CN107551962B - High-thermal-stability two-component organogel and preparation method thereof - Google Patents
High-thermal-stability two-component organogel and preparation method thereof Download PDFInfo
- Publication number
- CN107551962B CN107551962B CN201710841241.2A CN201710841241A CN107551962B CN 107551962 B CN107551962 B CN 107551962B CN 201710841241 A CN201710841241 A CN 201710841241A CN 107551962 B CN107551962 B CN 107551962B
- Authority
- CN
- China
- Prior art keywords
- organogel
- gelator
- component
- gel
- organic solvent
- 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
Images
Abstract
A high-thermal stability two-component organogel is prepared from the first gelatorN 1,N 3,N 5-tris (2-ethylhexyl) benzene-1, 3, 5-trimethylamide, the second gelator triethylamine hydrochloride and a low-polarity organic solvent. The two-component organogel provided by the invention constructs a porous three-dimensional reticular supramolecular structure through the synergistic effect between the first gelator and the second gelator, and the formed organogel has high thermal stability, namely gel-solution phase transition temperature.
Description
Technical Field
The invention belongs to the technical field of supermolecule chemistry and functional materials, relates to an organogel, and particularly relates to an organogel with high thermal stability and a preparation method of the organogel.
Background
Certain small organic molecules form stable organogels in organic solvents at very low concentrations (even below 1 wt.%), and such small organic molecules that are capable of gelling organic solvents are known as gelators. Through non-covalent bond effects such as hydrogen bond, pi-pi accumulation, van der waals force and the like, the gel factors can be self-assembled to form fiber structures with different sizes, and the fiber structures are mutually stacked and wound to finally form an ordered three-dimensional network structure. Meanwhile, the three-dimensional network structure can wrap the organic solvent, so that the system loses fluidity to form organogel. As a physical gel, organogels have the property of being thermoreversible, i.e., changing the ambient temperature, which will result in a transition between the gel state and the solution state. Therefore, the functionalized organogel has wide application prospect in the fields of soft materials, sensors, soft templates and the like.
In recent years, research on potential application values of organogels formed by designing and synthesizing novel organic small-molecule gelators in various aspects has received wide attention of researchers. However, most of the reported organogels have a low thermal reversible temperature, i.e., poor thermal stability, and a small increase in ambient temperature has a large effect on the thermal stability of the gel, for example, the gel used as a functional soft material is directly liquefied. The main driving force for forming the gel is weak non-covalent bond acting force such as hydrogen bond, pi-pi accumulation, van der waals force and the like, and the non-covalent bond acting force can be rapidly weakened along with the rise of temperature, so that the originally solidified organic gel is gradually converted into solution, and the potential application value of the organic gel is greatly reduced. Therefore, in the field of organogel research, although a large amount of gelators are synthesized every year, the formed gel has poor thermal stability, so that the gel is far from meeting the requirements of various potential applications in the field of functional materials.
The thermal stability of gels is currently improved mainly by several methods: 1. synthesizing a large amount of various potential gel factors, and screening out gel with better thermal stability by researching the gel capacity and the thermal stability in various solvents with different polarities; 2. purposefully designing and synthesizing a nitrogen-containing organic ligand, preparing metal organogel by trying the action of a large amount of metal ions on the nitrogen-containing organic ligand, and effectively improving the thermal stability of the gel through the coordination action between a nitrogen-containing group of the ligand and the metal ions; 3. on the basis of the known high-efficiency gelators, the chemical structure of the gelators is purposefully modified to be complicated, functional groups are increased, and the thermal stability of the formed gel is improved by improving the interaction of hydrogen bonds, pi-pi accumulation, van der Waals force and the like among the gelators.
Although the above method can improve the thermal stability of the gel, it is still difficult to realize the method. This is because during the synthesis of large quantities of various potential gelators or design of synthetic nitrogen-containing organic ligands, the discovery of most ideal gelators is by chance and no fixed rule is followed. The chemical structure of the modified known high-efficiency gelator is often complex, and the required synthesis steps are more, so that the preparation of the gelator is complex, the period is longer, and the practicability of the gelator is limited to a certain extent.
