CN1583752A - Synthesis of benzoxazole - Google Patents
Synthesis of benzoxazole Download PDFInfo
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- CN1583752A CN1583752A CN 200410013800 CN200410013800A CN1583752A CN 1583752 A CN1583752 A CN 1583752A CN 200410013800 CN200410013800 CN 200410013800 CN 200410013800 A CN200410013800 A CN 200410013800A CN 1583752 A CN1583752 A CN 1583752A
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Abstract
Synthesis method for benzo oxazole diamine, which involves organic compound synthesis process. Said p-phenylene-2,2'-bis (5-aminobenzo oxazole) of the present invention is prepared as follows: a. Formulate phosphoric acid and P2O5 into ploy(phosphoric acid) solution; b. Add to the resulting solution 2,4-diamiophenol hydrochloride and terephthalic acid; c. Add then reducing agent SnCl2; d. Followed by neutralization, extraction and drying, then the primary product is obtained; e. Subject the primary products to extraction and drying to get bright yellow powder. And said 2,6-bis primary product to extraction and drying to get bright yellow powder. And said 2,6-bis primary product to extraction and drying to get bright yellow powder. And said 2,6-bis primary product to extraction and drying to get bright yellow powder. And said 2,6-bis primary product to extraction and dyring to get bright yellow powder. And said 2,6-bis (p-aminobenzyl) benzo [1,2-d; 5,4-d'] dioxazole is prepared as follows: a. Formulate phosphoric acid and P2O5 into ploy(phosphoric acid) solution; b. Add to the resulting solution 4,6-metaphenylene diamine hydrochloride and p-aminobenzoic acid.
Description
The technical field is as follows:
the invention relates to a synthesis process of an organic compound, in particular to a synthesis process of benzoxazole diamine.
Background art:
in polyphosphoric acid, the synthesized benzoxazole compound is a compound which is attracted by the sixties, has good stability under the irradiation of ultraviolet light, can be widely applied as a laser dye in a near ultraviolet band, and can be used as a monomer of a novel high polymer. The benzoxazole diamine contains a benzoxazole ring, is an important organic synthesis intermediate, can react with other molecules by utilizing the benzoxazole ring and amino on the benzoxazole diamine to form an optical polymer containing the benzoxazole ring and a nonlinear optical material, and can also be used as a laser dye. In addition, through molecular design, a benzoxazole structure is introduced into a polymer chain, so that the aromatic heterocyclic polymer has excellent performance. P-phenylene-2, 2' -bis (5-aminobenzoxazole) is typically obtained by the condensation of 2, 4-diaminophenol hydrochloride and terephthalic acid in polyphosphoric acid, according to the following reaction equation:
typically 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']dioxazole is prepared by condensing 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid in polyphosphoric acid, and the reaction equation is as follows:
p-phenylene-2, 2' -bis (5-aminobenzoxazole) and 2, 6-bis (p-aminobenzene) benzo [1, 2-d; 5, 4-d']dioxazole is an important organic synthesis intermediate, and a benzoxazole ring or a benzobisoxazole ring and an amino group on the intermediate can be used for reacting with other molecules to form an optical polymer and a nonlinear optical material containing the benzoxazole ring. 2, 6-bis (p-aminophenyl) benzo [1, 2-d; the synthesis of 5, 4-d']dioxazole is reported rarely, and in the existing synthesis method (such as US4087409), 4, 6-diaminoresorcinol or 4, 6-diaminoresorcinol hydrochloride is directly used as raw material, and synthesized with p-aminobenzoic acid in polyphosphoric acid, so that the reaction is very easy to oxidize, and the yield is low. 2, 4-diaminophenol hydrochloride is an important intermediate in medical and dye industries and is widely applied, but 2, 4-diaminophenol hydrochloride is easy to oxidize, so that the key for synthesizing p-phenylene-2, 2' -bis (5-aminobenzoxazole) is to solve the problem of oxidation. The synthesis method adopted at present is that 2, 4-diaminophenol hydrochloride and terephthalic acid are subjected to condensation reaction in polyphosphoric acid, a crude product is extracted by acetone, a large amount of hot DMF is dissolved, water is precipitated, dried and sublimed for purification, and the purification method has the defects that DMF is difficult to be completely removed, the purity of the product is difficult to ensure, and the sublimed purification method is adopted, so that the yield is low. At present, no report of a method for synthesizing p-phenylene-2, 2' -bis (5-aminobenzoxazole) with high yield is provided at home and abroad. 