CN107597187B - Method for continuously producing (methyl) acrylic acid hydroxy ester and (methyl) acrylic acid diester and sulfonic acid resin catalyst - Google Patents
Method for continuously producing (methyl) acrylic acid hydroxy ester and (methyl) acrylic acid diester and sulfonic acid resin catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of compound synthesis methods, and provides a sulfonic acid resin catalyst and a method for continuously producing (methyl) acrylic acid hydroxy ester and (methyl) acrylic acid diester. The continuous production method comprises the following steps: (1) contacting dihydric alcohol, methyl (meth) acrylate and a polymerization inhibitor to form a reaction liquid, and continuously pumping the reaction liquid into a reaction device filled with a sulfonic acid resin catalyst for reaction to obtain a crude reaction liquid; (2) pumping the crude reaction liquid in the step (1) into a phase separation tank, and extracting by using a double solvent to respectively obtain a water phase containing (methyl) acrylic acid monoester and an oil phase containing (methyl) acrylic acid diester; (3) and (3) respectively rectifying the water phase and the oil phase in the step (2) to obtain a (methyl) acrylic acid hydroxyl ester product and a (methyl) acrylic acid diester product. The method simplifies product separation steps, and has low separation temperature and high product purity.
Description
Technical Field
The invention belongs to the technical field of compound synthesis methods, and particularly relates to a method for continuously producing (methyl) acrylic acid hydroxy ester and (methyl) acrylic acid diester and a preparation method of a sulfonic acid resin catalyst.
Background
Hydroxy (meth) acrylate is an important acrylate monomer, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate can be prepared by ring opening of (meth) acrylic acid with ethylene oxide and propylene oxide, but hydroxy (meth) acrylates having higher carbon numbers are often prepared by transesterification and esterification.
German patent document No. 1518572 discloses a process for producing 4-hydroxybutyl acrylate by the dehydration esterification of 1, 4-butanediol with acrylic acid, which uses sulfuric acid and p-toluenesulfonic acid as catalysts, resulting in a large amount of side reaction products, and which uses acids as catalysts, thus requiring a complicated neutralization step and simultaneously producing a large amount of waste water by neutralization.
Patent document CN 104220413 a discloses a preparation method of 4-hydroxybutyl acrylate, which uses acrylate and 1, 4-butanediol as raw materials, and in order to effectively convert the product into 4-hydroxybutyl acrylate, the scheme employs a low concentration catalyst and a lower reaction temperature; the method has the advantages of low conversion rate of 1 and 4 butanediol, increased separation difficulty in the later period, prolonged reaction time and reduced reaction efficiency. In addition, the homogeneous catalyst used in this patent increases the difficulty of catalyst recovery.
The diester (meth) acrylates are an important crosslinking agent and are conventionally prepared by transesterification and esterification. Patent document CN106518664A discloses a method for preparing polyethylene glycol 400 diacrylate, which uses acrylic acid and polyethylene glycol 400 as raw materials, and adds 8% NaCl solution and 0.8% Na solution into the mixture obtained after the reaction2CO3The solution is washed with water, thereby producing a largeAmount of spent brine. Patent document CN 102030641 a discloses a method for preparing 1, 4-butanediol dimethacrylate, and the catalyst used is an organic tin catalyst. Patent document CN 103755565A discloses a preparation method of neopentyl glycol dimethacrylate, which uses high concentration of nitroxide free radical to prevent product polymerization, and since the polymerization inhibitor is difficult to separate from the product, the product color number is high, which affects downstream use.
Thus, there is a need in the art for a simple and efficient preparation scheme for hydroxy (meth) acrylates and diesters of (meth) acrylic acid.
Disclosure of Invention
The invention aims to provide a sulfonic acid resin catalyst and a method for continuously producing (methyl) acrylic acid hydroxyl ester and (methyl) acrylic acid diester, aiming at a series of problems in the process of preparing (methyl) acrylic acid hydroxyl ester and (methyl) acrylic acid diester in the prior art; the continuous production method can simplify the product separation steps, and has low separation temperature and high product purity.
In order to achieve the above object, the present invention provides a sulfonic acid resin catalyst, which is prepared by polymerization of the following raw materials:
(1) an aryl-substituted ethylenic monomer,
(2) (meth) acrylic acid esters having a cycloalkane structure,
(3) a fluorosilicone containing a double bond.
According to the sulfonic acid resin catalyst provided by the invention, preferably, the aryl substituted vinyl monomer is selected from phenyl substituted vinyl monomers, and more preferably selected from styrene and/or stilbene.
Preferably, the double bond-containing fluorosilicone is selected from vinyltris- (trifluoro) methoxysilane and/or vinyltris (2,2, 2-trifluoro) ethoxysilane.
Preferably, the (meth) acrylate having a cycloalkane structure is selected from one or more of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate and cyclohexyl acrylate.
According to the sulfonic acid resin catalyst provided by the invention, preferably, the molar ratio of the aryl-substituted alkene monomer to the double-bond-containing fluorosilicone is 0.2-1: 1, preferably 0.4 to 0.8: 1, more preferably 0.5 to 0.7: 1. the molar ratio of the (methyl) acrylate with the cycloparaffin structure to the fluorosilicone containing double bonds is 0.2-5: 1, preferably 1 to 3: 1, more preferably 1.5 to 2.5: 1.
in a preferred embodiment of the present invention, the polymerization reaction system for preparing the sulfonic acid resin catalyst further comprises an auxiliary agent, the auxiliary agent comprising:
(4) a cross-linking agent which is a cross-linking agent,
(5) a pore-forming agent, a surfactant and a surfactant,
(6) and (3) an initiator.
Preferably, the crosslinking agent is selected from one or more of 1, 3-propanediol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 3-propanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 5-pentanediol dimethacrylate, and 1, 6-hexanediol dimethacrylate.
Preferably, the porogen is selected from C10-C40More preferably selected from C10-C30Further preferably one or more selected from decane, n-undecane, n-eicosane, n-pentadecane and n-pentacosane.
