CN103588703B - A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt - Google Patents
A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt Download PDFInfo
- Publication number
- CN103588703B CN103588703B CN201310617931.1A CN201310617931A CN103588703B CN 103588703 B CN103588703 B CN 103588703B CN 201310617931 A CN201310617931 A CN 201310617931A CN 103588703 B CN103588703 B CN 103588703B
- Authority
- CN
- China
- Prior art keywords
- aminopyridine
- production
- phosphate salt
- phosphate
- salt according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention relates to a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, belong to PIPD technical field of polymer preparation.By 2,3,5,6-4-aminopyridine hydrochloride salt in polyphosphoric acid, then through steps such as hydrolysis, suction filtration, precipitation, filtration, washing and vacuum-dryings, obtained 2,3,5,6-4-aminopyridine phosphoric acid salt.The whole process time shortens, and productive rate improves, and can reach 80%, so adopt method of the present invention to prepare 2,3,5,6-4-aminopyridine phosphoric acid salt, can improve the purity of product, enhance productivity, and reduces production cost.
Description
Technical field
The present invention relates to a kind of method preparing PIPD polymer raw material, more particularly, the present invention relates to a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, belong to PIPD technical field of polymer preparation.
Background technology
Poly-[2,5 – bis-Qiang Ji – 1,4 pyridobismidazoles] (be called for short PIPD) molecular backbone chain there is polar group, can in molecule and intermolecular formation hydrogen bond, so PIPD fiber not only has excellent tensile property, also demonstrate excellent anti-compression properties, its ultimate compression strength reaches 1.6GPa.
PIPD fiber normally adopts 2,3,5,6-4-aminopyridine hydrochloride (TAP) and 2,5-Dihydroxyterephthalic acid (DHTA) to be polymerized in polyphosphoric acid (PPA), then obtains by fiber spinning from crystalline state technology.But when preparing PIPD with 4-aminopyridine hydrochloride, need deviate from HCl gas, it is many unfavorable to bring to reaction: the first, the time of de-HCl gas is long, extends polymerization reaction time.The second, the gas of generation can produce a large amount of foam in the reaction solution of thickness, thus reduces stirring efficiency; The second, if not exclusively degassed, be difficult to the equivalence ratio of TAP and DHTA to control at 1:1, these 2 synthesis being all unfavorable for high molecular PIPD; Three, HCl gas has severe corrosive, and this makes reaction very high for the requirement of equipment material, adds cost prepared by fiber; 4th, utilize 4-aminopyridine hydrochloride to prepare PIPD, tin protochloride (SnCl need be used
2) make stablizer, but SnCl
2can heavy-metal pollution be caused, also may disturb polyreaction.
If substitute the raw material of 2,3,5,6-4-aminopyridine hydrochloride as preparation PIPD polymkeric substance with 2,3,5,6-4-aminopyridine phosphoric acid salt, so just can solve the problem.
It is CN1121728 that State Intellectual Property Office discloses a publication number in 1996.5.1, name is called the patent of invention of " rigid rod polymer based on pyridobisimidazole ", this patent relates to a kind of rigid rod 1ike polymer, wherein at least 50% recurring group is corresponding to following formula, and in residue group, 2, that 5-dihydroxyl can be substituted phenylene or unsubstituted arylidene substitute and/or pyridobisimidazole by the two imidazoles of benzo, benzo double thiazole, the two oxazole of benzo, pyrido double thiazole and/or the two oxazole of pyrido substitute.The polyphosphate solution of the described polymkeric substance of 10-21wt.% can spin the fiber with excellent properties.
A kind of 2 are disclosed in above-mentioned patent, 3,5,6-4-aminopyridine method for production of phosphate salt, 4-aminopyridine hydrochloride is dissolved in phosphoric acid by the method, obtained corresponding phosphoric acid salt, this method prepare 2,3,5, although 6-4-aminopyridine phosphoric acid salt can apply in the production of PIPD, solve some problems that de-HCl brings, but this synthesis technique long reaction time, productive rate low (only 60%), production efficiency is caused to reduce, and adopt aforesaid method obtained 2,3,5,6-4-aminopyridine phosphoric acid salt produces PIPD, also can reduce the quality of PIPD product.