4, 6-diaminoresorcinol or 4, 6-diaminoresorcinol hydrochloride has the same properties as 2, 4-diaminophenol hydrochloride in the synthesis of 2, 6-bis (p-aminobenzene) benzo [1, 2-d; 5, 4-d']dioxazole is very susceptible to oxidation, and thus, the problem of solving the oxidation is the problem of synthesizing 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']the reaction is critical. The synthesis method adopted at present is formed by condensing 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid in polyphosphoric acid, the yield is 75%, and the reason of the lower yield is the oxidation of 4, 6-diaminoresorcinol hydrochloride. If the synthesis of 2, 6-bis (p-aminophenyl) benzo [1, 2-d; in the reaction process of 5, 4-d']dioxazole, a reducing agent is added into polyphosphoric acid to inhibit the oxidation of 4, 6-diaminoresorcinol hydrochloride, so that the 4, 6-diaminoresorcinol hydrochloride is ensured to completely participate in the reaction, the yieldis greatly improved, the separation and purification process is simplified, and a foundation is laid for industrial production.
The invention content is as follows:
the invention aims to provide a synthesis method of benzoxazole diamine, which can conveniently and effectively prepare high-yield and high-purity benzoxazole diamine and simplify the separation and purification process. Benzoxazole diamines of the present invention include p-phenylene-2, 2' -bis (5-aminobenzoxazole) and 2, 6-bis (p-aminobenzene) benzo [1, 2-d; 5, 4-d']Two compounds of the bisoxazole, p-phenylene-2, 2' -bis (5-aminobenzoxazole) are prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration is controlled between 80 percent and 85 percent; b. controlling the temperature to be 60-120 ℃, adding 2, 4-diaminophenol hydrochloride and terephthalic acid reaction raw materials into a polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 2, 4-diaminophenol hydrochloride to the terephthalic acid is (2.1-3.0) to 1; c. then adding 5-10 mol mass of the reaction raw materialg/mol SnCl2Reducing agent, heating to 140-210 deg.CReacting for 2-4 hours to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. extracting the primary product, and drying in vacuum to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder.
2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']The bisoxazole is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration of (A) is controlled to be between 80 and 85 percent; b. controlling the temperature at 60-120 ℃, adding 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid reaction raw materials into polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the p-aminobenzoic acid is 1: 2.1-3.0; c. then adding 5-10 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 2-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. recrystallizing the primary product, and drying in vacuum to obtain yellow 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']A powder of a bisoxazole. The invention adopts SnCl2As reducing agent, directly added to polyphosphoric acid, Sn2+The catalyst has reducibility in an acid solution and can be oxidized even by oxygen in the air, and the reaction mechanism is as follows: . Due to SnCl2Can absorb a trace amount of oxygen in the reaction system and is oxidized into Sn4+Therefore, the 2, 4-diaminophenol hydrochloride and the 4, 6-diaminoresorcinol hydrochloride which are easy to be oxidized are protected, so that the reaction raw materials can completely participate in the reaction, and the reaction yield is greatly improved; and the oxidation product of the reducing agent is easy to dissolve in water and is easy to separate and purify. The invention provides a new synthetic method based on the original synthetic method, and a reducing agent SnCl is added into a reaction system for the first time2，4The 6-diamino resorcinol hydrochloride, p-aminobenzoic acid, 2, 4-diamino phenol hydrochloride andterephthalic acid are condensed into benzoxazole diamine in polyphosphoric acid, and the yield is improved by more than 15%. The method has the advantages of high yield, high purity and simple process.