Preferably, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, ammonium persulfate and potassium persulfate.
According to the sulfonic acid resin catalyst provided by the invention, preferably, the molar ratio of the cross-linking agent to the double-bond-containing fluorosilicone is 0.05-0.5: 1, more preferably 0.1 to 0.4: 1, more preferably 0.2 to 0.35: 1. the molar ratio of the pore-foaming agent to the double-bond-containing fluorosilicone is 0.2-2.0: 1, more preferably 0.5 to 1:1, more preferably 0.6 to 0.9: 1. the molar ratio of the initiator to the double-bond-containing fluorosilicone is 0.005-0.02: 1, more preferably 0.012 to 0.018:1, and still more preferably 0.014 to 0.016: 1.
In a preferred embodiment of the present invention, the sulfonic acid resin catalyst is prepared by a method comprising the steps of:
(a) contacting an aryl-substituted alkene monomer, double-bond-containing fluorosilicone, (methyl) acrylate with a cycloparaffin structure, a cross-linking agent, a pore-forming agent and an initiator to perform polymerization reaction to prepare polymer microspheres;
(b) swelling the prepared polymer microspheres, and then performing sulfonation reaction to prepare the sulfonic acid resin catalyst.
Preferably, in step (a), the polymerization reaction is carried out by a suspension polymerization process; the polymerization temperature is 65-100 ℃, and preferably 70-95 ℃; the polymerization time is 2-6h, preferably 3-5 h.
Preferably, in step (b), the swelling is carried out in a solvent; preferably, the solvent is selected from one or more of methanol, ethanol, diethyl ether, acetone, n-hexane and cyclohexane.
Preferably, the swelling time is from 3 to 6h, more preferably from 4 to 6 h.
According to the sulfonic acid resin catalyst provided by the present invention, preferably, in the step (b), the sulfonation reaction uses a sulfonation reagent selected from one or more of concentrated sulfuric acid, sulfur trioxide, sodium sulfite and chlorosulfonic acid.
Preferably, in step (b), the molar ratio of the sulfonating agent to the aryl-substituted alkene monomer is 1: (0.5-5), more preferably 1: (1-4), more preferably 1: (2-3).
According to the sulfonic acid resin catalyst provided by the invention, preferably, in the step (b), the temperature of the sulfonation reaction is 40-100 ℃, more preferably 50-80 ℃; the sulfonation reaction time is 5-10h, more preferably 6-8 h.
The surface energy of the sulfonic acid resin catalyst obtained by the invention is lower than that of the common resin as can be seen by GB-T1720-79(89) paint film adhesion measurement method and sessile drop method contact angle measurement method.
The present invention also provides a method for continuously producing a hydroxy (meth) acrylate and a diester (meth) acrylate, the method comprising the steps of:
(1) the dihydric alcohol, the methyl (meth) acrylate and the polymerization inhibitor are contacted to form a reaction liquid, and the reaction liquid is continuously injected into a reaction device filled with the sulfonic acid resin catalyst for reaction to obtain a crude reaction liquid;
(2) extracting the crude reaction liquid in the step (1) to respectively obtain a water phase containing (methyl) acrylic acid monoester and an oil phase containing (methyl) acrylic acid diester;
(3) and (3) respectively rectifying the water phase and the oil phase in the step (2) to obtain a (methyl) acrylic acid hydroxyl ester product and a (methyl) acrylic acid diester product.
According to the method provided by the invention, preferably, in the step (1), the dihydric alcohol is selected from C2～C10More preferably selected from C4～C8The linear aliphatic diol of (2) is more preferably selected from 1, 4-butanediol and/or 1, 6-hexanediol.
Preferably, in step (1), the polymerization inhibitor is selected from phenolic polymerization inhibitors, more preferably from substituted or unsubstituted phenols, and further preferably p-methylphenol.
In the present invention, the reaction apparatus used in step (1) may be a series of reactors, separators, buffers, flash evaporation apparatuses, and lines connecting these apparatuses, pumps for transferring materials, etc., which are well known to those skilled in the art. Preferably, the reaction apparatus comprises: the device comprises a first-stage reaction unit, a second-stage reaction unit and a third-stage reaction unit; the system comprises a first-stage reaction unit, a second-stage reaction unit, a third-stage reaction unit, a first-stage fixed bed reactor, a second-stage fixed bed reactor, a third-stage flash tank and a fourth-stage fixed bed reactor, wherein the first-stage fixed bed reactor in the first-stage reaction unit is connected with the first-stage flash tank, the second-stage fixed bed reactor in the second-stage reaction unit is connected with the second;
the storage tank filled with the methyl (meth) acrylate is connected with the first-stage fixed bed reactor, the second-stage fixed bed reactor and the third-stage fixed bed reactor, respectively, and the storage tank filled with the dihydric alcohol is connected with the first-stage fixed bed reactor.
In one embodiment of the present invention, as shown in fig. 1, the flow direction of the material in each apparatus is: the glycol material flow in the glycol storage tank and the methyl (meth) acrylate material flow in the (meth) acrylate storage tank are converged and enter a first-stage fixed bed reactor in a first-stage reaction unit, and the product flow after the reaction enters a first-stage flash tank; feeding the bottom material flow of the first-stage flash tank into a second-stage fixed bed reactor of a second-stage reaction unit, supplementing the methyl (meth) acrylate material flow in a (meth) acrylate storage tank into the second-stage fixed bed reactor, and feeding the product flow after reaction into a second-stage flash tank; and (3) feeding the bottom material flow of the second-stage flash tank into a third-stage fixed bed reactor of a third-stage reaction unit, supplementing the methyl (meth) acrylate material flow in a (meth) acrylate storage tank into the third-stage fixed bed reactor, and feeding the product flow after reaction into the third-stage flash tank. In the invention, the requirement can be met by using a three-stage reaction device.
More preferably, the reaction temperature of the first-stage fixed bed reactor is 80-100 ℃, and the residence time of the reaction liquid is 1-2 h; the temperature of the first-stage flash tank is 40-60 ℃, and the pressure is 10-25 KPa.