Summary of the invention
The present invention is intended to adopt phosphoric acid to prepare the phosphatic problem of 2,3,5,6-4-aminopyridine in solution prior art, provides a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, reaches shortening generated time, improve the object of product purity.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, is characterized in that: comprise following processing step:
A, 2,3,5,6-4-aminopyridine hydrochloride is dissolved in phosphorus pentoxide content at 50-80 DEG C is in the polyphosphoric acid of 75-85%;
B, after it dissolves completely, slowly drip deionized water and be hydrolyzed, hydrolysis time is 0.5-2h;
After C, hydrolysis reaction terminate, the hydrolysate obtained by step B carries out suction filtration under nitrogen protection, obtains filtrate;
Drip precipitation agent in D, the filtrate that obtains in step C muddy to system, obtain troubled liquor, described precipitation agent is the primary alconol of C2-C6;
E, the temperature of gained troubled liquor in step D is down to 0-20 DEG C, separates out to a large amount of white solid, then filter under nitrogen protection, wash, then vacuum-drying, namely obtain 2,3,5,6-4-aminopyridine phosphate powder.
In step, 2,3,5,6-described 4-aminopyridine hydrochlorides and the mass ratio of polyphosphoric acid are 1:1-3 in the present invention.
In step, the solvent temperature of described dissolving controls as 50-60 DEG C in the present invention.
In stepb, described deionized water and the volume ratio of polyphosphoric acid are 1-5:1 in the present invention.
In step D, described precipitation agent is ethanol or n-propyl alcohol in the present invention.
The present invention is in step e, and described vacuum drying temperature is 50-70 DEG C.
The present invention, in step e, 2,3,5,6-described 4-aminopyridine phosphate powder evenly sprays Hypophosporous Acid, 50 solution, then vacuum-drying.
The massfraction of above-mentioned Hypophosporous Acid, 50 solution is 35%, and the quality of Hypophosporous Acid, 50 solution is the 1-3% of 2,3,5,6-4-aminopyridine phosphate powder quality.
Above-mentioned vacuum drying temperature is 50-70 DEG C.
The Advantageous Effects that the present invention brings:
1, the invention provides a kind of 2, 3, 5, 6-4-aminopyridine method for production of phosphate salt, which solve in prior art and adopt phosphoric acid to prepare 2, 3, 5, the problem that 6-4-aminopyridine phosphoric acid salt productive rate is lower, the present invention is with 2, 3, 5, 6-4-aminopyridine hydrochloride is raw material, be dissolved in the polyphosphoric acid of specific phosphorus pentoxide content, precipitated by specific precipitation agent, add the specific process parameter control of each step, obtained 2, 3, 5, 6-4-aminopyridine phosphoric acid salt, its whole process time shortens, and productive rate improves, can 80% be reached, so adopt method of the present invention to prepare 2, 3, 5, 6-4-aminopyridine phosphoric acid salt, the purity of product can be improved, enhance productivity, reduce production cost.
2, the present invention 2,3,5, in 6-4-aminopyridine method for production of phosphate salt, be by 2,3,5,6-4-aminopyridine phosphate salt dissolves in polyphosphoric acid, and with 2, when 3,5,6-4-aminopyridine phosphoric acid salt prepares PIPD, also need to add polyphosphoric acid, like this when producing PIPD, new material can not be introduced, avoid the quality affecting PIPD product.
3, the product 2,3,5 prepared of the present invention, 6-4-aminopyridine phosphoric acid salt is as raw material, be used for producing in the process of PIPD, through degasification process, thus the many defects because degasification process causes polyreaction need not be overcome, shorten the time of PIPD polyreaction, improve stirring efficiency, be conducive to controlling the ratio between raw material, thus be conducive to the synthesis of PIPD, the requirement of equipment reduces in addition, reduces production cost.