The specific implementation mode is as follows:
the first embodiment is as follows: the p-phenylene-2, 2' -bis (5-aminobenzoxazole) of the present embodiment is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration is controlled between 80 percent and 85 percent; b. controlling the temperature to be 60-120 ℃, adding 2, 4-diaminophenol hydrochloride and terephthalic acid reaction raw materials into a polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 2, 4-diaminophenol hydrochloride to the terephthalic acid is (2.1-3.0) to 1; c. then adding 5-10 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, reacting for 2-4 hours at the temperature,obtaining a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. extracting the primary product, and drying in vacuum to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder.
The second embodiment is as follows: the p-phenylene-2, 2' -bis (5-aminobenzoxazole) of the present embodiment is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration is controlled between 82.5 percent and 83.5 percent; b. controlling the temperature to be 60-120 ℃, adding 2, 4-diaminophenol hydrochloride and terephthalic acid reaction raw materials into a polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 2, 4-diaminophenol hydrochloride to the terephthalic acid is (2.1-2.5) to 1; c. then adding 5-8 g/mol SnCl with molar mass as the reaction raw material2Reducing agent, heating to 140-2Reacting for 3-4 hours at the temperature of 10 ℃ to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. extracting the primary product, and drying in vacuum to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder.
The third concrete implementation mode: the p-phenylene-2, 2' -bis (5-aminobenzoxazole) of the present embodiment is prepared by: a. 71.32g of 85% strength by weight phosphoric acid and 121.74g P were added to a 500mL four-necked flask under nitrogen2O5Preparing a polyphosphoric acid solution; b. the temperature is reduced to 60 ℃, and 20.69g (0.105mol) of 2, 4-diaminophenol hydrochloride and 8.31g (0.05mol) of terephthalic acid are added into the polyphosphoric acid solution; c. then adding 0.5g of stannous chloride, heating to 210 ℃, and reacting for 4 hours at the temperature to obtain a reaction product; d. neutralizing, filtering and drying the reaction product by using a sodium carbonate aqueous solution to obtain an initial product; e. the crude product is subjected to Soxhlet extraction and vacuum drying by using ethanol and water respectively to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder, and the yield is 98%.
The fourth concrete implementation mode: the 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']The bisoxazole is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration of (A) is controlled to be between 80 and 85 percent; b. controlling the temperature at 60-120 ℃, adding 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid reaction raw materials into polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the p-aminobenzoic acid is 1: 2.1-3.5; c. then adding 5-10 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 2-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. recrystallizing the primary product, and vacuum drying to obtain yellow2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']Dioxazole compoundAnd (3) powder.
The fifth concrete implementation mode: the 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']The bisoxazole is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration of (A) is controlled to be 82.5-83.5%; b. controlling the temperature at 60-120 ℃, adding 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid reaction raw materials into polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the p-aminobenzoic acid is 1: 2.1-2.5; c. then adding 5-8 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 3-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reactionproduct to obtain an initial product; e. recrystallizing the primary product, and drying in vacuum to obtain yellow 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']A powder of a bisoxazole.
The sixth specific implementation mode: the 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']The bisoxazole is prepared by: a. 71.32g of 85% strength by weight phosphoric acid and 121.74g of P were placed in a 500mL four-necked flask under nitrogen2O5Preparing a polyphosphoric acid solution; b. cooling to 60 deg.C, adding 14.40g (0.105mol) of p-aminobenzoic acid and 10.65g (0.05mol) of 4, 6-diaminoresorcinol hydrochloride into the polyphosphoric acid solution; c. then adding 0.5g of stannous chloride, intermittently vacuumizing, removing HCl, heating to 210 ℃, and reacting for 4 hours at the temperature to obtain a reaction product; d. neutralizing the reaction product with sodium carbonate water solution, washing repeatedly, and drying the filtrate to obtain an initial product; e. recrystallizing the primary product by DMAc, and drying in vacuum to finally obtain yellow 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']The yield of the powder of the bisoxazole was 91%.