The reaction temperature of the second-stage fixed bed reactor is 100-120 ℃, and the residence time of the reaction liquid is 0.5-1 h; the temperature of the second-stage flash tank is 40-60 ℃, and the pressure is 10-25 KPa.
The reaction temperature of the third-stage fixed bed reactor is 110-; the temperature of the third-stage flash tank is 80-100 ℃, and the pressure is 10-25 KPa.
In the present invention, glycol and methyl (meth) acrylate are mixed and continuously fed into the first-stage reactor, and since methyl (meth) acrylate is lost in the process of removing by-produced methanol in the flash tank, methyl (meth) acrylate must be added to the inlets of the second-stage and third-stage fixed bed reactors.
More preferably, the molar ratio of the dihydric alcohol and the methyl (meth) acrylate entering the first-stage fixed bed reactor in the step (1) is 1:4 to 1: 12.
The molar ratio of the methyl (meth) acrylate fed into the second-stage fixed bed reactor to the methyl (meth) acrylate fed into the first-stage fixed bed reactor in the step (1) is 1: 1-1: 4.
The molar ratio of the methyl (meth) acrylate fed into the third-stage fixed bed reactor to the methyl (meth) acrylate fed into the first-stage fixed bed reactor in the step (1) is 1: 1-1: 2.
According to the method provided by the invention, the amount of the polymerization inhibitor is preferably 0.005-0.02 wt% of the amount of the methyl (meth) acrylate.
According to the method provided by the invention, preferably, in the step (2), the extraction is carried out by using a double solvent;
more preferably, the bi-solvent is water and an aromatic compound.
More preferably, the aromatic hydrocarbon compound is selected from one or more of benzene, toluene and xylene; toluene is most preferred.
More preferably, the mass ratio of water to the aromatic hydrocarbon compound in the double solvent is 1:5 to 5: 1.
More preferably, the mass ratio of the double solvent to the crude reaction solution is 1:5 to 5: 1.
In a preferred embodiment of the present invention, in step (3), the rectification is vacuum rectification;
preferably, the pressure of the top of the rectifying tower adopted by the water phase is 3-10KPa, and the temperature is 25-45 ℃; the pressure of the tower kettle is 4-11KPa, and the temperature is 40-65 ℃.
Preferably, the pressure of the top of a rectifying tower adopted by the oil phase is 5-12KPa, and the temperature is 30-50 ℃; the pressure of the tower kettle is 6-13KPa, and the temperature is 50-70 ℃.
In the present invention, the purpose of the selective vacuum distillation is: the boiling point of each component in the mixed phase can be reduced, and the polymerization of substances which are easy to polymerize at high temperature is avoided, so that the separation purpose is achieved; in addition, the steam consumption can be reduced, and the heat source is easy to realize.
In the process for continuously producing a hydroxy (meth) acrylate and a diester (meth) acrylate according to the present invention, the reaction apparatuses involved in the steps (2) and (3) are conventional in the art.
The pressure in the invention is absolute pressure.
The technical scheme of the invention has the following beneficial effects:
(1) two monomers of (methyl) acrylic acid hydroxyl ester and (methyl) acrylic acid diester can be effectively produced, and the (methyl) acrylic acid hydroxyl ester and (methyl) acrylic acid diester monomers with different proportions can be obtained by adjusting reaction parameters;
(2) the reaction equipment is continuous production equipment, so that on one hand, the production efficiency can be improved, the batch stability of a continuously reacted product is good, and the labor operation intensity is reduced; on the other hand, the separation problem of the catalyst and the polymerization inhibitor is not considered, so that the product separation step is simplified;
(3) on one hand, the prepared sulfonic acid resin catalyst has a cycloparaffin structure, so that the heat resistance of the sulfonic acid resin catalyst is improved, and the activity of the sulfonic acid resin catalyst is reduced little after the sulfonic acid resin catalyst is used for a long time at a high temperature; on the other hand, the surface energy of the fluoroethylene siloxane structure in the catalyst is reduced, so that the oligomer adhesion resistance of the catalyst is improved; the long-term continuous and stable operation of the process is ensured;
(4) the method has the advantages of simple steps, low cost, small pollution and great social and economic benefits.
Drawings
FIG. 1 is a schematic view of the reaction apparatus in the step (1) in the process for continuously producing a hydroxy (meth) acrylate and a diester (meth) acrylate of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below by way of examples. While the examples describe preferred embodiments of the invention, it should be understood that the invention can be embodied in various forms and should not be construed as limited to the embodiments set forth herein.
1. The raw material sources are as follows:
styrene, zilu petrochemical;
cyclohexyl (meth) acrylate, basf;
isobornyl (meth) acrylate, acolite;
1, 6-hexanediol diacrylate, sartomer;
n-undecane, wakay;
azobisisobutyronitrile, alatin;
1, 4-butanediol diacrylate, sartomer;
n-eicosane, alatin;
benzoyl peroxide, alatin;
vinyl tri- (trifluoro) methoxylsilane, self-made, referred to as chemical new material Vol42. No2105-107;
vinyl tri (2,2, 2-trifluoro) ethoxysilane, which is made by self and refers to a novel chemical material Vol42 No 2105-107;
butanediol, Xinjiang meike;
methyl methacrylate, alatin;
p-methylphenol, alatin;
hexanediol, basf;
xylene, chemical industry of west longu;
benzene, chemical industry of west longu.
2. Product Performance testing of sulfonic acid resin catalysts
The surface energy of the paint film is detected by a paint film adhesion measuring method and a sessile drop method contact angle measuring method of GB-T1720-79 (89).