4, preparation method of the present invention is on the basis of basic technical scheme, has carried out further restriction and optimization, comprise the optimization to dosage, temperature etc. to processing parameter, can improve the productive rate of product, purity and quality further.Wherein, the precipitation agent preferred alcohol described in step D or n-propyl alcohol, precipitation temperature 0-20 DEG C (0 DEG C is the most suitable) in these two kinds of precipitation agent matching step E, can reach good sedimentation effect while wananty costs is lower.
5, in prior art, utilize 2,3,5,6-4-aminopyridine hydrochloride to prepare PIPD, tin protochloride (SnCl need be used
2) make stablizer, but SnCl
2can heavy-metal pollution be caused, also may disturb polyreaction.The phosphatic storage stability of product 2,3,5,6-4-aminopyridine of the present invention is poor, allows its place in an inert atmosphere or under vacuum, through after a while, the degraded caused by oxygenizement is also inevitable.Due to above reason, the present invention, in step e, 2,3,5,6-described 4-aminopyridine phosphate powder evenly sprays Hypophosporous Acid, 50 solution, then vacuum-drying.Replace tin protochloride to stablize 2,3,5,6-4-aminopyridine phosphoric acid salt with Hypophosporous Acid, 50 like this, can avoid being oxidized the degraded caused, also prevent the heavy-metal pollution that tin protochloride causes in PIPD production process.
Embodiment
embodiment 1
A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, comprises following processing step:
A, 2,3,5,6-4-aminopyridine hydrochloride is dissolved in phosphorus pentoxide content at 50 DEG C is in the polyphosphoric acid of 75%;
B, after it dissolves completely, slowly drip deionized water and be hydrolyzed, hydrolysis time is 0.5h;
After C, hydrolysis reaction terminate, the hydrolysate obtained by step B carries out suction filtration under nitrogen protection, obtains filtrate;
Drip precipitation agent in D, the filtrate that obtains in step C muddy to system, obtain troubled liquor, described precipitation agent is the primary alconol of C2-C6;
E, the temperature of gained troubled liquor in step D is down to 0 DEG C, separates out to a large amount of white solid, then filter under nitrogen protection, wash, then vacuum-drying, namely obtain 2,3,5,6-4-aminopyridine phosphate powder.
embodiment 2
A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, comprises following processing step:
A, 2,3,5,6-4-aminopyridine hydrochloride is dissolved in phosphorus pentoxide content at 80 DEG C is in the polyphosphoric acid of 85%;
B, after it dissolves completely, slowly drip deionized water and be hydrolyzed, hydrolysis time is 2h;
After C, hydrolysis reaction terminate, the hydrolysate obtained by step B carries out suction filtration under nitrogen protection, obtains filtrate;
Drip precipitation agent in D, the filtrate that obtains in step C muddy to system, obtain troubled liquor, described precipitation agent is the primary alconol of C2-C6;
E, the temperature of gained troubled liquor in step D is down to 20 DEG C, separates out to a large amount of white solid, then filter under nitrogen protection, wash, then vacuum-drying, namely obtain 2,3,5,6-4-aminopyridine phosphate powder.
embodiment 3
A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, comprises following processing step:
A, 2,3,5,6-4-aminopyridine hydrochloride is dissolved in phosphorus pentoxide content at 65 DEG C is in the polyphosphoric acid of 80%;
B, after it dissolves completely, slowly drip deionized water and be hydrolyzed, hydrolysis time is 1.25h;
After C, hydrolysis reaction terminate, the hydrolysate obtained by step B carries out suction filtration under nitrogen protection, obtains filtrate;
Drip precipitation agent in D, the filtrate that obtains in step C muddy to system, obtain troubled liquor, described precipitation agent is the primary alconol of C2-C6;
E, the temperature of gained troubled liquor in step D is down to 10 DEG C, separates out to a large amount of white solid, then filter under nitrogen protection, wash, then vacuum-drying, namely obtain 2,3,5,6-4-aminopyridine phosphate powder.