Claims (6)
1. Process for the synthesis of benzoxazole diamines, which comprisesCharacterized in that p-phenylene-2, 2' -bis (5-aminobenzoxazole) is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration is controlled between 80 percent and 85 percent; b. controlling the temperature to be 60-120 ℃, adding 2, 4-diaminophenol hydrochloride and terephthalic acid reaction raw materials into a polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 2, 4-diaminophenol hydrochloride to the terephthalic acid is (2.1-3.0) to 1; c. then adding 5-10 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 2-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. extracting the primary product, and drying in vacuum to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder.
2. A synthesis process of benzoxazole diamine as claimed in claim 1, characterized in that p-phenylene-2, 2' -bis (5-aminobenzoxazole) is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration is controlled between 82.5 percent and 83.5 percent; b. controlling the temperature to be 60-120 ℃, adding 2, 4-diaminophenol hydrochloride and terephthalic acid reaction raw materials into a polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 2, 4-diaminophenol hydrochloride to the terephthalic acid is (2.1-2.5) to 1; c. then adding 5-8 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 3-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. extracting the primary product, and drying in vacuum to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder.
3. The benzene of claim 1A process for the synthesis of oxazole diamine characterized in that p-phenylene-2, 2' -bis (5-aminobenzoxazole) is prepared by: a. 71.32g of 85% strength by weight phosphoric acid and 121.74g P were added to a 500mL four-necked flask under nitrogen2O5Preparing a polyphosphoric acid solution; b. cooling to 60 ℃, and adding 20.69g of 2, 4-diaminophenol hydrochloride and 8.31g of terephthalic acid into the polyphosphoric acid solution; c. then adding 0.5g of stannous chloride, heating to 210 ℃, and reacting for 4 hours at the temperature to obtain a reaction product; d. neutralizing, filtering and drying the reaction product by using a sodium carbonate aqueous solution to obtain an initial product; e. the crude product is subjected to Soxhlet extraction and vacuum drying by using ethanol and water respectively to obtain bright yellow p-phenylene-2, 2' -bis (5-aminobenzoxazole) powder, and the yield is 98%.
4. A synthesis method of benzoxazole diamine, which is characterized in that 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']The bisoxazole is prepared by: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration of (A) is controlled to be between 80 and 85 percent; b. controlling the temperature at 60-120 ℃, adding 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid reaction raw materials into polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the p-aminobenzoic acid is 1: 2.1-3.0; c. then adding 5-10 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 2-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. recrystallizing the primary product, and drying in vacuum to obtain yellow 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']A powder of a bisoxazole.
5. A synthesis process of benzoxazole diamine as claimed in claim 4, characterized in that 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']Dioxazole compoundIs prepared by the following steps: a. under the protection of inert gas, phosphoric acid and P are mixed2O5Mixing to obtain polyphosphoric acid solution, wherein P in the solution2O5The concentration of (A) is controlled to be 82.5-83.5%; b. controlling the temperature at 60-120 ℃, adding 4, 6-diaminoresorcinol hydrochloride and p-aminobenzoic acid reaction raw materials into polyphosphoric acid solution, wherein the reaction raw materials account for 6-12% of the total weight of the solution, and the molar ratio of the 4, 6-diaminoresorcinol hydrochloride to the p-aminobenzoic acid is 1: 2.1-2.5; c. then adding 5-8 g/mol SnCl with molar mass as the reaction raw material2Heating the reducing agent to 140-210 ℃, and reacting for 3-4 hours at the temperature to obtain a reaction product; d. neutralizing, washing, filtering and drying the reaction product to obtain an initial product; e. recrystallizing the primary product, and drying in vacuum to obtain yellow 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']A powder of a bisoxazole.