Preparation of sulfonic acid resin catalyst:
preparation example 1:
(a) styrene, vinyl tri- (trifluoro) methoxysilane, cyclohexyl (meth) acrylate, 1, 6-hexanediol diacrylate, n-undecane and azobisisobutyronitrile in a molar ratio of 0.5: 1.5: 1: 0.2: 0.6: 0.014, carrying out feeding, and reacting for 5h at 70 ℃ by using suspension polymerization to prepare the low surface energy polymer microspheres;
(b) swelling the prepared polymer microspheres in methanol for 4h, and then adding sulfuric acid, wherein the molar ratio of the polymer microspheres to the sulfuric acid is 1:2, sulfonating at 50 ℃ for 8h, filtering, and washing with water to obtain the No. 1 sulfonic acid resin catalyst.
The sulfonic acid resin catalyst obtained by GB-T1720-79(89) paint film adhesion measuring method and sessile drop method contact angle measuring method is detected, the adhesion reaches 2 grade, and the contact angle reaches 103 degrees.
Preparation example 2:
(a) styrene, vinyl tri (2,2, 2-trifluoro) ethoxysilane, isobornyl (meth) acrylate, 1, 4-propylene glycol diacrylate, n-eicosane and benzoyl peroxide are mixed according to a molar ratio of 0.7: 2.5: 1: 0.35: 0.9: 0.016, and reacting for 3h at 95 ℃ by using suspension polymerization to prepare the low surface energy polymer microspheres;
(b) swelling the prepared polymer microsphere in n-hexane for 4h, and then adding sulfur trioxide, wherein the molar ratio of the polymer microsphere to the sulfur trioxide is 1: 3, sulfonating at 80 ℃ for 6 hours, filtering, and washing with water to obtain the 2# sulfonic acid resin catalyst.
The sulfonic acid resin catalyst obtained by GB-T1720-79(89) paint film adhesion measuring method and sessile drop method contact angle measuring method is used for detecting, the adhesion reaches 2 grades, and the contact angle reaches 110 degrees.
Preparation example 3:
(a) styrene, 1, 4-propylene glycol diacrylate, n-eicosane and benzoyl peroxide are mixed according to a molar ratio of 0.7: 0.35: 0.9: 0.016, and reacting for 3h at 95 ℃ by using suspension polymerization to prepare the low surface energy polymer microspheres;
(b) swelling the prepared polymer microsphere in n-hexane for 4h, and then adding sulfur trioxide, wherein the molar ratio of the polymer microsphere to the sulfur trioxide is 1: 3, sulfonating at 80 ℃ for 6 hours, filtering, and washing with water to obtain the 3# sulfonic acid resin catalyst.
The sulfonic acid resin catalyst obtained by GB-T1720-79(89) paint film adhesion measuring method and sessile drop method contact angle measuring method is used for detecting, the adhesion reaches 4 grades, and the contact angle reaches 82 degrees.
The performance test results of the sulfonic acid resin catalysts obtained in the three preparation examples show that the sulfonic acid resin catalysts obtained in the preparation examples 1 and 2 added with the fluorosilicone containing double bonds have low adhesive force level and large contact angle, which indicates that the surface energy of the catalysts is low; the sulfonic acid resin catalyst obtained in preparation example 3, in which no double bond-containing fluorosilicone was added, had a high adhesion level and a small contact angle, indicating that its surface energy was high.
Example 1:
(1) and preparing a reaction solution, wherein the catalyst in the fixed bed is a 1# sulfonic acid resin catalyst. Wherein, the molar ratio of the 1, 4-butanediol to the methyl methacrylate is 1:4, the polymerization inhibitor is p-methyl phenol, and the addition amount is 0.02 wt% of the methyl methacrylate. As shown in FIG. 1, at a space velocity of 1h-1Feeding the reaction solution into a first-stage fixed bed reactor, wherein the reaction temperature is 100 ℃, and then feeding the reaction solution into a first-stage flash tank, wherein the operating temperature of the flash tank is 60 ℃, and the pressure is 25 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl methacrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl methacrylate to the methyl methacrylate entering a first-stage fixed bed reactor is 1:1), the reaction liquid enters a second-stage fixed bed reactor, and the airspeed is 1h-1The reaction temperature is 120 ℃, and then the reaction liquid enters a second-stage flash tank, the operating temperature of the flash tank is 60 ℃, and the pressure is 25 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl methacrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl methacrylate to the methyl methacrylate entering the first-stage fixed bed reactor is 1:1), the reaction liquid enters a third-stage fixed bed reactor, and the airspeed is 4h-1And the reaction temperature is 130 ℃, and then the reaction liquid enters a third-stage flash tank, the operation temperature of the flash tank is 100 ℃, and the pressure is 25Kpa, so that crude reaction liquid is obtained.
The composition of the crude reaction solution, as measured in the gas phase, was as follows: 0.9 wt% of 1, 4-butanediol, 0.5 wt% of methyl methacrylate, 54.5 wt% of hydroxybutyl methacrylate and 44.1 wt% of 1, 4-butanediol dimethacrylate. The catalyst can stably run for 800 hours, and the activity of the catalyst is only reduced by 1.2 percent
(2) Continuously introducing the crude reaction liquid into a phase splitting tank, and respectively adding water and toluene into the phase splitting tank; wherein the mass ratio of water to toluene to the reaction solution is 1:5:1, and a water phase and an organic phase are obtained by extraction.
The aqueous phase had the following composition: 1.3 percent of 1, 4-butanediol, 0.1 percent of methyl methacrylate, 98.1 percent of hydroxybutyl methacrylate and 0.5 percent of 1, 4-butanediol dimethacrylate;
the organic phase composition was as follows: 0.3 wt% of 1, 4-butanediol, 0.8 wt% of methyl methacrylate, 1.3 wt% of hydroxybutyl methacrylate and 97.6 wt% of 1, 4-butanediol dimethacrylate.
