CN114456353B - Preparation method of bisphenol A epoxy resin with low toluene residue - Google Patents
Preparation method of bisphenol A epoxy resin with low toluene residue Download PDFInfo
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- CN114456353B CN114456353B CN202210270046.XA CN202210270046A CN114456353B CN 114456353 B CN114456353 B CN 114456353B CN 202210270046 A CN202210270046 A CN 202210270046A CN 114456353 B CN114456353 B CN 114456353B
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/025—Polycondensates containing more than one epoxy group per molecule characterised by the purification methods used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a preparation method of bisphenol A epoxy resin with low toluene residue, belonging to the technical field of epoxy resin synthesis. The invention adopts a mode of combining macroscopic stirring and mixing with microscopic molecular mixing in the water washing process, can sufficiently wash away the organic chlorine, the inorganic chlorine and the residual phase transfer catalyst generated in the reaction process, avoids the adsorption of the phase transfer catalyst on toluene, and is beneficial to the removal of toluene in the subsequent reduced pressure distillation process. The method provided by the invention can greatly reduce the toluene residue of bisphenol A epoxy resin, and the results of examples show that the toluene residue of bisphenol A epoxy resin prepared by the method can be reduced to below 10ppm, and the organic chlorine/inorganic chlorine is reduced to 0.001mol/100g.
Description
Technical Field
The invention relates to the technical field of epoxy resin synthesis, in particular to a preparation method of bisphenol A epoxy resin with low toluene residue.
Background
Bisphenol A epoxy resin contains a large amount of polar hydroxyl groups, ether bonds and active epoxy groups, and has excellent adhesion performance and reactivity with various substances such as metals, non-metals and the like. In addition, the rigid structure of benzene ring in the molecular chain endows the bisphenol A epoxy resin with excellent heat resistance, hardness and lower curing shrinkage, so that the bisphenol A epoxy resin is widely applied in the fields of heavy corrosion resistance and powder coating.
There is an increasing demand for electronic grade epoxy resins in the field of advanced manufacturing industry, particularly in the fields of electronic packaging, copper-clad boards, and the like. In order to strictly control the content of organic/inorganic chlorine in the electronic grade epoxy resin and improve the stability and safety of electronic products, a one-step water washing solvent method is generally adopted in the industry to prepare the electronic grade special E-20 bisphenol A epoxy resin, and the epoxy resin prepared by the process has the characteristics of low content of organic/inorganic chlorine and high purity, but a toluene solvent used in a large amount by the process inevitably brings the problems of high toluene residue in an epoxy resin system and the like. The toluene residue of the epoxy resin prepared by the one-step water washing solvent method is higher than 500ppm, which has negative influence on the safety and insulativity of electronic packaging products and copper-clad plates.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing bisphenol a epoxy resin with low toluene residue.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of bisphenol A epoxy resin with low toluene residue, which comprises the following steps:
(1) Heating and mixing bisphenol A, inorganic strong base and water to obtain alkaline solution of bisphenol A;
(2) Mixing the bisphenol A alkaline solution, epichlorohydrin, an alcohol cosolvent and a phase transfer catalyst, and carrying out polymerization reaction to obtain a polymerization reaction solution;
(3) Removing the water phase in the polymerization reaction liquid, and mixing the obtained residual liquid with toluene to obtain a toluene solution of a polymerization product;
(4) Washing the toluene solution of the polymer with water, and removing the water phase to obtain a water-washed polymerization product;
the water washing comprises the following steps: mixing the toluene solution of the polymer with hot water under stirring, and mixing microscopic molecules in the stirring and mixing process; the microscopic level molecular mixing is microwave mixing and/or ultrasonic mixing;
(5) And (3) carrying out reduced pressure distillation on the water-washed polymerization product to obtain the bisphenol A epoxy resin with low toluene residue.
Preferably, the temperature of the hot water in the step (4) is 85-95 ℃.
Preferably, the rotation speed of stirring and mixing in the step (4) is 500-800 r/min, and the time is 10-30 min.
