CN111978277A - Preparation method of bisphenol A type diether dianhydride - Google Patents
Preparation method of bisphenol A type diether dianhydride Download PDFInfo
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- CN111978277A CN111978277A CN201910429175.7A CN201910429175A CN111978277A CN 111978277 A CN111978277 A CN 111978277A CN 201910429175 A CN201910429175 A CN 201910429175A CN 111978277 A CN111978277 A CN 111978277A
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- bisphenol
- diether dianhydride
- type diether
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The invention discloses a preparation method of bisphenol A type diether dianhydride, and relates to the field of preparation of bisphenol A type diether dianhydride. The preparation method is characterized in that bisphenol A is subjected to salification and acidification under the protection of inert gas. Compared with the prior art, the invention has the beneficial effects that: the total yield of the bisphenol A type diether dianhydride is effectively improved, the discharge of waste acid and waste alkali in the production process is reduced, and the environment is protected; in the salt forming reaction, propyl ether is adopted, so that the concentration rate of the intermediate product A is effectively improved, and the propyl ether layer is concentrated by adopting a secondary rotary wiped film type molecular distillation method, so that the yield of the obtained intermediate product A is further improved, the yield reaches 97%, and the melting point is 146.1-147.8 ℃; in the acidification reaction, the intermediate product is dried and decolored through activated carbon, so that the purity of the intermediate product is effectively improved, the yield of the final bisphenol A type diether dianhydride reaches 96.7%, and the melting point is 196.4-197.2 ℃.
Description
Technical Field
The invention relates to the technical field of bisphenol A type diether dianhydride, in particular to a preparation method of bisphenol A type diether dianhydride.
Background
Bisphenol A type diether dianhydride is a chemical product, has a molecular formula of C31H20O8, and is a main raw material for producing polyimide products and composite materials thereof, wherein polyimide is a polymer containing imide rings (-CO-N-CO-) on a main chain, and the polymer containing a phthalimide structure is most important. Polyimide is used as a special engineering material and has been widely applied to the fields of aviation, aerospace, microelectronics, nano-scale, liquid crystal, separation membranes, laser and the like. In the last 60 th century, the research, development and utilization of polyimide was listed as one of the most promising engineering plastics in 21 st century in all countries. Polyimide, because of its outstanding characteristics in terms of performance and synthesis, has been fully recognized as a structural material or a functional material with great application prospects, which is called "problem-solving ability", and it is considered that the importance of bisphenol a type diether dianhydride is seen because of the fact that no polyimide is available and today's microelectronics technologies are not available.
At present, the preparation steps for synthesizing bisphenol A type diether dianhydride are long and tedious, the total yield is low, and a large amount of waste acid and waste alkali can be generated in the production and preparation process, thereby having great influence on the environment.
Disclosure of Invention
The invention aims to solve the technical problem of how to improve the total yield of bisphenol A type diether dianhydride.
In order to solve the technical problems, the invention provides a preparation method of bisphenol A type diether dianhydride, which can effectively improve the total yield of bisphenol A type diether dianhydride, reduce the discharge of waste acid and waste alkali in the production process and protect the environment.
A preparation method of bisphenol A type diether dianhydride is characterized in that: the bisphenol A is prepared by salifying and acidifying under the protection of inert gas, and the synthetic route is as follows:
wherein: the salifying catalyst is one of toluene and xylene; the acidification catalyst is one of hydrochloric acid and sulfuric acid.
Further, the salifying step comprises the following steps of mixing bisphenol A, a sodium ion-containing compound aqueous solution and 100-120 ml of distilled water in a flask through a stirring rod, heating to 60-75 ℃ for heating reflux, adding 300-320 ml of salifying catalyst after 1-1.5 h, keeping the heating temperature for continuous heating reflux for 5-7 h, then adding MPI, TBBA and propyl ether, heating to 80-86 ℃, stirring for reaction for 2-3 h, keeping the temperature at 70-78 ℃ for filtering and layering, and concentrating the propyl ether layer by adopting a rotary wiped film type molecular distillation method to obtain an intermediate product A.