(3) Introducing the water phase into a water phase rectifying tower, wherein the tower top pressure of the water phase rectifying tower is 10KPa, and the temperature is 45 ℃; the pressure of the tower kettle is 11KPa, and the temperature is 65 ℃; the obtained product of the hydroxybutyl methacrylate at the bottom of the tower consists of: 1.2 wt% of 1, 4-butanediol, 98.2 wt% of hydroxybutyl methacrylate and 0.6 wt% of 1, 4-butanediol dimethacrylate;
introducing an organic phase into an organic phase rectifying tower, wherein the tower top pressure of the organic phase rectifying tower is 5KPa, and the temperature is 30 ℃; the pressure of the tower kettle is 6KPa, and the temperature is 50 ℃; the obtained 1, 4-butanediol dimethacrylate product at the tower bottom comprises the following components: 0.4 wt% of 1, 4-butanediol, 1.4 wt% of hydroxybutyl methacrylate and 98.2 wt% of 1, 4-butanediol dimethacrylate.
Example 2:
(1) and preparing a reaction solution, wherein the catalyst in the fixed bed is a 1# sulfonic acid resin catalyst. Wherein, the molar ratio of the 1, 4-butanediol to the methyl acrylate is 1:8, the polymerization inhibitor is p-methyl phenol, and the addition amount is 0.01 wt% of the methyl methacrylate. As shown in FIG. 1, at a space velocity of 0.7h-1Feeding the reaction solution into a first-stage fixed bed reactor, wherein the reaction temperature is 90 ℃, and then feeding the reaction solution into a first-stage flash tank, wherein the operating temperature of the flash tank is 50 ℃, and the pressure is 20 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl acrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl acrylate to the methyl acrylate entering the first-stage fixed bed reactor is 1:2), the reaction liquid enters a second-stage fixed bed reactor, and the airspeed is 1.5h-1The reaction temperature is 110 ℃, and then the reaction liquid enters a second-stage flash tank, the operating temperature of the flash tank is 50 ℃, and the pressure is 20 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl acrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl acrylate to the methyl acrylate entering the first-stage fixed bed reactor is 1:2), the reaction liquid enters a third-stage fixed bed reactor, and the space velocity is 2h-1And the reaction temperature is 120 ℃, and then the reaction liquid enters a third-stage flash tank, the operation temperature of the flash tank is 83 ℃, and the pressure is 20Kpa, so that crude reaction liquid is obtained.
The composition of the crude reaction solution, as measured in the gas phase, was as follows: 1.2 wt% of 1, 4-butanediol, 1.5 wt% of methyl acrylate, 36.1 wt% of hydroxybutyl acrylate and 61.2 wt% of 1, 4-butanediol diacrylate. The catalyst can stably run for 800 hours, and the activity of the catalyst is only reduced by 1.5 percent
(2) And (3) continuously introducing the crude reaction liquid into a phase separation tank, respectively adding water and xylene into the phase separation tank, wherein the mass ratio of the water to the xylene to the reaction liquid is 1:1:1, and extracting to obtain a water phase and an organic phase.
The aqueous phase had the following composition: 2.9 wt% of 1, 4-butanediol, 0.2 wt% of methyl acrylate, 96 wt% of hydroxybutyl acrylate and 0.7 wt% of 1, 4-butanediol diacrylate;
the organic phase composition was as follows: 0.1 wt% of 1, 4-butanediol, 0.4 wt% of methyl acrylate, 1.9 wt% of hydroxybutyl acrylate and 97.6 wt% of 1, 4-butanediol diacrylate.
(3) Introducing the water phase into a water phase rectifying tower, wherein the pressure at the top of the water phase rectifying tower is 5KPa, and the temperature is 30 ℃; the pressure of the tower kettle is 6KPa, and the temperature is 50 ℃; the obtained product of the hydroxybutyl acrylate at the bottom of the tower consists of: 2.7 percent of 1, 4-butanediol, 96.5 percent of hydroxybutyl acrylate and 0.8 percent of 1, 4-butanediol diacrylate;
introducing an organic phase into an organic phase rectifying tower, wherein the tower top pressure of the organic phase rectifying tower is 8KPa, and the temperature is 40 ℃; the pressure of the tower kettle is 9KPa, the temperature is 58 ℃, and the obtained 1, 4-butanediol diacrylate product in the tower kettle comprises the following components: 0.1 wt% of 1, 4-butanediol, 2 wt% of hydroxybutyl acrylate and 97.9 wt% of 1, 4-butanediol diacrylate.
Example 3:
(1) and preparing a reaction solution, wherein the catalyst in the fixed bed is a No. 2 sulfonic acid resin catalyst. Wherein, the mol ratio of the 1, 6-hexanediol to the methyl acrylate is 1:12, the polymerization inhibitor is p-methyl phenol, and the addition amount is 0.005 wt% of the methyl methacrylate. As shown in FIG. 1, at a space velocity of 0.5h-1Feeding the reaction solution into a first-stage fixed bed reactor, wherein the reaction temperature is 80 ℃, and then feeding the reaction solution into a first-stage flash tank, wherein the operating temperature of the flash tank is 40 ℃, and the pressure is 10 Kpa; after the reaction liquid passes through the buffer tank (fresh methyl acrylate is supplemented in the buffer tank, the supplemented methyl acrylate enters the first stageThe mol ratio of the methyl acrylate in the fixed bed reactor is 1:4), and the methyl acrylate enters a second-stage fixed bed reactor with the space velocity of 1h-1The reaction temperature is 90 ℃, and then the reaction liquid enters a second-stage flash tank, the operation temperature of the flash tank is 40 ℃, and the pressure is 10 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl acrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl acrylate to the methyl acrylate entering the first-stage fixed bed reactor is 1:2), the reaction liquid enters a third-stage fixed bed reactor, and the airspeed is 4h-1And the reaction temperature is 110 ℃, and then the reaction liquid enters a third-stage flash tank, the operation temperature of the flash tank is 80 ℃, and the pressure is 10Kpa, so that crude reaction liquid is obtained.
The composition of the crude reaction solution, as measured in the gas phase, was as follows: 0.6 wt% of 1, 6-hexanediol, 4.2 wt% of methyl acrylate, 41.4 wt% of hydroxyhexyl acrylate, and 53.8 wt% of 1, 6-hexanediol diacrylate. The catalyst can stably run for 1000 hours, and the activity of the catalyst is only reduced by 0.9 percent
(2) And continuously introducing the crude reaction liquid into a phase separation tank, respectively adding water and dimethylbenzene into the phase separation tank, wherein the mass ratio of the water to the dimethylbenzene to the reaction liquid is 5:1:1, and extracting to obtain a water phase and an organic phase.