embodiment 4
A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, comprises following processing step:
A, 2,3,5,6-4-aminopyridine hydrochloride is dissolved in phosphorus pentoxide content at 55 DEG C is in the polyphosphoric acid of 84%;
B, after it dissolves completely, slowly drip deionized water and be hydrolyzed, hydrolysis time is 0.75h;
After C, hydrolysis reaction terminate, the hydrolysate obtained by step B carries out suction filtration under nitrogen protection, obtains filtrate;
Drip precipitation agent in D, the filtrate that obtains in step C muddy to system, obtain troubled liquor, described precipitation agent is the primary alconol of C2-C6;
E, the temperature of gained troubled liquor in step D is down to 2 DEG C, separates out to a large amount of white solid, then filter under nitrogen protection, wash, then vacuum-drying, namely obtain 2,3,5,6-4-aminopyridine phosphate powder.
embodiment 5
On the basis of embodiment 1-4:
Preferably, in step, 2,3,5,6-described 4-aminopyridine hydrochlorides and the mass ratio of polyphosphoric acid are 1:1.
Preferably or further, in step, the solvent temperature of described dissolving controls to be 50 DEG C.
Preferably, in stepb, described deionized water and the volume ratio of polyphosphoric acid are 1:1.
Preferably, in step D, described precipitation agent is ethanol or n-propyl alcohol.
Preferably, in step e, described vacuum drying temperature is 50 DEG C.
Preferably or further, in step e, even spray Hypophosporous Acid, 50 solution in 2,3,5,6-described 4-aminopyridine phosphate powder, then vacuum-drying.
Further, the massfraction of described Hypophosporous Acid, 50 solution is 35%, and the quality of Hypophosporous Acid, 50 solution is 1% of 2,3,5,6-4-aminopyridine phosphate powder quality.
Further, described vacuum drying temperature is 50 DEG C.
embodiment 6
On the basis of embodiment 1-4:
Preferably, in step, 2,3,5,6-described 4-aminopyridine hydrochlorides and the mass ratio of polyphosphoric acid are 1:3.
Preferably or further, in step, the solvent temperature of described dissolving controls to be 60 DEG C.
Preferably, in stepb, described deionized water and the volume ratio of polyphosphoric acid are 5:1.
Preferably, in step D, described precipitation agent is ethanol or n-propyl alcohol.
Preferably, in step e, described vacuum drying temperature is 70 DEG C.
Preferably or further, in step e, even spray Hypophosporous Acid, 50 solution in 2,3,5,6-described 4-aminopyridine phosphate powder, then vacuum-drying.
Further, the massfraction of described Hypophosporous Acid, 50 solution is 35%, and the quality of Hypophosporous Acid, 50 solution is 3% of 2,3,5,6-4-aminopyridine phosphate powder quality.
Further, described vacuum drying temperature is 70 DEG C.
embodiment 7
On the basis of embodiment 1-4:
Preferably, in step, 2,3,5,6-described 4-aminopyridine hydrochlorides and the mass ratio of polyphosphoric acid are 1:2.
Preferably or further, in step, the solvent temperature of described dissolving controls to be 55 DEG C.
Preferably, in stepb, described deionized water and the volume ratio of polyphosphoric acid are 3:1.
Preferably, in step D, described precipitation agent is ethanol or n-propyl alcohol.
Preferably, in step e, described vacuum drying temperature is 60 DEG C.
Preferably or further, in step e, even spray Hypophosporous Acid, 50 solution in 2,3,5,6-described 4-aminopyridine phosphate powder, then vacuum-drying.
Further, the massfraction of described Hypophosporous Acid, 50 solution is 35%, and the quality of Hypophosporous Acid, 50 solution is 2% of 2,3,5,6-4-aminopyridine phosphate powder quality.
Further, described vacuum drying temperature is 60 DEG C.
embodiment 8
On the basis of embodiment 1-4:
Preferably, in step, 2,3,5,6-described 4-aminopyridine hydrochlorides and the mass ratio of polyphosphoric acid are 1:2.5.
