preparation of methyl acrylate by methyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then use 1,2-dichloroethane as solvent, formaldehyde (in monomer The molar ratio of methyl acetate, triethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, and formaldehyde (in terms of monomers) is in 1,2-dichloroethane.
  • the concentration of the solution is 0.23mol / L
  • the above prepared solution is injected into the reactor through the material inlet
  • the reaction temperature is controlled at 22 ° C
  • the reaction pressure is 1 atm
  • the stirring speed is 490r / min
  • the reaction time is 3h
  • after the reaction is over The material was taken out through the material discharge port, and the yield and selectivity of methyl acrylate were 68.1% and 81.6%.
  • Preparation of ethyl acrylate by ethyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to ethyl acetate, diisopropylethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, formaldehyde
  • the concentration (in terms of monomer) in dichloromethane is 0.22 mol/L, and the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 370 r. /min, the reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of ethyl acrylate were 68.1% and 81.6%
  • Preparation of ethyl acrylate by ethyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then, using 1,2 dichloroethane as a solvent, the molar ratio of formaldehyde (by monomer) to ethyl acetate, triethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5.
  • the concentration of formaldehyde (in terms of monomer) in 1,2 dichloroethane is 0.24 mol/L, and the above prepared solution is injected into the reactor through the material inlet to control the reaction temperature to 20 ° C, and the reaction pressure is 1 atm.
  • the stirring speed was 380 r/min, and the reaction time was 3 h. After the reaction, the materials were taken out through the material discharge port, and the yield and selectivity of ethyl acrylate were 65.5% and 75.9%.
  • Preparation of ethyl acrylate by ethyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor At the port, the air in the reactor was replaced with nitrogen. Then, using 1,2 dichloroethane as a solvent, the molar ratio of formaldehyde (by monomer) to ethyl acetate, diisopropylethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5.
  • the concentration of formaldehyde (in terms of monomer) in 1,2 dichloroethane is 0.24 mol / L
  • the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction The pressure was 1 atm, the stirring speed was 390 r/min, and the reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of ethyl acrylate were 66.5% and 79.2%.
  • the concentration of formaldehyde (in terms of monomer) in 1,2 dichloroethane is 0.24 mol / L
  • the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction The pressure was 1 atm, the stirring speed was 410 r/min, and the reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of butyl acrylate were 51.8% and 60.6%.
  • Isobutyl acrylate was prepared from isobutyl acetate and paraformaldehyde: first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to butyl acetate, diisopropylethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, formaldehyde
  • the concentration of the monomer (in terms of monomer) in dichloromethane is 0.24 mol/L, and the above prepared solution is injected into the reactor through the material inlet to control the reaction temperature to 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 430 rpm. /min, the reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of isobutyl acrylate were 56.9% and 66.
  • Isobutyl acrylate was prepared from isobutyl acetate and paraformaldehyde: first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then, using 1,2 dichloroethane as a solvent, the molar ratio of formaldehyde (by monomer) to butyl acetate, diisopropylethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5.
  • the concentration of formaldehyde (in terms of monomer) in 1,2 dichloroethane is 0.24 mol / L
  • the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction The pressure was 1 atm, the stirring speed was 430 r/min, and the reaction time was 3 h. After the reaction, the materials were taken out through the material discharge port, and the yield and selectivity of isobutyl acrylate were 50.1% and 58.6%.
  • Isobutyl acrylate was prepared from isobutyl acetate and paraformaldehyde: first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using methylene chloride as a solvent, the molar ratio of formaldehyde (by monomer) to butyl acetate, triethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, formaldehyde (in single The concentration of the solution in the dichloromethane is 0.24 mol / L, the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 450 r / min. The reaction time was 3 h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of isobutyl acrylate were 52.4% and 61.4%.
  • cyclohexyl acrylate by cyclohexyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then, using dichloromethane as a solvent, the molar ratio of formaldehyde (by monomer) to cyclohexyl acetate, diisopropylethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5.
  • the concentration of formaldehyde (in terms of monomer) in dichloromethane is 0.24 mol/L, and the above prepared solution is injected into the reactor through the material inlet, the reaction temperature is controlled at 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 460r/min, the reaction time was 3h. After the reaction, the material was taken out through the material discharge port, and the yield and selectivity of cyclohexyl acrylate were 54.2% and 63.2%.
  • Preparation of cyclohexyl acrylate by cyclohexyl acetate and paraformaldehyde first open the nitrogen inlet and outlet of the reactor, and replace the air in the reactor with nitrogen. Then using methylene chloride as a solvent, the molar ratio of formaldehyde (by monomer) to cyclohexyl acetate, triethylamine and trimethylsilyl trifluoromethanesulfonate is 1:3:4.5:4.5, formaldehyde ( The concentration of the monomer in dichloromethane is 0.24 mol/L, and the prepared solution is injected into the reactor through the material inlet to control the reaction temperature to 20 ° C, the reaction pressure is 1 atm, and the stirring speed is 460 r / min. , the reaction time is 3h, after the reaction is completed, the material is taken out through the material discharge port, cyclohexyl acrylate The yield and selectivity were 51.3% and 60.3%.
  • the catalyst is ⁇ -Al 2 O 3 supported C S -WP salt and its oxide, C S content is 10%, W content is 1%, P content
  • the ⁇ -Al 2 O 3 carrier has a particle diameter of 0.4 to 0.9 mm.
  • the reaction temperature was 350 ° C
  • the molar ratio of methyl acetate:formaldehyde was 5:1
  • the space velocity was 1 h -1
  • the pressure was 0.1 MPa at normal pressure
  • the yield of methyl acrylate was 30.0%
  • the selectivity was 90.8%.
  • the catalyst is ⁇ -Al 2 O 3 supported C S -WP salt and its oxide, C S content is 10%, W content is 1%, P The content is 5%, and the particle size of the ⁇ -Al 2 O 3 carrier is 125-150 ⁇ m.
  • the mixing chamber preheat temperature was 220 deg.] C, the reaction temperature is 350 deg.] C, methyl acetate: formaldehyde ratio is 5:1, nitrogen as carrier gas, a space velocity of 1h -1, atmospheric pressure was 0.1MPa, the wear rate of the catalyst It was 0.3%; the yield of methyl acrylate was 31.7%, and the selectivity was 93.1%.
  • the new method for preparing acrylate by the low-temperature liquid phase method of the present application has a significantly lower reaction temperature, milder conditions and simple operation than the high-temperature gas-phase fixed bed and fluidized bed processes. And the yield of the product acrylate is significantly improved.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

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PCT/CN2017/086897 2017-05-19 2017-06-01 一种丙烯酸酯的低温液相制备方法 WO2018209735A1 (zh)

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