The aqueous phase had the following composition: 1.2 wt% of 1, 6-hexanediol, 0.5 wt% of methyl acrylate, 97.9 wt% of hydroxyhexyl acrylate, and 0.4 wt% of 1, 6-hexanediol diacrylate;
the organic phase composition was as follows: 0.1 wt% of 1, 6-hexanediol, 7.9 wt% of methyl acrylate, 0.2 wt% of hydroxybutyl acrylate and 91.8 wt% of 1, 6-hexanediol diacrylate.
(3) Introducing the water phase into a water phase separation tower, wherein the tower top pressure of a water phase rectifying tower is 3KPa, and the temperature is 25 ℃; the pressure of the tower kettle is 4KPa, and the temperature is 40 ℃; the obtained product of the hydroxybutyl acrylate at the bottom of the tower consists of: 1.3 wt% of 1, 6-hexanediol, 98.1 wt% of hydroxyhexyl acrylate and 0.6 wt% of 1, 6-hexanediol diacrylate;
introducing an organic phase into an organic phase separation tower, wherein the tower top pressure of the organic phase rectification tower is 5KPa, and the temperature is 30 ℃; the pressure of the tower kettle is 6KPa, the temperature is 50 ℃, and the obtained product of the 1, 6-hexanediol diacrylate in the tower kettle comprises the following components: 0.4 wt% of 1, 6-hexanediol, 0.5 wt% of hydroxyhexyl acrylate and 99.1 wt% of 1, 6-hexanediacrylate.
Comparative example 1:
(1) and preparing a reaction solution, wherein the catalyst in the fixed bed is a 3# sulfonic acid resin catalyst. Wherein, the molar ratio of the 1, 4-butanediol to the methyl methacrylate is 1:4, the polymerization inhibitor is p-methyl phenol, and the addition amount is 0.02 wt% of the methyl methacrylate. As shown in FIG. 1, at a space velocity of 1h-1Feeding the reaction solution into a first-stage fixed bed reactor, wherein the reaction temperature is 100 ℃, and then feeding the reaction solution into a first-stage flash tank, wherein the operating temperature of the flash tank is 60 ℃, and the pressure is 25 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl methacrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl methacrylate to the methyl methacrylate entering a first-stage fixed bed reactor is 1:1), the reaction liquid enters a second-stage fixed bed reactor, and the airspeed is 1h-1The reaction temperature is 120 ℃, and then the reaction liquid enters a second-stage flash tank, the operating temperature of the flash tank is 60 ℃, and the pressure is 25 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl methacrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl methacrylate to the methyl methacrylate entering the first-stage fixed bed reactor is 1:1), the reaction liquid enters a third-stage fixed bed reactor, and the airspeed is 4h-1And the reaction temperature is 130 ℃, and then the reaction liquid enters a third-stage flash tank, the operation temperature of the flash tank is 100 ℃, and the pressure is 25Kpa, so that crude reaction liquid is obtained.
The composition of the initial crude reaction solution, as measured in the gas phase, was as follows: 1.2 wt% of 1, 4-butanediol, 0.7 wt% of methyl methacrylate, 54.2 wt% of hydroxybutyl methacrylate and 43.9 wt% of 1, 4-butanediol dimethacrylate. As the reaction proceeded, the composition of the reaction solution fluctuated greatly and could not be separated continuously, and after 100h, the catalyst activity was only 37% of the initial value.
Comparative example 2:
(1) and preparing a reaction solution, wherein the catalyst in the fixed bed is a 3# sulfonic acid resin catalyst. Wherein, the mol ratio of the 1, 6-hexanediol to the methyl acrylate is 1:12, the polymerization inhibitor is p-methyl phenol, and the addition amount is 0.005 wt% of the methyl methacrylate. As shown in FIG. 1, at a space velocity of 0.5h-1Enters a first stage fixed bedThe reaction temperature of the reactor is 80 ℃, and then the reaction liquid enters a first-stage flash tank, the operating temperature of the flash tank is 40 ℃, and the pressure is 10 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl acrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl acrylate to the methyl acrylate entering the first-stage fixed bed reactor is 1:4), the reaction liquid enters a second-stage fixed bed reactor, and the airspeed is 1h-1The reaction temperature is 90 ℃, and then the reaction liquid enters a second-stage flash tank, the operation temperature of the flash tank is 40 ℃, and the pressure is 10 Kpa; after the reaction liquid passes through a buffer tank (fresh methyl acrylate is supplemented in the buffer tank, the molar ratio of the supplemented methyl acrylate to the methyl acrylate entering the first-stage fixed bed reactor is 1:2), the reaction liquid enters a third-stage fixed bed reactor, and the airspeed is 4h-1And the reaction temperature is 110 ℃, and then the reaction liquid enters a third-stage flash tank, the operation temperature of the flash tank is 80 ℃, and the pressure is 10Kpa, so that crude reaction liquid is obtained.
The initial composition of the crude reaction solution, as measured in the gas phase, was as follows: 0.8 wt% of 1, 6-hexanediol, 4.5 wt% of methyl acrylate, 41.2 wt% of hydroxyhexyl acrylate, and 53.5 wt% of 1, 6-hexanediol diacrylate. As the reaction proceeded, the composition of the reaction solution fluctuated greatly and could not be continuously separated, and after 100h, the catalyst activity was only 42% of the initial value.
As can be seen from the analysis of the experimental results of the above examples and comparative examples,
(1) according to the invention, through the cooperation of continuous production equipment and a heterogeneous catalyst (a low-surface-energy sulfonic acid resin catalyst), the separation process and steps of products can be simplified, the crude reaction liquid is divided into a water phase containing (methyl) acrylic acid monoester and an oil phase containing (methyl) acrylic acid diester through extraction, the separation of the catalyst and the polymerization inhibitor is not considered, and the high-temperature operation condition required by rectifying and separating the catalyst and the polymerization inhibitor is avoided.