Timme, A. et al report a gelatorN 1,N 3,N 5-tris (2-ethylhexyl)Yl) benzene-1, 3, 5-trimethylamide (Chemistry-A European Journal, 2012, 18, 8329-)), but only with regard to its chemical structure and properties in liquid crystals, and not with regard to the performance of the gelator in terms of its thermal stability.
Disclosure of Invention
The invention aims to provide a two-component organogel which can obviously improve the thermal stability of the formed organogel.
The invention also provides a preparation method of the two-component organogel.
The two-component organogel of the invention is prepared by a first gelatorN 1,N 3,N 5-tris (2-ethylhexyl) benzene-1, 3, 5-trimethylamide, the second gelator triethylamine hydrochloride and a low-polarity organic solvent.
In particular, the first gelatorN 1,N 3,N 5-tris (2-ethylhexyl) benzene-1, 3, 5-trimethylamide having the formula C33H57N3O3The structural formula is as follows. The first gelator can form gel in almost all types of organic solvents, such as halogenated hydrocarbons, alcohols, ethers, esters, amines, amides solvents, or mixed solvents thereof, within a short time, and is a gelator with high-efficiency gelling capability.
More specifically, 2-ethylhexylamine, trimesoyl chloride and triethylamine can be used as raw materials, and the first gelator is prepared by stirring and reacting in chloroform solvent at 30-50 ℃ for 8-24 h.
In the preparation method, the preferred molar ratio of the 2-ethylhexylamine, the trimesoyl chloride and the triethylamine is 3-10: 1: 3-10.
The dosage of the solvent chloroform is preferably 20-100 mL per 1g of the total amount of the raw materials.
The first gelator is white powdery solid and is obtained by washing the reaction liquid obtained by the reaction, collecting an organic phase, drying and removing a solvent.
The two-component organogel can be prepared by the following method: and dissolving the first gelator and the second gelator in a low-polarity organic solvent, and standing to form the two-component organogel.
Further, the process of dissolving the first gelator and the second gelator in the low-polarity organic solvent can be assisted by heating and ultrasonic treatment to assist the dissolution of the gelators.
In the two-component organogel prepared by the invention, the mass ratio of the first gelator to the second gelator is preferably 10-100: 1.
More preferably, in the process of preparing the two-component organogel, the total concentration range of the first gelator and the second gelator added to the low-polarity organic solvent is 5-30 mg/mL.
Wherein the low polarity organic solvent is relative to the polar organic solvent, and comprises non-polar and medium polarity organic solvents. The low-polarity organic solvent can be one of conventional low-polarity organic solvents such as cyclohexane, toluene, xylene, dioxane, tetrahydrofuran, dichloromethane, chloroform and the like. Preferred low polarity organic solvents are cyclohexane or toluene.
In the preparation process of the two-component organic gel, the standing is carried out at room temperature, and the standing time is not less than 5 hours. Preferably, the standing time at room temperature is 5-24 h.
On the basis of utilizing intermolecular hydrogen bond, pi-pi accumulation and van der waals force of the first gel factor, the invention reasonably utilizes the characteristic of poor solubility of the second gel factor in a low-polarity organic solvent, and constructs the two-component organic gel with high thermal stability through the synergistic effect between the first gel factor and the second gel factor.
Compared with the fibrous supramolecular structure of the traditional organogel, the supramolecular structure of the bi-component organogel prepared by the invention is a porous three-dimensional reticular system, so that the bi-component organogel has high thermal stability, namely higher gel-solution phase transition temperature.
The present invention tests the gel-solution phase transition temperature of organogels using the following method: the sealed small bottle (diameter is 12mm) containing the two-component organogel with different concentrations is placed in a vacuum oven upside down, the temperature is slowly increased at the temperature increasing speed of 12 ℃/h, and when the organogel slides to the bottom of the bottle under the action of gravity, the gel-solution phase transition temperature of the organogel is recorded.
The thermal stability of the two-component organogel is obviously higher than that of the organogel formed by the single component of the first gelator, and the thermal stability of the gel is obviously improved.
The preparation method of the two-component organogel is simple, the conditions are mild, the preparation process is fast, the thermal stability of the prepared organogel is good, and the two-component organogel has application potential in the aspects of optimizing the performance of a molecular self-assembly system, preparing a chemical sensor, preparing a novel nano functional soft material and the like.