6. A synthesis process of benzoxazole diamine as claimed in claim 4, characterized in that 2, 6-bis (p-aminophenyl) benzo [1, 2-d; 5, 4-d']The bisoxazole is prepared by: a. 71.32g of 85% strength by weight phosphoric acid and 121.74g P were added to a 500mL four-necked flask under nitrogen2O5Preparing a polyphosphoric acid solution; b. cooling to 60 ℃, and adding 14.40g of p-aminobenzoic acid and 10.65g of 4, 6-diaminoresorcinol hydrochloride into the polyphosphoric acid solution; c. then adding 0.5g of stannous chloride, intermittently vacuumizing, removing HCl, heating to 210 ℃, and reacting for 4 hours at the temperature to obtain a reaction product; d. neutralizing the reaction product with sodium carbonate water solution, washing repeatedly, and drying the filtrate to obtain an initial product; e. recrystallizing the primary product by DMAc, and drying in vacuum to finally obtain yellow 2, 6-di (p-aminobenzene) benzo [1, 2-d; 5, 4-d']The yield of the powder of the bisoxazole was 91%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326844C (en) * | 2005-06-16 | 2007-07-18 | 北京理工大学 | 2H-3,1-benzo oxole heterocyclic compound hynthesizing method |
| CN102604096A (en) * | 2012-02-07 | 2012-07-25 | 金发科技股份有限公司 | Method for preparing high-performance PBO (polyparaphenylene benzobisoxazole) resin |
| CN103880767A (en) * | 2014-04-17 | 2014-06-25 | 哈尔滨工业大学 | Preparation method for 2-(p-formylchloropropyl)-5-amino-6-hydroxyl benzoxazole |
| CN103965082A (en) * | 2014-05-22 | 2014-08-06 | 哈尔滨工业大学 | Benzene sulfonates containing amino and phenolic group and preparation method thereof |
| CN105237547A (en) * | 2015-11-17 | 2016-01-13 | 中国科学院长春应用化学研究所 | Preparation method of hydroxyl-containing benzoxazole diamine |
| CN109734908A (en) * | 2018-12-20 | 2019-05-10 | 武汉柔显科技股份有限公司 | The preparation method of polyamic acid and preparation method, polyimides and Kapton |
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2004
- 2004-06-02 CN CN 200410013800 patent/CN1583752A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326844C (en) * | 2005-06-16 | 2007-07-18 | 北京理工大学 | 2H-3,1-benzo oxole heterocyclic compound hynthesizing method |
| CN102604096A (en) * | 2012-02-07 | 2012-07-25 | 金发科技股份有限公司 | Method for preparing high-performance PBO (polyparaphenylene benzobisoxazole) resin |
| CN102604096B (en) * | 2012-02-07 | 2014-06-11 | 金发科技股份有限公司 | Method for preparing high-performance PBO (polyparaphenylene benzobisoxazole) resin |
| CN103880767A (en) * | 2014-04-17 | 2014-06-25 | 哈尔滨工业大学 | Preparation method for 2-(p-formylchloropropyl)-5-amino-6-hydroxyl benzoxazole |
| CN103880767B (en) * | 2014-04-17 | 2016-03-16 | 哈尔滨工业大学 | A kind of preparation method of 2-(to formyl chloro phenyl)-5-amino-6-hydroxyl base benzoxazole |
| CN103965082A (en) * | 2014-05-22 | 2014-08-06 | 哈尔滨工业大学 | Benzene sulfonates containing amino and phenolic group and preparation method thereof |
| CN105237547A (en) * | 2015-11-17 | 2016-01-13 | 中国科学院长春应用化学研究所 | Preparation method of hydroxyl-containing benzoxazole diamine |
| CN109734908A (en) * | 2018-12-20 | 2019-05-10 | 武汉柔显科技股份有限公司 | The preparation method of polyamic acid and preparation method, polyimides and Kapton |
| CN109734908B (en) * | 2018-12-20 | 2021-01-12 | 武汉柔显科技股份有限公司 | Polyamide acid and preparation method thereof, polyimide and preparation method of polyimide film |
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