(2) When the water phase and the oil phase are rectified and separated, the separation temperature is low (the water phase is rectified below 70 ℃, the oil phase is rectified below 80 ℃), and the purity of the obtained product is high: the purity of the (methyl) acrylic acid hydroxyl ester is more than 96 wt%, and the purity of the (methyl) acrylic acid diester is more than 97.9 wt%.
(3) The sulfonic acid resin catalyst has low surface energy, high heat resistance and strong oligomer adhesion resistance, effectively prolongs the service life of the catalyst, and ensures long-term operation and normal operation of the used continuous production process.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (49)
1. The sulfonic acid resin catalyst is characterized by being prepared by polymerization reaction of raw materials comprising the following components:
(1) an aryl-substituted ethylenic monomer,
(2) (meth) acrylic acid esters having a cycloalkane structure,
(3) a fluorosilicone containing a double bond;
the polymerization reaction system for preparing the sulfonic acid resin catalyst further comprises an auxiliary agent, wherein the auxiliary agent comprises:
(4) a cross-linking agent which is a cross-linking agent,
(5) a pore-forming agent, a surfactant and a surfactant,
(6) an initiator;
the sulfonic acid resin catalyst is prepared by adopting a method comprising the following steps:
(a) contacting an aryl-substituted alkene monomer, double-bond-containing fluorosilicone, (methyl) acrylate with a cycloparaffin structure, a cross-linking agent, a pore-forming agent and an initiator to perform polymerization reaction to prepare polymer microspheres;
(b) swelling the prepared polymer microspheres, and then performing sulfonation reaction to prepare the sulfonic acid resin catalyst.
2. The sulfonic acid resin catalyst of claim 1, wherein the aryl-substituted vinyl monomer is selected from phenyl-substituted vinyl monomers.
3. The sulfonic acid resin catalyst of claim 2, wherein the aryl-substituted vinyl monomer is selected from styrene and/or stilbene.
4. The sulfonic acid resin catalyst according to claim 1, characterized in that the double bond-containing fluorosilicone is selected from vinyltris- (trifluoro) methoxysilane and/or vinyltris (2,2, 2-trifluoro) ethoxysilane.
5. The sulfonic acid resin catalyst according to claim 1, characterized in that the (meth) acrylate having a cycloalkane structure is selected from one or more of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate and cyclohexyl acrylate.
6. The sulfonic acid resin catalyst according to any one of claims 1 to 5, wherein the molar ratio of the aryl-substituted vinyl monomer to the double bond-containing fluorosilicone is from 0.2 to 1: 1;
the molar ratio of the (methyl) acrylate with the cycloparaffin structure to the fluorosilicone containing double bonds is 0.2-5: 1.
7. the sulfonic acid resin catalyst according to claim 6, wherein the molar ratio of the aryl-substituted vinyl monomer to the double bond-containing fluorosilicone is from 0.4 to 0.8: 1.
8. the sulfonic acid resin catalyst according to claim 7, wherein the molar ratio of the aryl-substituted vinyl monomer to the double bond-containing fluorosilicone is from 0.5 to 0.7: 1.
9. the sulfonic acid resin catalyst according to claim 6, wherein the molar ratio of the (meth) acrylate having a cycloalkane structure to the double bond-containing fluorosilicone is from 1 to 3: 1.
10. the sulfonic acid resin catalyst according to claim 9, characterized in that the molar ratio of the (meth) acrylate having a cycloalkane structure to the double bond-containing fluorosilicone is 1.5 to 2.5: 1.
11. the sulfonic acid resin catalyst of claim 1, wherein the crosslinking agent is selected from one or more of 1, 3-propanediol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 3-propanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 5-pentanediol dimethacrylate, and 1, 6-hexanediol dimethacrylate.
12. The sulfonic acid resin catalyst of claim 1, wherein the porogen is selected from C10-C40Is one or more of linear or branched saturated alkanes.
13. The sulfonic acid resin catalyst of claim 12, wherein the porogen is selected from the group consisting of C10-C30Is one or more of linear or branched saturated alkanes.
14. The sulfonic acid resin catalyst of claim 13, wherein the porogen is selected from one or more of decane, n-undecane, n-eicosane, n-pentadecane, and n-pentacosane.
15. The sulfonic acid resin catalyst of claim 1, wherein the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, ammonium persulfate, and potassium persulfate.
16. The sulfonic acid resin catalyst according to any one of claims 1, 11 to 15, wherein the molar ratio of the crosslinking agent to the double bond-containing fluorosilicone is from 0.05 to 0.5: 1;
the molar ratio of the pore-foaming agent to the double-bond-containing fluorosilicone is 0.2-2.0: 1;
the molar ratio of the initiator to the double-bond-containing fluorosilicone is 0.005-0.02: 1.
17. the sulfonic acid resin catalyst according to claim 16, wherein the molar ratio of the crosslinking agent to the double bond-containing fluorosilicone is from 0.1 to 0.4: 1.
18. the sulfonic acid resin catalyst according to claim 17, wherein the molar ratio of the crosslinking agent to the double bond-containing fluorosilicone is from 0.2 to 0.35: 1.
19. the sulfonic acid resin catalyst of claim 16, wherein the molar ratio of porogen to double bond-containing fluorosilicone is from 0.5 to 1: 1.
20. the sulfonic acid resin catalyst of claim 19, wherein the molar ratio of porogen to double bond-containing fluorosilicone is from 0.6 to 0.9: 1.
21. the sulfonic acid resin catalyst of claim 16, wherein the molar ratio of the initiator to the double bond-containing fluorosilicone is 0.012-0.018: 1.
22. The sulfonic acid resin catalyst of claim 21, wherein the molar ratio of the initiator to the double bond-containing fluorosilicone is 0.014-0.016: 1.
23. The sulfonic acid resin catalyst of claim 1, wherein in step (a), the polymerization reaction is carried out by a suspension polymerization process; the polymerization reaction temperature is 65-100 ℃; the polymerization reaction time is 2-6 h.
