CN110878009B - Preparation method of bisphenol A salt - Google Patents
Preparation method of bisphenol A salt Download PDFInfo
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- CN110878009B CN110878009B CN201811029937.6A CN201811029937A CN110878009B CN 110878009 B CN110878009 B CN 110878009B CN 201811029937 A CN201811029937 A CN 201811029937A CN 110878009 B CN110878009 B CN 110878009B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The invention provides a preparation method of bisphenol A salt. Bisphenol A and inorganic strong base directly react without solvent to obtain bisphenol A salt. The preparation method comprises the following steps: (1) Crushing and mixing bisphenol A and inorganic strong base to obtain an ultrafine mixture; (2) Heating and stirring the mixture for reaction to obtain a crude product; (3) The crude product was distilled under reduced pressure to remove the residual excess bisphenol A, and cooled to obtain bisphenol A salt as a solid powder. The method has the advantages that no solvent is used in the whole reaction process, the reaction is simple and rapid, the yield is high, and the product purity is high.
Description
Technical Field
The invention belongs to the field of organic metal salt synthesis, and particularly relates to a preparation method of bisphenol A salt.
Technical Field
Bisphenol a is a cheap and widely used chemical raw material, and is used as an important monomer for synthesizing various polymers, such as polycarbonate, epoxy resin, polyimide, polysulfone and the like. The preparation of polymers such as polyimide, polysulfone and the like using bisphenol a as a monomer usually involves a nucleophilic reaction, i.e. bisphenol a is first prepared into a bisphenol a salt, which is used as a nucleophile to participate in the reaction. The purity and activity of the bisphenol A salt are directly related to the effect of the subsequent polymerization and the properties of the final polymer, and the preparation method is very critical. Since bisphenol a salts are poor in stability and are easily oxidized or lose activity by contact with protic compounds including water, it is a problem to be studied how to efficiently and stably produce high-purity bisphenol a salts.
The conventional process for producing bisphenol A salt is mainly to react bisphenol A with a strong base in a nonpolar hydrocarbon solvent, gradually promote the reaction by removing the generated water, and then evaporate the excess solvent to obtain a bisphenol A salt solid. The method has the advantages of slow reaction speed, poor purity of the prepared bisphenol A salt and complex equipment requirement. On the basis, the technical personnel in the field also make some improvements, for example, in patent CN200410065695, benzene/toluene and aprotic polar solvent such as dimethyl sulfoxide, dimethyl formamide and the like are mixed to be used as mixed solvent, bisphenol compound and alkali are refluxed to carry water, and then benzene/toluene is evaporated to obtain the mixture of bisphenol A salt and polar solvent. However, the method has low reaction solid content (20-30%), long reaction time (refluxing for 4-6 h), and can not remove all water. Patent CN201580020086 uses o-dichlorobenzene as solvent, passes aqueous alkali solution into o-dichlorobenzene containing bisphenol a at high temperature (160 ℃) and immediately divides water, when bisphenol a salt is formed and precipitated, it is dissolved again with isopropanol, and finally all solvent is evaporated to obtain dry bisphenol a salt. The method solves the problem of bisphenol A salt wall formation, but the implementation steps are complicated, and the final drying process is long (vacuum drying at 150 ℃ for 12 hours). Patent CN200910241383 discloses a method for preparing a stable bisphenol a sodium salt solution, which comprises preparing alkali into alkali liquor, adding antioxidant, adding bisphenol a, dissolving to form solution, and avoiding oxidation of sodium salt by antioxidant, but the antioxidant and other impurities in the solution are difficult to remove, and the sodium salt in the form of solution is very inconvenient to use.
Therefore, there is a need in the art for a simple and efficient method for producing bisphenol a salts with high yield and high product purity.
Disclosure of Invention
The invention aims to solve the problems of low reaction efficiency, complex equipment and poor product purity of the existing bisphenol A salt preparation method, and provides the bisphenol A salt preparation method which has high production efficiency, high product purity and less three wastes.