Preferably or further, in step, the solvent temperature of described dissolving controls to be 58 DEG C.
Preferably, in stepb, described deionized water and the volume ratio of polyphosphoric acid are 2:1.
Preferably, in step D, described precipitation agent is ethanol or n-propyl alcohol.
Preferably, in step e, described vacuum drying temperature is 66 DEG C.
Preferably or further, in step e, even spray Hypophosporous Acid, 50 solution in 2,3,5,6-described 4-aminopyridine phosphate powder, then vacuum-drying.
Further, the massfraction of described Hypophosporous Acid, 50 solution is 35%, and the quality of Hypophosporous Acid, 50 solution is 1.2% of 2,3,5,6-4-aminopyridine phosphate powder quality.
Further, described vacuum drying temperature is 53 DEG C.
Claims (8)
1. a 4-aminopyridine method for production of phosphate salt, is characterized in that: comprise following processing step:
A, 2,3,5,6-4-aminopyridine hydrochloride is dissolved in phosphorus pentoxide content at 50-80 DEG C is in the polyphosphoric acid of 75-85%;
B, after it dissolves completely, slowly drip deionized water and be hydrolyzed, hydrolysis time is 0.5-2h;
After C, hydrolysis reaction terminate, the hydrolysate obtained by step B carries out suction filtration under nitrogen protection, obtains filtrate;
Drip precipitation agent in D, the filtrate that obtains in step C muddy to system, obtain troubled liquor, described precipitation agent is ethanol or n-propyl alcohol;
E, the temperature of gained troubled liquor in step D is down to 0-20 DEG C, separates out to a large amount of white solid, then filter under nitrogen protection, wash, then vacuum-drying, namely obtain 2,3,5,6-4-aminopyridine phosphate powder.
2. a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt according to claim 1, is characterized in that: in step, and 2,3,5,6-described 4-aminopyridine hydrochlorides and the mass ratio of polyphosphoric acid are 1:1-3.
3. a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt according to claim 1 and 2, is characterized in that: in step, and the solvent temperature of described dissolving controls as 50-60 DEG C.
4. a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt according to claim 1, it is characterized in that: in stepb, described deionized water and the volume ratio of polyphosphoric acid are 1-5:1.
5. a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt according to claim 1, it is characterized in that: in step e, described vacuum drying temperature is 50-70 DEG C.
6. a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt according to claim 1 or 5, is characterized in that: in step e, even spray Hypophosporous Acid, 50 solution in 2,3,5,6-described 4-aminopyridine phosphate powder, then vacuum-drying.
7. according to claim 6 a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt, is characterized in that: the massfraction of described Hypophosporous Acid, 50 solution is 35%, and the quality of Hypophosporous Acid, 50 solution is 2, the 1-3% of 3,5,6-4-aminopyridine phosphate powder quality.