24. The sulfonic acid resin catalyst of claim 23, wherein in step (a), the polymerization temperature is from 70 to 95 ℃; the polymerization reaction time is 3-5 h.
25. The sulfonic acid resin catalyst according to claim 1, wherein in step (b), the swelling is carried out in a solvent.
26. The sulfonic acid resin catalyst of claim 25, wherein the solvent is selected from one or more of methanol, ethanol, diethyl ether, acetone, n-hexane, and cyclohexane.
27. The sulfonic acid resin catalyst of claim 25, wherein the swelling time is from 3 to 6 hours.
28. The sulfonic acid resin catalyst of claim 27, wherein the swelling time is from 4 to 6 hours.
29. The sulfonic acid resin catalyst according to claim 1, wherein in step (b), the sulfonation reaction uses a sulfonating agent selected from one or more of concentrated sulfuric acid, sulfur trioxide, sodium sulfite, and chlorosulfonic acid.
30. The sulfonic acid resin catalyst of claim 1, wherein the molar ratio of the sulfonating agent to the aryl-substituted alkene monomer is 1: (0.5-5).
31. The sulfonic acid resin catalyst of claim 30, wherein the molar ratio of the sulfonating agent to the aryl-substituted alkene monomer is from 1: (1-4).
32. The sulfonic acid resin catalyst of claim 31, wherein the molar ratio of the sulfonating agent to the aryl-substituted alkene monomer is from 1: (2-3).
33. The sulfonic acid resin catalyst of claim 29, wherein the temperature of the sulfonation reaction is 40-100 ℃; the sulfonation reaction time is 5-10 h.
34. The sulfonic acid resin catalyst of claim 33, wherein the temperature of the sulfonation reaction is 50-80 ℃; the sulfonation reaction time is 6-8 h.
35. A method for continuously producing a hydroxy (meth) acrylate and a diester (meth) acrylate, the method comprising the steps of:
(1) contacting dihydric alcohol, methyl (meth) acrylate and a polymerization inhibitor to form a reaction liquid, and continuously pumping the reaction liquid into a reaction device filled with the sulfonic acid resin catalyst of any one of claims 1 to 34 for reaction to obtain a crude reaction liquid; the reaction apparatus comprises: the first-stage reaction unit is connected with the first-stage flash tank through the first-stage fixed bed reactor, the second-stage reaction unit is connected with the second-stage flash tank through the second-stage fixed bed reactor, and the third-stage reaction unit is connected with the third-stage flash tank through the third-stage fixed bed reactor; the storage tank filled with the methyl (meth) acrylate is respectively connected with the first-stage fixed bed reactor, the second-stage fixed bed reactor and the third-stage fixed bed reactor, and the storage tank filled with the dihydric alcohol is connected with the first-stage fixed bed reactor;
(2) extracting the crude reaction liquid in the step (1) to respectively obtain a water phase containing (methyl) acrylic acid monoester and an oil phase containing (methyl) acrylic acid diester;
(3) and (3) respectively rectifying the water phase and the oil phase in the step (2) to obtain a (methyl) acrylic acid hydroxyl ester product and a (methyl) acrylic acid diester product.
36. The method of claim 35, wherein in step (1), the glycol is selected from C2～C10The linear aliphatic diol of (1).
37. The method according to claim 36, wherein in step (1), the diol is selected from the group consisting of C4～C8The linear aliphatic diol of (1).
38. The method according to claim 37, wherein in step (1), the diol is selected from 1, 4-butanediol and/or 1, 6-hexanediol.
39. The method as claimed in claim 35, wherein the reaction temperature of the first-stage fixed bed reactor is 80-100 ℃, and the residence time of the reaction solution is 1-2 h; the temperature of the first-stage flash tank is 40-60 ℃, and the pressure is 10-25 KPa.
40. The method as claimed in claim 35, wherein the reaction temperature of the second-stage fixed bed reactor is 100-120 ℃, and the residence time of the reaction solution is 0.5-1 h; the temperature of the second-stage flash tank is 40-60 ℃, and the pressure is 10-25 KPa.
41. The method as claimed in claim 35, wherein the reaction temperature of the third-stage fixed bed reactor is 110-; the temperature of the third-stage flash tank is 80-100 ℃, and the pressure is 10-25 KPa.
42. The method as claimed in claim 35, wherein the molar ratio of the dihydric alcohol and the methyl (meth) acrylate fed into the first-stage fixed bed reactor in the step (1) is 1:4 to 1: 12.
43. The method as claimed in claim 35, wherein the molar ratio of the methyl (meth) acrylate fed into the second-stage fixed bed reactor in the step (1) to the methyl (meth) acrylate fed into the first-stage fixed bed reactor is 1:1 to 1: 4.
44. The method according to claim 35, wherein the molar ratio of the methyl (meth) acrylate fed into the third-stage fixed bed reactor in the step (1) to the methyl (meth) acrylate fed into the first-stage fixed bed reactor is 1:1 to 1: 2.
45. The method of claim 35, wherein in step (2), the extraction is performed using a bi-solvent.
46. The method of claim 45, wherein the bi-solvent is water and an aromatic compound.
47. The method as claimed in claim 46, wherein the aromatic hydrocarbon compound is selected from one or more of benzene, toluene and xylene.
48. The method as claimed in claim 46, wherein the mass ratio of water to aromatic hydrocarbon compound in the bi-solvent is 1:5-5: 1.
49. The method as claimed in claim 45, wherein the mass ratio of the bi-solvent to the crude reaction solution is 1:5 to 5: 1.
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| CN113083363B (en) * | 2019-12-23 | 2022-09-16 | 万华化学集团股份有限公司 | Resin catalyst and preparation method and application thereof |
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| CN115010842B (en) * | 2022-05-20 | 2024-02-02 | 万华化学集团股份有限公司 | Fluorine-containing strong-alkaline anion resin catalyst, preparation method thereof and preparation method of hydroxyethyl (meth) acrylate |
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