In order to achieve the aim, the technical scheme of the invention is as follows:
a method for preparing a bisphenol a salt, comprising the steps of:
(1) Crushing and mixing bisphenol A and inorganic strong base to obtain an ultrafine mixture;
(2) Heating and stirring the mixture for reaction to obtain a crude product;
(3) The crude product was distilled under reduced pressure to remove the residual excess bisphenol A, and cooled to obtain bisphenol A salt as a solid powder.
In the present invention, the molar ratio of bisphenol A in step (1) to the metal atom in the strong inorganic base is (1.2 to 1.7): 2, preferably (1.3 to 1.5): 2. The excessive bisphenol A can ensure the full performance of the salt forming reaction, avoid the residue of inorganic base, reduce the overall viscosity of the reaction system and be beneficial to the heat transfer and the stirring of the reaction.
In the invention, the inorganic strong base in step (1) is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium amide, sodium amide, potassium hydride and sodium hydride, preferably sodium hydroxide and/or potassium hydroxide.
In the invention, the particle size of the superfine mixture in the step (1) is less than 2000 meshes. In order to obtain the superfine mixture with the granularity, a superfine pulverizer comprising a jet mill, a ball mill, a zirconia pulverizer and other pulverizing devices can be adopted, or other feasible pulverizing means can be adopted. The granularity of the raw materials refers to the undersize of the screen with corresponding meshes.
In the invention, the reaction temperature of the step (2) is 160-180 ℃, and the stirring speed is 50-100 rpm. The reaction temperature cannot be lower than 160 ℃, otherwise, bisphenol A cannot be melted, and the reaction speed is very slow; meanwhile, the reaction temperature cannot be higher than 180 ℃, otherwise, the bisphenol A is easy to decompose.
In the invention, the step (2) is reacted under the protection of flowing protective gas, the flow rate of the protective gas is 0.5-3L/min, and the protective gas is preheated to be consistent with the reaction temperature before being used. The protective gas has the following functions in reaction: protecting the generated sodium salt from being oxidized by oxygen; the water produced is carried away by continuous gas displacement. Too low a flow rate of the shielding gas results in less efficient water entrainment, while too high a flow rate may flush away the reactants in the reactor. The preheating protective gas has the following functions: so that the generated water is not condensed into liquid; the reaction temperature of the reactor is kept stable. The preheating purpose can be realized by arranging an air heater in front of the air inlet pipe.
In the invention, the protective gas in the step (2) is one or more of nitrogen, carbon dioxide, helium, neon, argon and xenon.
In the present invention, the step (2) is carried out to terminate the reaction when no moisture is detected in the discharged gas. And (2) as the reaction proceeds, the moisture generated by the reaction is carried out of the reaction container along with the airflow of the protective gas. The corresponding gas moisture detection device is arranged at the air outlet, so that the moisture generated by the reaction can be conveniently monitored. After the reaction is finished, the reaction product bisphenol A salt and the bisphenol A remained due to the excess are mainly in the reactor.
In the invention, the reduced pressure distillation conditions of the step (3) are that the vacuum degree is-0.05 to-0.1 MPa (gauge pressure), the temperature is 220 to 250 ℃, and the time is 1 to 2 hours. The purpose of the distillation under reduced pressure is to remove the excess residual bisphenol A in the crude product. Under these conditions, the excess bisphenol A gradually decomposes into phenol and acetone, and is discharged from the reactor by distillation under reduced pressure. The discharged gas is washed by a hot alkaline aqueous solution to remove decomposition products of bisphenol A.
The invention has the positive effects that:
(1) No solvent is used, the solid content of the reaction feeding is high, the reaction speed is high, and therefore, the production efficiency is high;
(2) The product does not contain impurities such as solvent and the like, and feeding materials with different molar ratios ensures that the reaction is more sufficient and the product purity is high;
(3) The used protective gas can be recycled and continuously used after simple dehydration, the decomposition products of the excessive bisphenol A can be conveniently collected by washing, and the three wastes generated in the whole preparation process are less;
(4) The equipment is simple, the operation is convenient, devices such as solvent distillation recovery and the like are not needed, and the overall investment is small.