Preferably, the frequency of the microwave mixing in the step (4) is 300 MHz-30 GHz;
the frequency of the ultrasonic mixing is 1.7 MHz-5.0 MHz.
Preferably, the number of times of washing in the step (4) is 1 to 3.
Preferably, the temperature of the heating and mixing in the step (1) is 40-60 ℃.
Preferably, the mass ratio of bisphenol A to epichlorohydrin is 200:90-160;
the mass ratio of the bisphenol A to the alcohol cosolvent is 200:5-20;
the mass ratio of bisphenol A to the phase transfer catalyst is 200:0.2-5.
Preferably, the alcohol cosolvent is one or more of propanol, isopropanol and n-butanol;
the phase transfer catalyst is one or more of triphenylphosphine, triphenylphosphine methyl phosphine bromide, tetrabutylammonium bromide, benzyl trimethyl ammonium chloride and ethyl triphenyl ammonium bromide.
Preferably, the temperature of the polymerization reaction is 90-100 ℃ and the time is 30-90 min.
Preferably, the vacuum degree of the reduced pressure distillation is-0.001 to-0.01 MPa.
The invention provides a preparation method of bisphenol A epoxy resin with low toluene residue, which adopts a one-step solvent water washing method to prepare bisphenol A epoxy resin, specifically, bisphenol A, inorganic strong base and water are heated and mixed to obtain alkaline solution of bisphenol A, and then the alkaline solution of bisphenol A, epichlorohydrin, alcohol cosolvent and phase transfer catalyst are mixed for polymerization reaction to obtain polymerization reaction liquid; then adding the crude product in toluene-soluble polymerization reaction liquid, and removing water-soluble impurities through water washing. The invention adopts a mode of combining macroscopic stirring and mixing with microscopic molecular mixing in the water washing process, can sufficiently wash away the organic chlorine, the inorganic chlorine and the residual phase transfer catalyst generated in the reaction process, avoids the adsorption of the phase transfer catalyst on toluene, and is beneficial to the removal of toluene in the subsequent reduced pressure distillation process. The method provided by the invention can greatly reduce the toluene residue of bisphenol A epoxy resin, and the results of examples show that the toluene residue of bisphenol A epoxy resin prepared by the method can be reduced to below 10ppm, and the organic chlorine/inorganic chlorine is reduced to 0.001mol/100g.
Detailed Description
The invention provides a preparation method of bisphenol A epoxy resin with low toluene residue, which comprises the following steps:
(1) Heating and mixing bisphenol A, inorganic strong base and water to obtain alkaline solution of bisphenol A;
(2) Mixing the bisphenol A alkaline solution, epichlorohydrin, an alcohol cosolvent and a phase transfer catalyst, and carrying out polymerization reaction to obtain a polymerization reaction solution;
(3) Removing the water phase in the polymerization reaction liquid, and mixing the obtained residual liquid with toluene to obtain a toluene solution of a polymerization product;
(4) Washing the toluene solution of the polymer with water, and removing the water phase to obtain a water-washed polymerization product;
the water washing comprises the following steps: mixing the toluene solution of the polymer with hot water under stirring, and mixing microscopic molecules in the stirring and mixing process; the microscopic level molecular mixing is microwave mixing and/or ultrasonic mixing;
(5) And (3) carrying out reduced pressure distillation on the water-washed polymerization product to obtain the bisphenol A epoxy resin with low toluene residue.
The invention mixes bisphenol A, inorganic strong alkali and water by heating to obtain alkaline solution of bisphenol A. In the present invention, the inorganic strong base is preferably sodium hydroxide and/or potassium hydroxide. In the invention, preferably, inorganic strong alkali is mixed with water to obtain inorganic strong alkali aqueous solution, and bisphenol A is mixed with the inorganic strong alkali aqueous solution. In the present invention, the mass concentration of the inorganic strong alkali aqueous solution is preferably 10 to 40%, more preferably 10 to 30%; the mass ratio of bisphenol A to the inorganic strong alkaline aqueous solution is preferably 200:150-500, more preferably 200:200-400.