8. a kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt according to claim 6, is characterized in that: described vacuum drying temperature is 50-70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310617931.1A CN103588703B (en) | 2013-11-29 | 2013-11-29 | A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310617931.1A CN103588703B (en) | 2013-11-29 | 2013-11-29 | A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103588703A CN103588703A (en) | 2014-02-19 |
| CN103588703B true CN103588703B (en) | 2015-08-05 |
Family
ID=50079058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310617931.1A Active CN103588703B (en) | 2013-11-29 | 2013-11-29 | A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103588703B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121728A (en) * | 1993-04-28 | 1996-05-01 | 阿克佐诺贝尔公司 | Rigid rod polymer based on pyridobisimidazole |
| WO1999027169A1 (en) * | 1997-11-21 | 1999-06-03 | Akzo Nobel N.V. | Flame-retardant materials |
| CN101289419A (en) * | 2008-06-06 | 2008-10-22 | 哈尔滨工业大学 | Process for preparing 2,3,5,6-tetraminopyridine hydrochloride |
| CN101330845A (en) * | 2005-12-16 | 2008-12-24 | 纳幕尔杜邦公司 | Thermal performance garments comprising an outer shell fabric of PIPD and aramid fibers |
| CN101417973A (en) * | 2008-10-17 | 2009-04-29 | 哈尔滨工业大学 | Method for preparing 2,3,5,6-tetra aminopyridine-2,5-dihydroxy terephthalate |
| CN103102274A (en) * | 2011-11-11 | 2013-05-15 | 浙江工业大学 | Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof |
-
2013
- 2013-11-29 CN CN201310617931.1A patent/CN103588703B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121728A (en) * | 1993-04-28 | 1996-05-01 | 阿克佐诺贝尔公司 | Rigid rod polymer based on pyridobisimidazole |
| WO1999027169A1 (en) * | 1997-11-21 | 1999-06-03 | Akzo Nobel N.V. | Flame-retardant materials |
| CN101330845A (en) * | 2005-12-16 | 2008-12-24 | 纳幕尔杜邦公司 | Thermal performance garments comprising an outer shell fabric of PIPD and aramid fibers |
| CN101289419A (en) * | 2008-06-06 | 2008-10-22 | 哈尔滨工业大学 | Process for preparing 2,3,5,6-tetraminopyridine hydrochloride |
| CN101417973A (en) * | 2008-10-17 | 2009-04-29 | 哈尔滨工业大学 | Method for preparing 2,3,5,6-tetra aminopyridine-2,5-dihydroxy terephthalate |
| CN103102274A (en) * | 2011-11-11 | 2013-05-15 | 浙江工业大学 | Preparation and application of 1,2,4,5-tetra amino benzene and hydrochloride thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103588703A (en) | 2014-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119534B (en) | One birdss of the same feather flock together hydroxyl to phenylene Benzo-dioxazole polymer and its preparation and application | |
| CN103588703B (en) | A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt | |
| CN110872259A (en) | Method for continuously producing 5-acetoacetylaminobenzimidazolone | |
| CN101050278B (en) | Half dullspon slices of caprone and production method | |
| CN106750302B (en) | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone | |
| CN111087274B (en) | Method for preparing bis (norbornadiene) rhodium tetrafluoroborate | |
| CN1247536C (en) | Process for preparing guanidine hydrochloride | |
| CN103242528A (en) | Method for synthesizing linear high molecular weight polyphenyl thioether | |
| CN101280472B (en) | Special-shaped monofilament section and production method thereof | |
| CN102936342B (en) | Semi-continuous preparation method of poly-p-phenylene benzobisoxazazole polymer | |
| KR102204083B1 (en) | Method for preparing polyamide resin | |
| CN110551284B (en) | Preparation method of poly (p-phenylene-benzobisoxazole) fibers | |
| CN109694389A (en) | A kind of preparation method of fosfomycin sodium | |
| CN114195791A (en) | Multi-element ionic liquid and preparation method and application thereof | |
| CN103408752A (en) | Preparation method of poly(m-phenylene isophthalamide) fibrid colloid polymer | |
| WO2019033485A1 (en) | Method for preparing extruded nylon elastomer in twin-screw reactor | |
| KR101938615B1 (en) | Method for preparing polyamide resin | |
| CN112940022A (en) | Preparation method of dimethylamine borane | |
| CN101514178B (en) | Method for synthesizing N-methylpyrrolidone | |
| CN110563615A (en) | Water/alcohol soluble micromolecule hole transport material and preparation method thereof | |
| CN107573502B (en) | Preparation method of long carbon chain nylon 1211 | |
| CN103160950A (en) | Preparation method for ultraviolet-resistant PBO fibers | |
| CN115651191B (en) | Method for preparing semi-aromatic polyamide and semi-aromatic polyamide prepared by method | |
| CN102276425A (en) | Preparation method of bisphenol F, tricyclic phenolic resin and tetracyclic phenolic resin | |
| CN114854016B (en) | Preparation method of low-ion precipitation polyphenylene sulfide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |