CN114685777B - Bisphenol A polyoxyethylene ether synthesis process - Google Patents
Bisphenol A polyoxyethylene ether synthesis process Download PDFInfo
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- CN114685777B CN114685777B CN202210334483.3A CN202210334483A CN114685777B CN 114685777 B CN114685777 B CN 114685777B CN 202210334483 A CN202210334483 A CN 202210334483A CN 114685777 B CN114685777 B CN 114685777B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
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Abstract
The application relates to the field of bisphenol A polyoxyethylene ether synthesis, and in particular discloses a bisphenol A polyoxyethylene ether synthesis process, which comprises the following steps: s1: preparing a bisphenol A preform; s2: mixing bisphenol A preformed body, solvent and ethylene oxide for addition reaction, and filtering to obtain an initial product; s3: curing the initial product, and removing the solvent to obtain the bisphenol A polyoxyethylene ether; the bisphenol A preform comprises a powdery bisphenol A raw material and a powdery catalyst, and is prepared by pressing the raw material into annular particles with the diameter of 2-5cm by using a die. The application has the advantages of reducing energy consumption in the bisphenol A polyoxyethylene ether synthesis process and improving reaction efficiency.
Description
Technical Field
The application relates to the field of bisphenol A polyoxyethylene ether, in particular to a bisphenol A polyoxyethylene ether synthesis process.
Background
Bisphenol A polyoxyethylene ether is generally used as a toughening agent of cathode electrophoretic paint, can improve the flexibility, corrosion resistance and interlayer adhesion of the cathode electrophoretic paint, can improve the mechanical strength of the paint, can enhance the ageing resistance, and has good chemical corrosion resistance and electrical property characteristics.
Bisphenol A polyoxyethylene ether is mainly prepared by taking bisphenol A as an initiator and directly carrying out addition reaction with ethylene oxide under the action of different types of catalysts (acid catalyst, alkaline earth catalyst, composite alkaline catalyst and the like).
In the traditional bisphenol A polyoxyethylene ether synthesis process, an initiator bisphenol A is heated at 158 ℃ firstly, and the melted bisphenol A reacts with ethylene oxide and a catalyst, so that the process is complex and the energy consumption is high.
Disclosure of Invention
The application provides a bisphenol A polyoxyethylene ether synthesis process for improving the synthesis economy and the reaction efficiency of bisphenol A polyoxyethylene ether.
A bisphenol A polyoxyethylene ether synthesis process comprises the following steps:
s1: preparing a bisphenol A preform;
s2: mixing bisphenol A preformed body, solvent and ethylene oxide for addition reaction, and filtering to obtain an initial product;
s3: curing the initial product, and removing the solvent to obtain the bisphenol A polyoxyethylene ether;
the bisphenol A preform comprises a powdery bisphenol A raw material and a powdery catalyst, and is prepared by pressing the raw material into annular particles with the diameter of 2-5cm by using a die.
By adopting the technical scheme, the bisphenol A raw material and the powdery catalyst are prefabricated into annular particles with moderate size, and the annular particles are matched with a proper solvent, so that the bisphenol A can be dissolved at normal temperature or at a lower heating temperature (such as 40-60 ℃), the step of preheating the bisphenol A in the traditional process is avoided, and the consumption of energy sources is saved.
In addition, the state of the catalyst and bisphenol A in the solution tends to be uniform in the dissolution and disintegration process of the annular preform, and when the ethylene oxide is uniformly mixed gradually, the reaction between the ethylene oxide and bisphenol A is also started, so that the time that the ethylene oxide can react after the bisphenol A and the catalyst are uniformly mixed can be avoided, the reaction efficiency is improved, the steps are reduced, and the economic benefit is improved.
Preferably, the raw materials of the bisphenol A preform further comprise an ethanol supplement, and the ethanol supplement is prepared from the following components in parts by weight: 60-80 parts of alcohol with the mass fraction of more than or equal to 95 percent and 10-15 parts of calcium acetate solution with the mass fraction of 40-50 percent; adding a calcium acetate solution into alcohol according to a proportion, stirring until the ethanol supplement is sticky, uniformly stirring and mixing the ethanol supplement with other raw materials of the bisphenol A preform according to a weight ratio of 1:1-5 with the powdery bisphenol A raw materials, and then pressing; the solvent in the step S2 is a mixed solution of dilute sulfuric acid and ethanol.
By adopting the technical scheme, after the prepared gel-like ethanol supplement is mixed and mixed into the raw materials of the bisphenol A preform, the bonding strength between the powdery bisphenol A raw materials and the catalyst in the pressing process is better, the formed annular bisphenol A preform is not easy to disintegrate in the unreacted processes of storage and the like, and the stability is improved. When the cyclic bisphenol A preform is added into the solvent, the dilute sulfuric acid and the ethanol supplement are combined to release ethanol due to the existence of the dilute sulfuric acid solution, so that the local ethanol concentration in the solution near the cyclic particles is increased, and the dissolving process of bisphenol A is accelerated; and after the gradual reaction of the ethanol supplement releases ethanol, the cyclic bisphenol A preform structure is more easily disintegrated, so that the dissolving process of bisphenol A is further improved.
Preferably, 8-15 parts of sodium carbonate powder and 8-15 parts of boric acid powder are added into the ethanol supplement, and the sodium carbonate powder and the boric acid powder are mixed and pressed into particles with the particle size of 1-5mm and then added into the ethanol supplement which is solidified to be gel.
The water content of the colloidal ethanol supplement is extremely low. The mixed particles of the sodium carbonate powder and the boric acid powder added in the ethanol supplement can disintegrate under the condition of meeting water or acid solution and the like, and carbon dioxide bubbles are generated. Therefore, when the annular bisphenol A preformed body is mixed with the solvent for dissolution, bubbles are continuously generated on the surface of the annular bisphenol A preformed body in the disintegration process, the bubbles can push the preformed body which is not completely dissolved but is disintegrated into small particles to float upwards on one hand, and on the other hand, the bubbles can promote the dissolved bisphenol A to be rapidly and fully diffused in the solution, so that the contact time of ethylene oxide and bisphenol A is shortened, and the reaction efficiency is improved.
Preferably, a part of the bisphenol a preform is further assembled with a spherical core, the spherical core including an elliptical magnet and an ethanol supplement included outside the magnet; and in the step S1, an electromagnetic device for driving the magneton to move in the inner ring of the reaction kettle is arranged in the reaction kettle for dissolving the bisphenol A preform.
Through adopting above-mentioned technical scheme, embedding spherical inner core in the annular bisphenol A prefabrication body, spherical inner core on the one hand is through the interaction of magneton and electromagnetic means, and magneton can drive spherical inner core and annular bisphenol A prefabrication body together and carry out annular motion in the solution to strengthen the stirring effect of solution, and in the in-process that bisphenol A prefabrication body moved, probably bump between the bisphenol A prefabrication body of difference, thereby the disintegration process of accelerating bisphenol A prefabrication body, further improve bisphenol A's dissolution process. The moving speed of the bisphenol A preformed body with the magnetic spherical inner core can be conveniently controlled by controlling the electromagnetic device, and when the moving speed is faster, the disintegration process of the bisphenol A preformed body is faster and the bisphenol A preformed body is easier to uniformly mix.
Preferably, the preparation of the spherical inner core, the preparation of the bisphenol A preformed body and the assembly of the bisphenol A preformed body and the spherical inner core are all completed in sequence in the same die;
the mold comprises an upper mold and a lower mold, wherein a plurality of hemispherical first cavities for forming spherical inner cores by pressing are uniformly formed on the matching surfaces of the upper mold and the lower mold, annular grooves for forming bisphenol A preformed bodies by pressing are formed on the vertical matching surfaces of the upper mold and the lower mold along the circumferential direction of the first cavities, pressing grooves penetrating through the upper mold are formed in the groove bottoms of the annular grooves on the upper mold, and supplementing grooves for filling powdery bisphenol A raw materials are formed in the groove bottoms of the annular grooves on the lower mold;
when the ethanol supplement needs to be pressed, a blocking piece is mounted above the upper die in a matched manner, the blocking piece comprises a first pressing plate matched with the upper surface of the upper die and a plurality of first annular pressing blocks uniformly arranged on one side of the first pressing plate close to the upper die, the first annular pressing blocks are in sliding fit with the pressing grooves, and the annular pressing blocks penetrate through the pressing grooves and are abutted against the groove bottoms of the annular grooves on the lower die;
when annular bisphenol A particles need to be filled, a forming part is arranged above the upper die in a matched manner, the assembly part comprises a second pressing plate matched with the upper surface of the upper die and a plurality of second annular pressing blocks uniformly arranged on one side of the second pressing plate close to the upper die, the second annular pressing blocks are in sliding fit with the pressing grooves, and the end surfaces of the second annular pressing blocks are flush with the groove bottoms of the annular grooves on the upper die;
when annular bisphenol A particles need to be pressed, a filling piece is arranged below the lower die in a matched mode, the filling piece comprises a third pressing plate matched with the lower surface of the lower die and a plurality of third annular pressing blocks uniformly arranged on one side, close to the lower die, of the third pressing plate, the third annular pressing blocks are in sliding fit with the complementary grooves, and the end faces of the third annular pressing blocks are flush with the groove bottoms of annular grooves on the lower die;
the upper die is provided with a pressing piece in a matched mode, the pressing piece comprises a fourth pressing plate matched with the upper surface of the upper die and a plurality of fourth annular pressing blocks uniformly arranged on one side, close to the upper die, of the fourth pressing plate, the fourth annular pressing blocks are in sliding fit with the pressing groove, and the fourth annular pressing blocks penetrate through the pressing groove and extend into the annular groove on the upper die.
Preferably, the specific preparation steps of the bisphenol A preform are as follows:
a1: preparing a spherical inner core, assembling the blocking piece and the upper die in a matched manner, putting an elliptic magnet into the first cavity, filling a gelatinous ethanol supplement into the first cavity, assembling and compacting the upper die and the lower die, and then taking out the blocking piece;
a2: filling bisphenol A preform raw materials, completing the matching and assembling of a formed part and an upper die, filling the bisphenol A preform raw materials into annular grooves of the upper die and a lower die from a supplementing groove, completing the matching and assembling of the filled part and the lower die after filling, and removing the formed part;
a3: preparing a bisphenol A prefabricated body, assembling the bisphenol A prefabricated body and the spherical inner core, assembling a pressing piece and an upper die in a matched manner, and extruding by using a cylinder until a fourth pressing plate is attached to the upper surface of the upper die; and removing the upper die and the lower die to obtain the bisphenol A preform.
By the aid of the die and the preparation steps, the assembly of the bisphenol A preform and the spherical inner core can be conveniently and rapidly prepared, and the cost is low.
Preferably, before filling the bisphenol A preform material in the step A2, a layer of 60% calcium acetate solution is sprayed on the groove wall and the groove bottom of the annular groove.
By adopting the technical scheme, the calcium acetate solution is sprayed and attached on the groove wall and the groove bottom of the annular groove, so that the ethanol supplement in the bisphenol A preform filled in the annular groove can be further solidified under the action of the calcium acetate. Thus, during the pressing of the bisphenol A preform, the bisphenol A preform is more stable after being produced.
Preferably, the catalyst is selected from one or more of sodium carbonate, potassium hydroxide, sodium methoxide and potassium methoxide.
The alkaline catalyst can improve the alkaline strength of the solution, and the improvement of the alkaline strength can promote the dissolution of bisphenol A.
Preferably, in the step S2, the bisphenol a preform and the solvent are mixed and stirred for 20min, and then the ethylene oxide aqueous solution is injected from the bottom of the solvent.
According to the technical scheme, the ethylene oxide aqueous solution is injected from the bottom of the solvent, and as the density of the ethylene oxide is lower than that of water, the ethylene oxide gradually diffuses from the bottom of the solvent to the upper side of the solvent. The main place of dissolution is above the solvent due to the generation of carbon dioxide bubbles, and the dissolved bisphenol A gradually diffuses downwards due to the concentration difference, so that the bisphenol A is continuously dissolved, continuously diffused and continuously contacted and mixed with ascending ethylene oxide for reaction, and the dissolution and the reaction of the bisphenol A can be basically carried out synchronously.
And the small particles after the disintegration of the annular bisphenol A preform are positioned at the uppermost layer of the solution under the assistance of carbon dioxide bubbles, and after the ethylene oxide is diffused to the uppermost layer of the solution, the small particles are basically dissolved completely, so that the reaction is initiated, and the reaction efficiency is improved.
Preferably, the bottom of the solvent is provided with a slow release layer, and the slow release layer adopts an asbestos layer with the thickness of 1/4-1/3 of the depth of the solvent.
The asbestos layer can reduce the diffusion speed of the ethylene oxide, so that the ethylene oxide can be matched with the dissolution speed of the bisphenol A, and the preparation efficiency and quality of the bisphenol A polyoxyethylene ether are improved.
In summary, the application has the following beneficial effects:
1. the application adopts the steps of pressing bisphenol A raw material and catalyst into annular preform particles in advance and matching with solvent for dissolution, thereby avoiding the process of heating and melting bisphenol A in the traditional process, reducing the energy loss and improving the reaction efficiency of bisphenol A.
2. In the application, the ethanol supplement is preferably added into bisphenol A preformed body particles to be used as a binder, a disintegrating agent and a solvent supplement, so that the storage stability and the dissolution efficiency of the bisphenol A preformed body are improved.