In the present invention, the heating and mixing are preferably performed under stirring, and the stirring speed is preferably 60 to 200r/min, more preferably 120 to 150r/min. The temperature of the heating and mixing is preferably 40 to 60 ℃, more preferably 40 to 50 ℃, and the time of the heating and mixing is not particularly required, so that bisphenol A can be completely dissolved.
After the alkaline solution of bisphenol A is obtained, the alkaline solution of bisphenol A, epichlorohydrin, an alcohol cosolvent and a phase transfer catalyst are mixed for polymerization reaction to obtain a polymerization reaction solution. In the invention, the mass ratio of bisphenol A to epichlorohydrin is preferably 200:90-160, more preferably 200:120-140; the mass ratio of bisphenol A to the alcohol cosolvent is preferably 200:5-20, more preferably 200:10-15; the mass ratio of bisphenol A to the phase transfer catalyst is preferably 200:0.2-5, more preferably 200:2-5.
In the invention, the alcohol cosolvent is one or more of propanol, isopropanol and n-butanol; the phase transfer catalyst is one or more of triphenylphosphine, triphenylphosphine methyl phosphine bromide, tetrabutylammonium bromide, benzyl trimethyl ammonium chloride and ethyl triphenyl ammonium bromide.
In the present invention, the polymerization is preferably carried out under stirring at a rate of preferably 200 to 600r/min, more preferably 400 to 600r/min. In the present invention, the temperature of the polymerization reaction is preferably 90 to 100 ℃, more preferably 95 to 100 ℃; the rate of heating to the polymerization reaction temperature is preferably 3 to 5 ℃/5min. In the present invention, the polymerization time is preferably 30 to 90 minutes, more preferably 30 to 60 minutes, since the polymerization temperature is raised to the polymerization temperature and then the polymerization time is calculated.
After the polymerization reaction liquid is obtained, the invention removes the water phase in the polymerization reaction liquid, and mixes the obtained residual liquid with toluene to obtain toluene solution of a polymerization product. In the present invention, the means for removing the aqueous phase is preferably liquid separation after standing.
In the present invention, the mass ratio of bisphenol A to toluene is preferably 200:200-300. In the present invention, the mixing means is preferably stirring mixing.
After the toluene solution of the polymerization product is obtained, the toluene solution of the polymer is washed by water, and the water phase is removed to obtain the water-washed polymerization product. In the present invention, the water washing includes: mixing the toluene solution of the polymer with hot water under stirring, and mixing microscopic molecules while stirring; the microscopic level molecular mixing is microwave mixing and/or ultrasonic mixing.
In the present invention, the temperature of the hot water is preferably 85 to 95 ℃, more preferably 90 to 95 ℃. In the invention, the mass ratio of bisphenol A to hot water is preferably 200:200-300.
In the invention, the rotation speed of the stirring and mixing is preferably 500-800 r/min, more preferably 600-700 r/min; the time is preferably 10 to 30 minutes, more preferably 20 to 30 minutes.
In the present invention, the frequency of the microwave mixing is preferably 300MHz to 30GHz, more preferably 500MHz to 10GHz, and even more preferably 1 to 5GHz.
In the present invention, the frequency of the ultrasonic mixing is preferably 1.7MHz to 5.0MHz, more preferably 2.0 to 4.0MHz.
In the present invention, the means for removing the aqueous phase is preferably liquid separation after standing.
In the present invention, the number of times of the washing is preferably 1 to 3, more preferably 2 to 3.
After the water-washed polymerization product is obtained, the water-washed polymerization product is subjected to reduced pressure distillation to obtain the bisphenol A epoxy resin with low toluene residue. In the present invention, the vacuum degree of the reduced pressure distillation is preferably-0.001 to-0.01 MPa. In the present invention, the temperature of the reduced pressure distillation is preferably 90 to 120℃and the time is preferably 30 to 60 minutes. The invention removes the solvent and unreacted epoxy chloropropane by the reduced pressure distillation, and the residual product is bisphenol A epoxy resin with low toluene residue.