Detailed Description
According to the technical solution, the following embodiments are given, which are not intended to limit the scope of the present invention.
Elemental analysis test: agilent ICP-OES720, ICP quantitative test, and detection of the content of metal elements in the synthesized product. The content of metal elements in the product is compared with a theoretical value to be used as a basis for evaluating the purity of the product. And (3) testing conditions: the pump number is 15rpm and the power is 1.3kW.
Specific information on the chemical raw materials involved is shown in table 1:
table 1 chemical raw material information table
Example 1
22.83g of bisphenol A and 5g of sodium hydroxide solid were accurately weighed and put into an ultrafine pulverizer to be pulverized, thereby obtaining a mixture powder having a particle size of 2500 mesh. The resulting mixture was charged into a round-bottomed flask connected with a gas inlet duct, a gas moisture tester, an anchor paddle stirrer and a vacuum pump, while introducing argon gas at a rate of 1.5L/min, which was heated to 180 ℃ in advance by an air heater. The round bottom flask was heated to 180 ℃ by a salt bath and the stirring was turned on to 60rpm. And (3) when the reaction is carried out until the moisture content can not be detected at the air outlet, closing the air inlet valve, increasing the temperature to 250 ℃, simultaneously starting the vacuum pump until the vacuum degree is-0.05 MPa, and stopping heating after the vacuum distillation is carried out for 1 h. 16.47g of bisphenol A sodium salt solid are obtained in a yield of 96.75% (based on sodium hydroxide). Elemental analysis showed 16.74% elemental sodium (16.90% theoretical).
Example 2
228.3g of bisphenol A and 31.92g of lithium hydroxide were put into an ultrafine pulverizer, and ultrafine mixture powder having a particle size of 3500 mesh was obtained by sufficient pulverization. And adding the mixed powder into a reaction kettle, wherein the reaction kettle is connected with an air inlet guide pipe, a gas moisture tester, an anchor stirring paddle and a vacuum pump, and nitrogen is introduced into the reaction kettle in advance to exhaust air. The reaction vessel was gradually warmed to 160 ℃ and the stirring speed was set to 50rpm. After the reaction was started, nitrogen gas heated to 160 ℃ by an air heater was introduced into the reaction vessel at a flow rate of 0.5L/min, while the moisture in the discharged nitrogen gas was monitored by a gas moisture tester, and the reaction was stopped when no more moisture was produced. And (3) closing an air inlet valve, raising the temperature of the kettle to 220 ℃, starting a vacuum pump until the vacuum degree is-0.1 MPa, and carrying out reduced pressure distillation on the redundant bisphenol A for 2 hours. The final product was 158.4g of lithium bisphenol A as a solid in 98.83% yield (based on lithium hydroxide). Elemental analysis showed a lithium content of 5.30% (theoretical value 5.80%).
Example 3
42.53g of potassium carbonate flake solid is firstly ground into coarse particles, then mixed with 91.32g of bisphenol A particles, and put into a superfine pulverizer for further pulverization and mixing, and finally superfine powder with 3000 meshes is obtained. Then the crushed mixture is poured into a stainless steel reactor which is provided with an air inlet conduit, a gas moisture tester, an anchor stirring paddle and a vacuum pump in advance, and carbon dioxide is introduced into the reactor through an air inlet pipe for gas protection. The reactor was heated to 170 ℃ with a stirring speed of 100rpm, while carbon dioxide gas previously heated to 170 ℃ via an air heater was introduced into the reactor at a flow rate of 2L/min. And monitoring the moisture content through a gas moisture tester connected with the gas outlet along with the reaction, stopping the reaction until no moisture is generated, and closing the gas inlet valve. And continuously heating the reactor to 230 ℃, starting a vacuum pump to evaporate redundant bisphenol A, setting the vacuum degree to be-0.05 MPa, stopping heating after distilling for 1 hour, and taking out the solid. 91.7g of white potassium bisphenol A salt solid powder was obtained in 97.9% yield (based on potassium carbonate). Elemental analysis showed 25.55% potassium (25.63% theoretical).
Example 4
44.16g of sodium carbonate flake solid and 114.15g of bisphenol A granules are simply ground and put into a jet mill together for grinding to obtain ultrafine powder with the granularity of 4000 meshes. And then putting the crushed mixed material into an oil bath kettle, wherein a vacuum pump, an air inlet and outlet valve and a helical ribbon type stirring paddle are connected to the kettle. Carbon dioxide gas was heated to 175 ℃ by a heater, and then introduced into the reactor at a flow rate of 3L/min, and the oil bath temperature was similarly set to 175 ℃. The stirring speed was turned on at 80rpm. And monitoring the moisture content in the carbon dioxide gas by a gas moisture tester continuously connected with the gas outlet, closing the gas inlet valve when no moisture is generated, heating to 240 ℃, simultaneously starting a vacuum pump to the negative pressure of-0.09 MPa, and carrying out reduced pressure distillation for 2 hours. After final cooling, 109.26g of white bisphenol A sodium salt solid powder was obtained in 96.3% yield (based on sodium carbonate). Elemental analysis showed 16.81% sodium (theoretical 16.90%).
Example 5
456.6g of bisphenol A and 160.3g of potassium hydroxide solid were simply mixed and ground, and then the mixture was pulverized in an air flow pulverizer so that the particle size of the mixture was 3500 mesh. The mixture powder was charged into a 2L glass four-necked flask and the anchor stirrer was turned on to a speed of 90rpm. High purity helium was heated to 160 ℃ and passed into the flask at a flow rate of 1L/min. Starting to heat to 160 ℃ for reaction, monitoring the moisture content through a gas moisture tester connected with the gas outlet, stopping the reaction until no moisture is generated, and closing the gas inlet valve. Then the vacuum pump is opened and the temperature is raised to 250 ℃, and after the reduced pressure distillation for 1.5h under the negative pressure of-0.09 MPa, the temperature is reduced to obtain 423.85g of white solid powder of bisphenol A sylvite, the yield is 97.5 percent (based on potassium hydroxide). Elemental analysis showed 25.52% potassium (25.63% theoretical).
Comparative example 1
Bisphenol a salts were prepared with reference to patent CN 201510861128. Adding 300ml of toluene into a reaction kettle which is connected with a water separator and protected by inert gas, heating to 70 ℃, sequentially adding 228.3g of bisphenol A and 84g of sodium hydroxide, violently stirring to uniformly disperse the bisphenol A and the sodium hydroxide, then adding 440ml of residual toluene, continuously stirring, heating to 120 ℃, and carrying out reflux reaction for 2 hours until the toluene does not carry out generated moisture. After the salt-forming reaction was completed, all toluene was distilled off, and nitrogen gas was used for purging until toluene was evaporated to dryness, thereby obtaining 245g of a white bisphenol a sodium salt powdery solid with a yield of 90%. The content of sodium element was 14.40% (theoretical value 16.89%) by elemental analysis.
Comparative example 2
Bisphenol a salts were prepared with reference to patent CN 201510861128. 45.66g of bisphenol A and 30.4g of potassium carbonate solid particles were accurately weighed, sufficiently crushed and uniformly mixed, put into a four-necked flask connected with a water separator, a condenser tube, a nitrogen inlet tube and mechanical stirring, 228g of ethylbenzene was previously added into the flask, and the air in the flask was replaced with nitrogen. 65g of water are added, stirring is started and the temperature is gradually raised to 125 ℃ and the reflux water is initially taken up by a water separator. As the water split proceeded, the boiling point of the system was increased continuously, and when the temperature was increased to 136 ℃ and no more water was generated, the temperature was further set to 150 ℃ to distill off the solvent. Finally, the flask was purged with nitrogen to obtain 54.46g of a white powdery solid of potassium bisphenolate in 89.5% yield. The content of potassium element was 22.20% (theoretical value 25.68%) by elemental analysis.
As can be seen from the comparison of examples and comparative examples, the bisphenol A salt produced by the process of the present invention has a higher yield and a higher purity.
Claims (11)
1. A method for preparing a bisphenol a salt, comprising the steps of:
(1) Crushing and mixing bisphenol A and inorganic strong base to obtain an ultrafine mixture;
(2) Heating and stirring the mixture for reaction to obtain a crude product;
(3) Distilling the crude product under reduced pressure to remove residual excessive bisphenol A, and cooling to obtain bisphenol A salt solid powder; wherein the reaction temperature in the step (2) is 160-180 ℃; and (2) carrying out reaction under the protection of flowing protective gas.
2. The process according to claim 1, wherein the molar ratio of bisphenol A to the metal atom in the strong inorganic base in step (1) is (1.2 to 1.7): 2.
3. The process according to claim 1, wherein the molar ratio of bisphenol A to the metal atom in the strong inorganic base in step (1) is (1.3 to 1.5): 2.
4. The preparation method according to claim 1 or 2, wherein the inorganic strong base in step (1) is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium amide, sodium amide, potassium hydride and sodium hydride.
5. The method according to claim 1 or 2, wherein the strong inorganic base in step (1) is sodium hydroxide and/or potassium hydroxide.
6. The method of claim 1, wherein the particle size of the ultra-fine mixture in step (1) is greater than 2000 mesh.
7. The production method according to claim 1, wherein the stirring speed in the step (2) is 50 to 100rpm.
8. The method according to claim 1, wherein the flow rate of the shielding gas in the step (2) is 0.5 to 3L/min, and the shielding gas is preheated to be in conformity with the reaction temperature before use.
9. The method according to claim 1, wherein the protective gas in the step (2) is one or more of nitrogen, carbon dioxide, helium, neon, argon and xenon.
10. The production method according to claim 1, wherein the step (2) is carried out to terminate the reaction when moisture is not monitored in the discharged gas.
11. The preparation method according to claim 1, wherein the reduced pressure distillation condition in the step (3) is a vacuum degree of-0.05 to-0.1 MPa, a temperature of 220 to 250 ℃ and a time of 1 to 2 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603353A (en) * | 2003-09-30 | 2005-04-06 | 合肥工业大学 | Synthesis process for polycarbonate with super high molecular weight |
| CN101735020A (en) * | 2009-12-17 | 2010-06-16 | 武汉工业学院 | Process for the catalytic synthesis of bisphenol fluorene by using concentrated sulphuric acid |
| CN106232677A (en) * | 2014-04-15 | 2016-12-14 | 沙特基础工业全球技术有限公司 | The method of preparation Polyetherimide |
| CN107459443A (en) * | 2017-09-25 | 2017-12-12 | 甘肃省化工研究院 | A kind of preparation method of 2,6 di-t-butyl phenates |
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- 2018-09-05 CN CN201811029937.6A patent/CN110878009B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603353A (en) * | 2003-09-30 | 2005-04-06 | 合肥工业大学 | Synthesis process for polycarbonate with super high molecular weight |
| CN101735020A (en) * | 2009-12-17 | 2010-06-16 | 武汉工业学院 | Process for the catalytic synthesis of bisphenol fluorene by using concentrated sulphuric acid |
| CN106232677A (en) * | 2014-04-15 | 2016-12-14 | 沙特基础工业全球技术有限公司 | The method of preparation Polyetherimide |
| CN107459443A (en) * | 2017-09-25 | 2017-12-12 | 甘肃省化工研究院 | A kind of preparation method of 2,6 di-t-butyl phenates |
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