Further, the operation steps of the rotary wiped film type molecular distillation method are as follows, preheating a wiped film device to 70 ℃, controlling the feeding rate to be 55-60 rnL/h, controlling the rotating speed of the wiped film device to be 80-90 r/Min, and then carrying out secondary separation, wherein the distillation temperature of the primary separation is 95-110 ℃, the pressure is 9-11 Pa, the distillation temperature of the secondary separation is 120-140 ℃, and the pressure is 12-15 Pa.
Further, the compound aqueous solution containing sodium ions in the salt forming step is a 50% sodium hydroxide aqueous solution in parts by mass, and the material ratio of the bisphenol A to the sodium hydroxide aqueous solution is 1: 2.
Further, the salifying catalyst is toluene, and the mass ratio of MPI to TBBA is 26: 1.
Further, the acidification step is specifically as follows, the intermediate product A generated in the salification step, a compound aqueous solution containing sodium ions and 1200-1400 ml of distilled water are mixed in a flask, the temperature is raised to 150-180 ℃ for heating reflux, filtering is carried out after stirring for 4-5 h, an acidification catalyst is added, the pH value of the melt is adjusted to 1-1.3, the melt is stirred for 3-4 h again and then is kept stand for precipitation, then the precipitate is filtered and cleaned, activated carbon is used for decoloring and drying, glacial acetic acid is added for dissolving, and the acidification catalyst is added again for cooling, filtering and washing to obtain the finished product bisphenol A type diether dianhydride.
Further, the compound containing sodium ions in the acidification step is a 30% sodium hydroxide aqueous solution in parts by mass, and the material ratio of the intermediate product A to the sodium hydroxide aqueous solution is 1: 1.8.
Furthermore, hydrochloric acid is adopted as the acidification catalyst in the acidification step, and the concentration of the hydrochloric acid is 4.2-5 mol/L.
Further, the acetic acid content in the glacial acetic acid is 98-99%.
Further, the inert gas is one of argon, nitrogen and neon.
The invention has the beneficial effects that:
1) the total yield of the bisphenol A type diether dianhydride is effectively improved, the discharge of waste acid and waste alkali in the production process is reduced, and the environment is protected;
2) in the salt forming reaction, propyl ether is adopted, so that the concentration rate of the intermediate product A is effectively improved, and the propyl ether layer is concentrated by adopting a secondary rotary wiped film type molecular distillation method, so that the yield of the obtained intermediate product A is further improved, the yield reaches 97%, and the melting point is 146.1-147.8 ℃;
3) in the acidification reaction, the intermediate product is dried and decolored through activated carbon, so that the purity of the intermediate product is effectively improved, the yield of the final bisphenol A type diether dianhydride reaches 96.7%, and the melting point is 196.4-197.2 ℃.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention.
Example 1
A preparation method of bisphenol A type diether dianhydride is prepared by bisphenol A through salifying and acidifying steps under the protection of inert gas, and the synthetic route is as follows:
wherein: the salifying catalyst is one of toluene and xylene; the acidification catalyst is one of hydrochloric acid and sulfuric acid.
In this embodiment, the salt formation step is specifically as follows, bisphenol a, an aqueous solution of a compound containing sodium ions, and 120ml of distilled water are mixed in a flask through a stirring rod, then heated to 60 ℃ for heating reflux, 300ml of a salt formation catalyst is added after 1.5h, heating reflux is continued for 7h while maintaining the heating temperature, then MPI, TBBA, and propyl ether are added, heated to 80 ℃ for stirring reaction for 3h, then maintained at 70 ℃ for filtration and layering, and the propyl ether layer is concentrated by a rotary wiped film molecular distillation method, so as to obtain an intermediate product a.
In this example, the molecular distillation method of the rotary wiped film type was operated by preheating the wiped film reactor to 70 ℃ and controlling the feed rate at 60 rnL/h and the speed of the wiped film reactor at 80 r/Min, followed by the secondary separation at a distillation temperature of 110 ℃ and a pressure of 9Pa, and at a distillation temperature of 140 ℃ and a pressure of 12 Pa.
In this example, the aqueous solution of the compound containing sodium ions in the salt formation step is a 50% aqueous solution of sodium hydroxide in parts by mass, and the material ratio of bisphenol a to the aqueous solution of sodium hydroxide is 1: 2.
In this example, the salt-forming catalyst was toluene and the mass ratio of MPI to TBBA was 26: 1.
In this embodiment, the acidification step is specifically as follows, mixing the intermediate product a generated in the salt formation step, a compound aqueous solution containing sodium ions and 1400ml of distilled water in a flask, heating to 150 ℃ for heating reflux, stirring for 5h, filtering, adding an acidification catalyst, adjusting the PH value of the melt to 1, stirring again for 4h, standing for precipitation, filtering and cleaning the precipitate, decolorizing and drying with activated carbon, adding glacial acetic acid for dissolution, adding the acidification catalyst again, cooling, filtering and washing with water, and obtaining the finished product bisphenol a type diether dianhydride.
In this example, the compound containing sodium ions in the acidification step is a 30% sodium hydroxide aqueous solution in parts by mass, and the material ratio of the intermediate product a to the sodium hydroxide aqueous solution is 1: 1.8.
In this example, hydrochloric acid was used as the acidification catalyst in the acidification step, and the concentration of hydrochloric acid was 4.2 mol/L.
In this example, the acetic acid content in glacial acetic acid was 99%.
In the present embodiment, the inert gas is one of argon, nitrogen and neon.
Example 2
A preparation method of bisphenol A type diether dianhydride is prepared by bisphenol A through salifying and acidifying steps under the protection of inert gas, and the synthetic route is as follows:
wherein: the salifying catalyst is one of toluene and xylene; the acidification catalyst is one of hydrochloric acid and sulfuric acid.
In this embodiment, the salt formation step is specifically as follows, bisphenol a, an aqueous solution of a compound containing sodium ions, and 100ml of distilled water are mixed in a flask through a stirring rod, then heated to 75 ℃ for heating reflux, 320ml of a salt formation catalyst is added after 1 hour, heating reflux is continued for 5 hours while maintaining the heating temperature, then MPI, TBBA, and propyl ether are added, heated to 86 ℃ for stirring reaction for 2 hours, then the temperature is maintained at 78 ℃ for filtration and layering, and then the propyl ether layer is concentrated by a rotary wiped film type molecular distillation method, so as to obtain an intermediate product a.
In this example, the molecular distillation method of the rotary wiped film type was operated by preheating the wiped film reactor to 70 ℃ and controlling the feed rate to 55 rnL/h and the speed of the wiped film reactor to 90 r/Min, followed by the secondary separation at a distillation temperature of 95 ℃ and a pressure of 11Pa for the primary separation and at a distillation temperature of 120 ℃ and a pressure of 15Pa for the secondary separation.
In this example, the aqueous solution of the compound containing sodium ions in the salt formation step is a 50% aqueous solution of sodium hydroxide in parts by mass, and the material ratio of bisphenol a to the aqueous solution of sodium hydroxide is 1: 2.
In this example, the salt-forming catalyst was toluene and the mass ratio of MPI to TBBA was 26: 1.
In this embodiment, the acidification step is specifically as follows, the intermediate product a generated in the salt formation step, a sodium ion-containing compound aqueous solution and 1200ml of distilled water are mixed in a flask, heated to 180 ℃ for heating reflux, stirred for 4 hours, filtered, added with an acidification catalyst, adjusted to a PH value of the melt of 1.3, stirred for 3 hours again, stood for precipitation, filtered and cleaned, decolorized and dried with activated carbon, added with glacial acetic acid for dissolution, and added with the acidification catalyst again for cooling, filtering and washing to obtain the finished product bisphenol a type diether dianhydride.
In this example, the compound containing sodium ions in the acidification step is a 30% sodium hydroxide aqueous solution in parts by mass, and the material ratio of the intermediate product a to the sodium hydroxide aqueous solution is 1: 1.8.
In this example, hydrochloric acid was used as the acidification catalyst in the acidification step, and the concentration of hydrochloric acid was 5 mol/L.
In this example, the acetic acid content in glacial acetic acid was 98%.
In the present embodiment, the inert gas is one of argon, nitrogen and neon.
Example 3
A preparation method of bisphenol A type diether dianhydride is prepared by bisphenol A through salifying and acidifying steps under the protection of inert gas, and the synthetic route is as follows:
wherein: the salifying catalyst is one of toluene and xylene; the acidification catalyst is one of hydrochloric acid and sulfuric acid.
In this embodiment, the step of forming salt is specifically as follows, mixing bisphenol a, an aqueous solution of a compound containing sodium ions, and 110ml of distilled water in a flask through a stirring rod, then heating to 65 ℃ for heating reflux, adding 310ml of a salt forming catalyst after 1.2h, keeping the heating temperature, continuing to heat reflux for 6h, then adding MPI, TBBA, and propyl ether, heating to 83 ℃ for stirring reaction for 2.5h, then keeping the temperature at 75 ℃ for filtering and layering, and then concentrating the propyl ether layer by using a rotary wiped film type molecular distillation method to obtain an intermediate product a.
In this example, the molecular distillation method of the rotary wiped film type was operated by preheating the wiped film reactor to 70 ℃ and controlling the feed rate to 57 rnL/h and the speed of the wiped film reactor to 85 r/Min, followed by the secondary separation at a distillation temperature of 100 ℃ and a pressure of 10Pa, and at a distillation temperature of 130 ℃ and a pressure of 13 Pa.
In this example, the aqueous solution of the compound containing sodium ions in the salt formation step is a 50% aqueous solution of sodium hydroxide in parts by mass, and the material ratio of bisphenol a to the aqueous solution of sodium hydroxide is 1: 2.
In this embodiment, the salifying catalyst is toluene, and the mass ratio of MPI to TBBA is 26: 1.
In this embodiment, the step of acidification is specifically as follows, mixing the intermediate product a generated in the step of salification, a compound aqueous solution containing sodium ions and 1300ml of distilled water in a flask, heating to 170 ℃ for heating reflux, stirring for 4.5h, filtering, adding an acidification catalyst, adjusting the PH value of the melt to 1.2, stirring again for 3.4h, standing for precipitation, filtering and cleaning the precipitate, decolorizing and drying with activated carbon, adding glacial acetic acid for dissolution, adding the acidification catalyst again, cooling, filtering and washing with water, and obtaining the finished product of bisphenol a diether dianhydride.
In this example, the compound containing sodium ions in the acidification step is a 30% sodium hydroxide aqueous solution in parts by mass, and the material ratio of the intermediate product a to the sodium hydroxide aqueous solution is 1: 1.8.
In the present embodiment, hydrochloric acid is used as the acidification catalyst in the acidification step, and the concentration of the hydrochloric acid is 4.7 mol/L.
In this example, the acetic acid content of the glacial acetic acid was 98.5%.
In this embodiment, the inert gas is one of argon, nitrogen and neon.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of bisphenol A type diether dianhydride is characterized in that: the bisphenol A is prepared by salifying and acidifying under the protection of inert gas, and the synthetic route is as follows:
wherein: the salifying catalyst is one of toluene and xylene; the acidification catalyst is one of hydrochloric acid and sulfuric acid.
2. The process according to claim 1, wherein the bisphenol A type diether dianhydride comprises: the salifying step is specifically as follows, bisphenol A, a sodium ion-containing compound aqueous solution and 100-120 ml of distilled water are mixed in a flask through a stirring rod, then the temperature is raised to 60-75 ℃ for heating reflux, 300-320 ml of salifying catalyst is added after 1-1.5 h, the heating temperature is kept for heating reflux continuously for 5-7 h, MPI, TBBA and propyl ether are added, the temperature is raised to 80-86 ℃ for stirring reaction for 2-3 h, then the temperature is kept at 70-78 ℃ for filtering and layering, and a rotating wiped film type molecular distillation method is adopted to concentrate a propyl ether layer, so that an intermediate product A is obtained.
3. The process according to claim 2, wherein the bisphenol A type diether dianhydride comprises: the operation steps of the rotary wiped film type molecular distillation method are as follows, preheating a wiped film device to 70 ℃, controlling the feeding rate to be 55-60 rnL/h, controlling the rotating speed of the wiped film device to be 80-90 r/Min, and then carrying out secondary separation, wherein the distillation temperature of the primary separation is 95-110 ℃, the pressure is 9-11 Pa, the distillation temperature of the secondary separation is 120-140 ℃, and the pressure is 12-15 Pa.
4. The process according to claim 2, wherein the bisphenol A type diether dianhydride comprises: the compound aqueous solution containing sodium ions in the salifying step is a 50% sodium hydroxide aqueous solution in parts by weight, and the material ratio of the bisphenol A to the sodium hydroxide aqueous solution is 1: 2.
5. The process according to claim 3, wherein the bisphenol A type diether dianhydride comprises: the salifying catalyst is toluene, and the mass ratio of MPI to TBBA is 26: 1.
6. The process according to claim 5, wherein the bisphenol A type diether dianhydride comprises: and the acidification step is specifically as follows, mixing the intermediate product A generated in the salifying step, a sodium ion-containing compound aqueous solution and 1200-1400 ml of distilled water in a flask, heating to 150-180 ℃ for heating reflux, stirring for 4-5 h, filtering, adding an acidification catalyst, adjusting the pH value of the melt to 1-1.3, stirring for 3-4 h again, standing for precipitation, filtering and cleaning the precipitate, decoloring and drying by using active carbon, adding glacial acetic acid for dissolving, adding the acidification catalyst again, cooling, filtering and washing by water to obtain the finished product bisphenol A type diether dianhydride.
7. The method according to claim 6, wherein the bisphenol A type diether dianhydride comprises: the compound containing sodium ions in the acidification step is a 30% sodium hydroxide aqueous solution in parts by mass, and the material ratio of the intermediate product A to the sodium hydroxide aqueous solution is 1: 1.8.
8. The process according to claim 7, wherein the bisphenol A type diether dianhydride comprises: the acidification catalyst in the acidification step is hydrochloric acid, and the concentration of the hydrochloric acid is 4.2-5 mol/L.
9. The method according to claim 8, wherein the bisphenol A type diether dianhydride comprises: the acetic acid content in the glacial acetic acid is 98-99%.
10. The process according to claim 1, wherein the bisphenol A type diether dianhydride comprises: the inert gas is one of argon, nitrogen and neon.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634904A (en) * | 2004-11-12 | 2005-07-06 | 南京工业大学 | Process for synthesis of aryl bis-ether dianhydrides monomer |
| CN101402625A (en) * | 2008-10-15 | 2009-04-08 | 南京工业大学 | Process for producing aromatic diaether dianhydride monomer |
| CN104529966A (en) * | 2015-01-11 | 2015-04-22 | 景炜杰 | Preparation method of bisphenol A diether dianhydride |
| CN108148029A (en) * | 2017-12-27 | 2018-06-12 | 上海固创化工新材料有限公司 | A kind of preparation method of two ether dianhydride of bisphenol-A |
| CN110483454A (en) * | 2019-09-06 | 2019-11-22 | 湖南师范大学 | A kind of preparation method of two ether dianhydride of aromatic series |
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2019
- 2019-05-22 CN CN201910429175.7A patent/CN111978277A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634904A (en) * | 2004-11-12 | 2005-07-06 | 南京工业大学 | Process for synthesis of aryl bis-ether dianhydrides monomer |
| CN101402625A (en) * | 2008-10-15 | 2009-04-08 | 南京工业大学 | Process for producing aromatic diaether dianhydride monomer |
| CN104529966A (en) * | 2015-01-11 | 2015-04-22 | 景炜杰 | Preparation method of bisphenol A diether dianhydride |
| CN108148029A (en) * | 2017-12-27 | 2018-06-12 | 上海固创化工新材料有限公司 | A kind of preparation method of two ether dianhydride of bisphenol-A |
| CN110483454A (en) * | 2019-09-06 | 2019-11-22 | 湖南师范大学 | A kind of preparation method of two ether dianhydride of aromatic series |
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Application publication date: 20201124 |