The epoxy value of the bisphenol A epoxy resin with low toluene residue obtained by the method is preferably 0.11-0.25 mol/100g, more preferably 0.15-0.2 mol/100g; the toluene residue of the obtained low toluene residue bisphenol A epoxy resin is lower than 10ppm.
The following is a detailed description of the preparation method of the low toluene residual bisphenol A epoxy resin provided by the present invention in connection with examples, but they should not be construed as limiting the scope of the present invention.
Example 1
S1: 200 parts of bisphenol A is added into a 1000ml three-neck flask, 436 parts of 11% concentration sodium hydroxide solution is added, and the mixture is stirred and heated to 45 ℃ at 120r/min until the mixture is completely dissolved;
s2: 120 parts of epichlorohydrin, 10 parts of n-butanol cosolvent and 3 parts of triphenylphosphine bromide phase transfer catalyst are added into the system at one time, the temperature is continuously stirred and raised to 98 ℃ at 500r/min, the temperature raising rate is controlled at 4 ℃/5min, the stirring at the rotating speed is maintained for 60min, and the reaction is finished.
S3: and (3) standing the system, removing the aqueous solution in the system, adding 200 parts of toluene solution, continuously stirring until the toluene solution is completely dissolved, adding 200 parts of hot water at 90 ℃ again, carrying out molecular-level micro-mixing and 600r/min macro-stirring combination by adopting ultrasonic waves with the frequency of 3MHz, mixing for 20 minutes, standing, removing the aqueous phase, and washing for 2 times.
S4: and (3) distilling the epoxy resin toluene solution after water washing under reduced pressure to remove the solvent and unreacted epichlorohydrin, thus obtaining the required bisphenol A epoxy resin with low toluene residue.
Example 2
S1: 200 parts of bisphenol A is added into a 1000ml three-neck flask, 250 parts of 21% sodium hydroxide solution is added, and the mixture is stirred and heated to 49 ℃ under 130r/min until the mixture is completely dissolved;
s2: 140 parts of epichlorohydrin, 15 parts of n-butyl alcohol cosolvent and 4 parts of tetrabutylammonium bromide phase transfer catalyst are added into the system at one time, the temperature is continuously stirred and raised to 95 ℃ at 500r/min, the temperature raising rate is controlled at 5 ℃/5min, the stirring at the rotating speed is maintained for 50min, and the reaction is finished.
S3: and (3) standing the system, removing the aqueous solution in the system, adding 300 parts of toluene solution, continuously stirring until the toluene solution is completely dissolved, adding 200 parts of hot water at 95 ℃ again, carrying out molecular-level micro-mixing and 700r/min macro-stirring combination by adopting 2GHz frequency microwaves, mixing for 20 minutes, standing, removing the aqueous phase, and washing for 2 times.
S4: and (3) distilling the epoxy resin toluene solution after water washing under reduced pressure to remove the solvent and unreacted epichlorohydrin, thus obtaining the required bisphenol A epoxy resin with low toluene residue.
Example 3
S1: 200 parts of bisphenol A is added into a 1000ml three-neck flask, 350 parts of 13% concentration sodium hydroxide solution is added, and the mixture is stirred and heated to 43 ℃ under 130r/min until the mixture is completely dissolved;
s2: 125 parts of epoxy chloropropane, 10 parts of isopropanol cosolvent and 4 parts of ethyl triphenylammonium bromide phase transfer catalyst are added into the system at one time, the temperature is continuously stirred and raised to 98 ℃ at 400r/min, the temperature raising rate is controlled at 4 ℃/5min, the stirring is kept at the rotating speed for 60min, and the reaction is finished.