3. According to the application, the disintegration efficiency and the mixing and dissolving efficiency of the bisphenol A preform are improved by adopting a mode of matching and assembling the spherical inner core and a part of annular bisphenol A preform.
4. According to the application, by adding ethylene oxide from the bottom of the solution and matching with the bisphenol A preform, bisphenol A diffuses from top to bottom in the solution, and ethylene oxide diffuses from bottom to top, so that dissolution and reaction can be performed in the solution in a partitioning mode at the same time, and the reaction efficiency is improved.
Drawings
Fig. 1 is a partial sectional view of a mold in embodiment 1 of the present application for showing the connection relationship between a stopper and upper and lower molds;
fig. 2 is a partial sectional view of a mold in embodiment 1 of the present application for showing the connection relationship between a molded article and an upper mold and a lower mold;
fig. 3 is a partial sectional view of the mold in embodiment 1 of the present application for showing the connection relationship between the filler and the pressing member and the upper and lower molds.
Description of the drawings: 1. an upper die; 11. a first cavity; 12. an annular groove; 13. a pressing groove; 14. a replenishment tank; 2. a lower die; 3. a blocking member; 31. a first platen; 32. a first annular briquette; 4. a molding member; 41. a second pressing plate; 42. a second annular briquette; 5. a filler; 51. a third platen; 52. a third annular briquette; 6. pressing; 61. a fourth pressing plate; 62. a fourth annular briquette; 7. a magnet.
Detailed Description
The application is described in further detail below with reference to figures 1-3 and examples.
Examples
Example 1
The embodiment 1 discloses a bisphenol A polyoxyethylene ether synthesis process, which comprises the following steps:
s1: bisphenol A preform was prepared. The bisphenol A preform comprises a powdery bisphenol A raw material and a powdery catalyst in a mass ratio of 100:1, wherein the catalyst is a mixture of sodium carbonate and potassium hydroxide in a mass ratio of 1:10. Uniformly mixing the powdery bisphenol A raw material and the powdery catalyst in proportion, and extruding by using a die to obtain the annular bisphenol A preform with the diameter of 5cm and the thickness of 1 cm.
The die structure mainly comprises an upper die 1 and a lower die 2, wherein a plurality of hemispherical first cavities 11 are uniformly formed in the matching surface of the lower die 2, and a plurality of hemispherical protruding blocks used for being matched with the first cavities 11 are fixedly connected to the matching surface of the upper die 1. The vertical matching surfaces on the upper die 1 and the lower die 2 are provided with annular grooves 12 for pressing the bisphenol A preformed body along the circumferential direction of the first cavity 11. The bottom of the annular groove 12 on the upper die 1 is provided with a pressing groove 13 penetrating through the upper die 1; the bottom of the annular groove 12 on the lower die 2 is provided with a supplementing groove 14 for filling the powdery bisphenol A raw material.
The upper part of the upper die 1 can be matched and provided with a forming part 4 and a pressing part 6, and the forming part 4 comprises a second pressing plate 41 matched with the upper surface of the upper die 1 and a plurality of second annular pressing blocks 42 uniformly and fixedly connected to one side of the second pressing plate 41 close to the upper die 1. The second annular pressing block 42 is in sliding fit with the pressing groove 13, and the end face of the second annular pressing block 42 is flush with the groove bottom of the annular groove 12 on the upper die 1. The pressing piece 6 comprises a fourth pressing plate 61 matched with the upper surface of the upper die 1 and a plurality of fourth annular pressing blocks 62 uniformly arranged on one side of the fourth pressing plate 61 close to the upper die 1, the fourth annular pressing blocks 62 are in sliding fit with the pressing grooves 13, and the fourth annular pressing blocks 62 penetrate through the pressing grooves 13 and extend into the annular grooves 12 on the upper die 1.
The packing 5 is installed in the cooperation of the below of bed die 2, and packing 5 includes the third clamp plate 51 that cooperatees with bed die 2 lower surface and even fixed connection in a plurality of third annular briquetting 52 of third clamp plate 51 near bed die 2 one side, third annular briquetting 52 and supplementary groove 14 sliding fit, and third annular briquetting 52 terminal surface flushes with the ring channel 12 tank bottom on the bed die 2.
The steps of pressing annular bisphenol A prefabricated member by the die are as follows:
a1: filling bisphenol A preform raw materials, completing the matching and assembling of the molding part 4 and the upper die 1, then filling the bisphenol A preform raw materials into annular grooves 12 of the upper die 1 and the lower die 2 from a supplementing groove 14, completing the matching and assembling of the filling part 5 and the lower die 2 after filling, and removing the molding part 4;
a2: preparing a bisphenol A preform, assembling the bisphenol A preform and a spherical inner core, assembling a pressing piece 6 and the upper die 1 in a matched manner, and extruding by using a cylinder until a fourth pressing plate 61 is attached to the upper surface of the upper die 1; and removing the upper die 1 and the lower die 2 to obtain the bisphenol A preform.
S2: adding bisphenol A preformed body, solvent and ethylene oxide into a reaction kettle according to the mass ratio of 20:50:1, mixing, heating and reacting for 40min, cooling and filtering to obtain the initial product. The solvent is a mixture of ethanol and dimethylbenzene in a mass ratio of 1:2.
S3: and (3) curing the initial product, and removing the solvent under reduced pressure to obtain the bisphenol A polyoxyethylene ether.
Example 2
The difference from example 1 is that the diameter of the annular bisphenol A preform is 2cm.
Example 3
The difference from example 1 is that the diameter of the annular bisphenol A preform is 3cm.
Example 4
Example 4 differs from example 1 in that the raw material of the bisphenol A preform is further added with an ethanol supplement in a mass ratio of 1:5 with respect to the powdered bisphenol A raw material. The ethanol supplement comprises the following components in parts by weight: 80 parts of 98% alcohol and 15 parts of 40% calcium acetate solution.
Before compacting bisphenol A preform material, adding calcium acetate solution into alcohol in proportion, stirring until the mixture is sticky, adding powdery bisphenol A material and powdery catalyst into ethanol supplement, stirring uniformly, and then adding into a die for compacting.
The solvent in the step S2 is a mixed solution of dilute sulfuric acid and ethanol with the mass fraction of 15%, and the mass ratio of the dilute sulfuric acid to the ethanol is 1:1.
Example 5
Example 5 differs from example 4 in that the ethanol supplement is prepared from the following components in parts by weight: 60 parts of 98% alcohol and 10 parts of 40% calcium acetate solution.
Example 6
Example 6 differs from example 4 in that the ethanol supplement is prepared from the following components in parts by weight: 70 parts of 98% alcohol and 13 parts of 40% calcium acetate solution.
Example 7
The difference from example 4 is that 8kg of sodium carbonate powder and 8kg of boric acid powder were added to the ethanol supplement, and the sodium carbonate powder and the boric acid powder were uniformly mixed and pressed into granules having a particle size of 5 mm.
Before compacting, the bisphenol A preform raw material is added into alcohol according to a certain proportion, stirred until the mixture is sticky, extruded to remove more than 60% of water, then added with powder bisphenol A raw material, powder catalyst, sodium carbonate powder and boric acid powder compacted granules, continuously stirred uniformly, and then added into a die for compacting.
Example 8
The difference from example 7 is that the amounts of sodium carbonate powder and boric acid powder are 10kg.
Example 9
The difference from example 7 is that the amounts of sodium carbonate powder and boric acid powder are 15kg.
Example 10
The difference from example 7 is that 50% of bisphenol a preform having a spherical core assembled therein was prepared by the following mold 2 and method.
The difference between the mold and the embodiment 1 is that the first cavity 11 is uniformly formed on the matching surface of the upper mold 1, and the spherical cavity can be formed after the upper mold 2 and the lower mold 2 are matched.
The upper die 1 is provided with a blocking piece 3 in a matched mode, the blocking piece 3 comprises a first pressing plate 31 matched with the upper surface of the upper die 1 and a plurality of first annular pressing blocks 32 uniformly arranged on one side, close to the upper die 1, of the first pressing plate 31, the first annular pressing blocks 32 are in sliding fit with the pressing groove 13, and the annular pressing blocks penetrate through the pressing groove 13 to abut against the groove bottom of the annular groove 12 on the lower die 2.
The preparation steps of the bisphenol A preform are as follows:
a1: preparing a spherical inner core, completing the matching and assembling of the blocking piece 3 and the upper die 1, putting the elliptic magnet 7 into the first cavity 11, filling the gel-like ethanol supplement into the first cavity 11, assembling and compacting the upper die 1 and the lower die 2, and then taking out the blocking piece 3;
a2: filling bisphenol A preform raw materials, completing the matching and assembling of the molding part 4 and the upper die 1, then filling the bisphenol A preform raw materials into annular grooves 12 of the upper die 1 and the lower die 2 from a supplementing groove 14, completing the matching and assembling of the filling part 5 and the lower die 2 after filling, and removing the molding part 4;
a3: preparing a bisphenol A preform, assembling the bisphenol A preform and a spherical inner core, assembling a pressing piece 6 and the upper die 1 in a matched manner, and extruding by using a cylinder until a fourth pressing plate 61 is attached to the upper surface of the upper die 1; and removing the upper die 1 and the lower die 2 to obtain the bisphenol A preform.
An electromagnetic device for driving the magnet 7 to move in the reaction kettle is arranged on the reaction kettle.
Example 11
The difference from example 10 is that step S2 is: the bisphenol A preform was mixed with the solvent and stirred for 20 minutes, and then an aqueous ethylene oxide solution was added from the bottom of the solvent at a flow rate of 2 m/s.
Example 12
The difference from example 11 is that the bottom of the reaction vessel was filled with an asbestos layer, and the ratio of the thickness of the asbestos layer to the height of the solution in the reaction vessel was 1:4.
Example 13
The difference from example 4 is that a layer of 60% by mass of calcium acetate solution is sprayed on the walls and the bottoms of the annular grooves before filling the bisphenol A preform material in step A2.
Comparative example
Comparative example 1 discloses a bisphenol a polyoxyethylene ether synthesis process, which is prepared by the following steps:
s1, heating bisphenol A to 158 ℃ for melting, then adding a solid Na2CO3 and KOH mixed catalyst, uniformly stirring, discharging nitrogen for a plurality of times, discharging residual air in a kettle, and closing the reaction kettle;
and S2, introducing ethylene oxide into the solution obtained in the step S1 to react, wherein the reaction temperature is 150 ℃.
And S3, curing the reaction product, and refining to obtain the bisphenol A polyoxyethylene ether.
The amounts of bisphenol A, catalyst and ethylene oxide used were the same as in example 1.
Comparative example 2
The difference from example 7 is that the powdered bisphenol A starting material, the powdered catalyst are dissolved in a solvent and ethylene oxide is subsequently added.
Performance test
The performance index of the bisphenol A polyoxyethylene ether finished product prepared in the example 1 is detected, and the detection result is as follows:
| index name | Index value |
| Appearance of | Colorless to pale yellow transparent liquid |
| Hydroxyl value mgKOH/g | 200-250 |
| Acid value mgKOH/g | 0.1 |
| The water content is less than or equal to | 0.1 |
| Color Pt-Co number is less than or equal to | 80 |
| K+/ppm≤ | 10 |
| Na+/ppm≤ | 10 |
The performance index of the bisphenol A polyoxyethylene ether products of examples 2-11 and comparative examples 1-2 was measured and was similar to that of example 1.
The yields of bisphenol A polyoxyethylene ether as the main component were examined and shown in the following table.
Conclusion: firstly, indexes of the bisphenol A polyoxyethylene ether prepared in the embodiment of the application are similar to those of bisphenol A polyoxyethylene ether prepared in a traditional mode, and the bisphenol A polyoxyethylene ether is proved to be better prepared into qualified bisphenol A polyoxyethylene ether in a synthetic mode compared with the traditional preparation mode, but bisphenol A is not required to be heated and melted in advance in the application, and the whole energy consumption is still lower than that of the traditional heating mode although the bisphenol A prefabricated body is prepared in advance.
Next, the yield of example 1 is higher than those of comparative examples 1 and 2, indicating that the uniformity of dissolution, and thus the uniformity of reaction, can be improved by supporting the bisphenol a raw material and the catalyst in advance with the cyclic particles in the present application.
Example 1 shows that the higher yields of examples 4, 5 and 6 compared to examples 4, 5 and 6 indicate that the addition of the ethanol supplement allows the bisphenol a starting material to be maintained or even increased during dissolution, thus allowing more complete and uniform dissolution of bisphenol a, and faster dissolution, and faster diffusion during re-reaction, i.e., increased yields from the side.
Examples 7, 8 and 9 compared with example 4, it can be seen that after the particles formed by mixing sodium carbonate and boric acid are added in the ethanol supplement, the disintegration of bisphenol a raw material and the carbon dioxide bubbles formed by the reaction of sodium carbonate and boric acid can improve the diffusion of dissolved bisphenol a in the solution, accelerate the contact between bisphenol a and ethylene oxide, and simultaneously accelerate the faster disintegration of undissolved bisphenol a, thereby improving the dissolution degree of bisphenol a, thereby improving the reaction progress to a certain extent and improving the yield.
As can be seen by comparing example 10 with example 7, there is also a certain increase in yield after assembly of the spherical core. It is possible that the magnetons in the spherical core, when driving the annular bisphenol a preform into motion, accelerate the disintegration of bisphenol a and, to some extent, maintain a balance between the contact between dissolved bisphenol a and the acceleration with ethylene oxide and the accelerated cleavage of solid bisphenol a, thereby increasing the rate and progress of the reaction and hence the yield.
Example 11 shows that by changing the addition position of ethylene oxide, the disintegration of bisphenol a and the dissolution of bisphenol a are better balanced, and only the downward-diffused portion of bisphenol a reacts with ethylene oxide in advance, so that the reaction is continuously initiated to a certain extent, the reactants are continuously increased, the synthesis reaction is higher, the reaction is more complete, and the yield is higher.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (7)
1. The bisphenol A polyoxyethylene ether synthesis process is characterized by comprising the following steps of:
s1: preparing a bisphenol A preform;
s2: mixing bisphenol A preformed body, solvent and ethylene oxide for addition reaction, and filtering to obtain an initial product;
s3: curing the initial product, and removing the solvent to obtain the bisphenol A polyoxyethylene ether;
the raw materials of the bisphenol A preform comprise powdery bisphenol A raw materials and powdery catalyst, and the preparation method comprises the steps of pressing the raw materials into annular particles with the diameter of 2-5cm by using a die;
the raw materials of the bisphenol A preform further comprise an ethanol supplement, and the ethanol supplement is prepared from the following components in parts by weight: 60-80 parts of alcohol with the mass fraction of more than or equal to 95 percent and 10-15 parts of calcium acetate solution with the mass fraction of 40-50 percent; adding a calcium acetate solution into alcohol according to a proportion, stirring until the ethanol supplement is sticky, uniformly stirring and mixing the ethanol supplement with other raw materials of the bisphenol A preform according to a weight ratio of 1:1-5 with the powdery bisphenol A raw materials, and then pressing; the solvent in the step S2 is a mixed solution of dilute sulfuric acid and ethanol;
8-15 parts of sodium carbonate powder and 8-15 parts of boric acid powder are added into the ethanol supplement, and the sodium carbonate powder and the boric acid powder are mixed and pressed into particles with the particle size of 1-5mm and then added into the solidified ethanol supplement;
the catalyst is selected from one or more of sodium carbonate, potassium hydroxide, sodium methoxide and potassium methoxide.
2. The bisphenol a polyoxyethylene ether synthesis process according to claim 1, wherein: a part of bisphenol A prefabrication body is also assembled with a spherical inner core, and the spherical inner core comprises an elliptic magnet (7) and a solidified ethanol supplement covered outside the magnet (7); an electromagnetic device for driving the magnet (7) to move in the inner ring of the reaction kettle is arranged in the reaction kettle for dissolving the bisphenol A preformed body in the step S1.
3. The bisphenol a polyoxyethylene ether synthesis process according to claim 2, wherein: the preparation of the spherical inner core, the preparation of the bisphenol A preformed body and the assembly of the bisphenol A preformed body and the spherical inner core are all completed in sequence in the same die; the mold comprises an upper mold (1) and a lower mold (2), wherein a plurality of hemispherical first cavities (11) for forming spherical inner cores by pressing are uniformly formed on the matching surfaces of the upper mold (1) and the lower mold (2), annular grooves (12) for forming bisphenol A preformed bodies by pressing are formed in the vertical matching surfaces of the upper mold (1) and the lower mold (2) along the circumferential direction of the first cavities (11), pressing grooves (13) penetrating through the upper mold (1) are formed in the bottoms of the annular grooves (12) on the upper mold (1), and supplementing grooves (14) for filling powdery bisphenol A raw materials are formed in the bottoms of the annular grooves (12) on the lower mold (2); when an ethanol supplement is required to be pressed, a blocking piece (3) is mounted above the upper die (1) in a matched mode, the blocking piece (3) comprises a first pressing plate (31) matched with the upper surface of the upper die (1) and a plurality of first annular pressing blocks (32) uniformly arranged on one side, close to the upper die (1), of the first pressing plate (31), the first annular pressing blocks (32) are in sliding fit with the pressing groove (13), and the annular pressing blocks penetrate through the pressing groove (13) to be abutted against the groove bottom of the annular groove (12) on the lower die (2); when annular bisphenol A particles need to be filled, a forming part (4) is mounted above the upper die (1) in a matched mode, the forming part (4) comprises a second pressing plate (41) matched with the upper surface of the upper die (1) and a plurality of second annular pressing blocks (42) uniformly arranged on one side, close to the upper die (1), of the second pressing plate (41), the second annular pressing blocks (42) are in sliding fit with the pressing grooves (13), and the end faces of the second annular pressing blocks (42) are flush with the bottoms of annular grooves (12) on the upper die (1); when annular bisphenol A particles need to be pressed, a filling piece (5) is mounted below the lower die (2) in a matched mode, the filling piece (5) comprises a third pressing plate (51) matched with the lower surface of the lower die (2) and a plurality of third annular pressing blocks (52) uniformly arranged on one side, close to the lower die (2), of the third pressing plate (51), the third annular pressing blocks (52) are in sliding fit with the supplementing grooves (14), and the end faces of the third annular pressing blocks (52) are flush with the groove bottoms of annular grooves (12) on the lower die (2); the upper die (1) is provided with a pressing piece (6) in a matched mode, the pressing piece (6) comprises a fourth pressing plate (61) matched with the upper surface of the upper die (1) and a plurality of fourth annular pressing blocks (62) uniformly arranged on one side, close to the upper die (1), of the fourth pressing plate (61), the fourth annular pressing blocks (62) are in sliding fit with the pressing groove (13), and the fourth annular pressing blocks (62) penetrate through the pressing groove (13) to extend into an annular groove (12) on the upper die (1).
4. A bisphenol a polyoxyethylene ether synthesis process according to claim 3, wherein: the specific preparation steps of the bisphenol A preform are as follows:
a1: preparing a spherical inner core, completing the matching and assembling of the blocking piece (3) and the upper die (1), putting the oval-shaped magnet (7) into the first cavity (11), filling gel-like ethanol supplement into the first cavity (11), assembling and compacting the upper die (1) and the lower die (2), and then taking out the blocking piece (3);
a2: filling bisphenol A preformed body raw materials, completing the matching and assembling of a formed part (4) and an upper die (1), then filling the bisphenol A preformed body raw materials into annular grooves (12) of the upper die (1) and a lower die (2) from a supplementing groove (14), completing the matching and assembling of a filling part (5) and the lower die (2) after filling, and removing the formed part (4);
a3: preparing a bisphenol A prefabricated body, assembling the bisphenol A prefabricated body and a spherical inner core, assembling a pressing piece (6) and an upper die (1) in a matched mode, and extruding by using an air cylinder until a fourth pressing plate (61) is attached to the upper surface of the upper die (1); and (3) removing the upper die (1) and the lower die (2) to obtain the bisphenol A preform.
5. The bisphenol a polyoxyethylene ether synthesis process according to claim 4, wherein: before the bisphenol A preform raw material is filled in the step A2, a layer of 60% calcium acetate solution is sprayed on the groove wall and the groove bottom of the annular groove.
6. The bisphenol a polyoxyethylene ether synthesis process according to claim 1, wherein: in the step S2, the bisphenol A preformed body and the solvent are mixed and stirred, and then the ethylene oxide aqueous solution is added from the bottom of the solvent.
7. The bisphenol a polyoxyethylene ether synthesis process of claim 6, wherein: the bottom of the solvent is provided with a slow-release layer, and the slow-release layer adopts an asbestos layer with the thickness of 1/4-1/3 of the depth of the solvent.
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| CN101367714A (en) * | 2008-08-25 | 2009-02-18 | 杭州白浪助剂有限公司 | Preparation method of bisphenol A polyethenoxy ether toughening agent |
| JP2009057405A (en) * | 2007-08-30 | 2009-03-19 | Sanyo Chem Ind Ltd | Granulation method for polyoxyethylene ether of bisphenol a |
| CN107488531A (en) * | 2017-08-29 | 2017-12-19 | 广州立白企业集团有限公司 | A kind of neutral Instant detergent bar composition and preparation method thereof |
| CN109049280A (en) * | 2018-07-16 | 2018-12-21 | 昆明理工大学 | A kind of production equipment and application method of space structure precast body |
| CN113396940A (en) * | 2021-07-07 | 2021-09-17 | 杭州龙能科技有限公司 | Ultralow temperature resistant disinfectant |
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|---|---|---|---|---|
| JP2009057405A (en) * | 2007-08-30 | 2009-03-19 | Sanyo Chem Ind Ltd | Granulation method for polyoxyethylene ether of bisphenol a |
| CN101367714A (en) * | 2008-08-25 | 2009-02-18 | 杭州白浪助剂有限公司 | Preparation method of bisphenol A polyethenoxy ether toughening agent |
| CN107488531A (en) * | 2017-08-29 | 2017-12-19 | 广州立白企业集团有限公司 | A kind of neutral Instant detergent bar composition and preparation method thereof |
| CN109049280A (en) * | 2018-07-16 | 2018-12-21 | 昆明理工大学 | A kind of production equipment and application method of space structure precast body |
| CN113396940A (en) * | 2021-07-07 | 2021-09-17 | 杭州龙能科技有限公司 | Ultralow temperature resistant disinfectant |
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