S3: and (3) standing the system, removing the aqueous solution in the system, adding 300 parts of toluene solution, continuously stirring until the toluene solution is completely dissolved, adding 200 parts of hot water at 95 ℃ again, carrying out molecular-level micro-mixing and 650r/min macro-stirring combination by adopting 3GHz frequency microwaves, mixing for 20 minutes, standing, removing the aqueous phase, and washing for 2 times.
S4: and (3) distilling the epoxy resin toluene solution after water washing under reduced pressure to remove the solvent and unreacted epichlorohydrin, thus obtaining the required bisphenol A epoxy resin with low toluene residue.
Example 4
S1: 200 parts of bisphenol A is added into a 1000ml three-neck flask, 280 parts of 19% sodium hydroxide solution is added, and the temperature is raised to 45 ℃ by stirring at 140r/min until the solution is completely dissolved;
s2: 155 parts of epoxy chloropropane, 13 parts of propanol cosolvent and 2 parts of benzyl trimethyl ammonium chloride phase transfer catalyst are added into the system at one time, the temperature is continuously stirred and raised to 99 ℃ at 450r/min, the temperature raising rate is controlled at 5 ℃/5min, the stirring at the rotating speed is maintained for 40min, and the reaction is finished.
S3: and (3) standing the system, removing the aqueous solution in the system, adding 200 parts of toluene solution, continuously stirring until the toluene solution is completely dissolved, adding 300 parts of hot water at 95 ℃ again, carrying out molecular-level micro-mixing and 700r/min macro-stirring combination by adopting 2MHz frequency ultrasonic waves, mixing for 20 minutes, standing, removing the aqueous phase, and washing for 2 times.
S4: and (3) distilling the epoxy resin toluene solution after water washing under reduced pressure to remove the solvent and unreacted epichlorohydrin, thus obtaining the required bisphenol A epoxy resin with low toluene residue.
Comparative example 1
Compared with example 1, the difference is that step S3 is only performed with 600r/min macroscopic stirring, without 3MHz frequency ultrasonic mixing, and the rest operations are the same, to obtain bisphenol A epoxy resin.
Comparative example 2
In comparison with example 1, the difference is that step S3 is only 3MHz frequency ultrasonic mixing, 600r/min macro stirring is not performed, and the rest of the operations are the same, to obtain bisphenol A epoxy resin.
Comparative example 3
Compared with example 2, the difference is that the step S3 only carries out macroscopic stirring mixing at 700r/min, does not carry out microwave mixing at the frequency of 2GHz, and the rest operations are the same, thus obtaining the bisphenol A epoxy resin.
Comparative example 4
Compared with example 2, the difference is that step S3 only carries out microwave mixing at the frequency of 2GHz, does not carry out macroscopic stirring mixing at the frequency of 700r/min, and the rest operations are the same, thus obtaining the bisphenol A epoxy resin.
The bisphenol A epoxy resins obtained in the above examples and comparative examples were tested for epoxy value, toluene residual amount, organic chlorine residual amount and inorganic chlorine residual amount, and the results are shown in Table 1.
Wherein, 1), the test method of the epoxy value refers to national standard: measuring the epoxy equivalent amount of the GB/T4612-2008 plastic epoxy compound;
2) The test method of toluene residue refers to national standard: measuring benzene, toluene, ethylbenzene and xylene contents in the GB/T23990-2009A method coating by gas chromatography;
3) The method for testing the residual amount of the organic chlorine refers to national standards: determination of chlorine content of GB/T4618.2-2008 Plastic epoxy resin part 2: easy saponification of chlorine;
4) The method for testing the inorganic chlorine residue refers to national standard: determination of chlorine content of GB/T4618.1-2008 Plastic epoxy resin part 2: inorganic chlorine.
TABLE 1 detection results of bisphenol A epoxy resins obtained in examples and comparative examples
As can be seen from Table 1, bisphenol A epoxy resin was produced by the method of the present invention, and the toluene residual amount of the bisphenol A epoxy resin was reduced to less than 10ppm, and the organochlorine/inorganic chlorine was reduced to 0.0015mol/100g.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The preparation method of the bisphenol A epoxy resin with low toluene residue comprises the following steps:
(1) Heating and mixing bisphenol A, inorganic strong base and water to obtain alkaline solution of bisphenol A;
(2) Mixing the bisphenol A alkaline solution, epichlorohydrin, an alcohol cosolvent and a phase transfer catalyst, and carrying out polymerization reaction to obtain a polymerization reaction solution; the temperature of the polymerization reaction is 90-100 ℃, and the heat preservation time is 30-90 min;
the mass ratio of bisphenol A to epichlorohydrin is 200:90-160;
the mass ratio of the bisphenol A to the alcohol cosolvent is 200:5-20;
the mass ratio of bisphenol A to the phase transfer catalyst is 200:0.2-5;
(3) Removing the water phase in the polymerization reaction liquid, and mixing the obtained residual liquid with toluene to obtain a toluene solution of a polymerization product;
(4) Washing the toluene solution of the polymer with water, and removing the water phase to obtain a water-washed polymerization product;
the water washing comprises the following steps: mixing the toluene solution of the polymer with hot water under stirring, and mixing microscopic molecules in the stirring and mixing process; the microscopic level molecular mixing is microwave mixing and/or ultrasonic mixing;
the temperature of the hot water is 85-95 ℃;
the rotation speed of stirring and mixing is 500-800 r/min, and the time is 10-30 min;
the frequency of microwave mixing is 300 MHz-30 GHz;
the ultrasonic mixing frequency is 1.7 MHz-5.0 MHz;
(5) And (3) carrying out reduced pressure distillation on the water-washed polymerization product to obtain the bisphenol A epoxy resin with low toluene residue.
2. The preparation method according to claim 1, wherein the number of times of water washing in the step (4) is 1 to 3.
3. The preparation method of claim 1, wherein the heating and mixing temperature in the step (1) is 40-60 ℃.
4. The method of claim 1, wherein the alcoholic co-solvent is one or more of propanol, isopropanol, and n-butanol;
the phase transfer catalyst is one or more of triphenylphosphine, triphenylphosphine methyl phosphine bromide, tetrabutylammonium bromide, benzyl trimethyl ammonium chloride and ethyl triphenyl ammonium bromide.
5. The method according to claim 1, wherein the vacuum degree of the reduced pressure distillation is-0.001 to-0.01 MPa.
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| JP3044412B2 (en) * | 1991-07-08 | 2000-05-22 | 東都化成株式会社 | Manufacturing method of high purity epoxy resin |
| CN101265320A (en) * | 2007-03-16 | 2008-09-17 | 西北工业大学 | Method for preparing low content of organic chlorine epoxy resin |
| CN101613458B (en) * | 2008-06-25 | 2013-06-05 | 中国石油化工集团公司 | Method for preparing bisphenol-A liquid epoxy resin |
| CN102850519B (en) * | 2011-07-31 | 2014-10-08 | 江苏扬农锦湖化工有限公司 | Synthetic method of epoxy resin |
| CN103827161B (en) * | 2011-09-27 | 2016-11-23 | 蓝立方知识产权有限责任公司 | For making the reciprocating vibration plate formula tower reactor of epoxy resin epoxy |
| WO2016127492A1 (en) * | 2015-02-10 | 2016-08-18 | 北京化工大学 | Novel tetra-phenolic compound/tetra-functionality epoxy resin, preparation method and application |
| CN113024772B (en) * | 2019-12-24 | 2022-12-09 | 山东圣泉新材料股份有限公司 | Bisphenol A novolac epoxy resin and preparation method thereof |
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| JP2009051021A (en) * | 2007-08-23 | 2009-03-12 | Jsr Corp | Producing method for resin composition molding |
| CN106749106A (en) * | 2016-12-23 | 2017-05-31 | 湖北绿色家园材料技术股份有限公司 | The synthetic method of ethylene glycol diglycidylether |
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