Drawings
FIG. 1 is a NMR spectrum of the first gelator prepared in example 1.
FIG. 2 is a graph of gel-solution phase transition temperature versus concentration for a two-component organogel formed in toluene and a first gelator-forming organogel.
FIG. 3 is a plot of gel-solution phase transition temperature versus concentration for a two-component organogel formed in cyclohexane and a first gelator-forming organogel.
FIG. 4 is a transmission electron micrograph of the two-component organogel prepared in example 7.
FIG. 5 is a scanning electron micrograph of an organogel formed from the first gelator of example 7.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1.
856mg of 2-ethylhexylamine, 500mg of trimesoyl chloride and 670mg of triethylamine were weighed out and dissolved in 150mL of dry chloroform, followed by reaction with stirring at 35 ℃ for 12 hours. After the reaction liquid is cooled to room temperature, the reaction liquid is extracted for three times by deionized water, an organic phase is collected, dried by anhydrous sodium sulfate, filtered and the solvent is dried by decompression and spin-drying to obtain the first gelatorN 1,N 3,N 5-tris (2-ethylhexyl) benzene-1, 3, 5-trimethylamide as a white powder solid 813mg in 79% yield.
FIG. 1 is a drawing ofN 1,N 3,N 5-hydrogen nuclear magnetic resonance spectrum of tris (2-ethylhexyl) benzene-1, 3, 5-trimethylamide. And (3) representing solvent peaks in the spectrogram, wherein all characteristic peaks give clear attribution, and the spectrogram does not contain any impurity peak, so that the purity of the prepared first gel factor is higher.
Example 2.
Weighing 9.5mg of the first gelator and 0.5mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of toluene, heating to 85 ℃, carrying out intense ultrasound until the gelators are completely dissolved in the toluene, naturally cooling to room temperature, and standing for 9h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to a gel-solution phase transition temperature of 73 ℃.
Organogels were formed in toluene using the first gelator alone under the same conditions and were tested to have a gel-solution phase transition temperature of 51 ℃.
Example 3.
Weighing 11.4mg of the first gelator and 0.6mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of toluene, heating at 88 ℃ and carrying out intense ultrasound until the gelators are completely dissolved in the toluene, naturally cooling to room temperature, and standing for 8h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to determine the organogel to have a gel-solution phase transition temperature of 77 ℃.
Organogels were formed in toluene using the first gelator alone under the same conditions and were tested to have a gel-solution phase transition temperature of 54 ℃.
Example 4.
Weighing 13.3mg of the first gelator and 0.7mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of toluene, heating to 85 ℃, carrying out intense ultrasound until the gelators are completely dissolved, naturally cooling to room temperature, and standing for 6 hours to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to have a gel-solution phase transition temperature of 82 ℃.
Organogels were formed in toluene under the same conditions using the first gelator alone and were tested to have a gel-solution phase transition temperature of 56 ℃.
Example 5.
Weighing 15.2mg of the first gelator and 0.8mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of toluene, heating at 96 ℃ and carrying out intense ultrasound until the gelators are completely dissolved in the toluene, naturally cooling to room temperature, and standing for 9h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to have a gel-solution phase transition temperature of 86 ℃.
Organogels were formed in toluene using the first gelator alone under the same conditions and were tested to have a gel-solution phase transition temperature of 58 ℃.
Example 6.
Weighing 17.1mg of the first gelator and 0.9mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of toluene, heating at 88 ℃ and performing intense ultrasonic treatment until the gelators are completely dissolved, naturally cooling to room temperature, and standing for 5h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to determine a gel-solution phase transition temperature of 89 ℃ for the organogel.
Organogels were formed in toluene using the first gelator alone under the same conditions and were tested to have a gel-solution phase transition temperature of 60 ℃.
FIG. 2 is a graph showing the relationship between the gel-solution phase transition temperature and the concentration of the organogel formed by the two-component organogel and the first gelator in examples 2-6. The spectrogram shows that the gel-solution phase transition temperature of the two-component organogel is obviously higher than that of the organogel formed by the first gelator under different concentration conditions, which indicates that the thermal stability of the two-component organogel is far better than that of the organogel formed by the first gelator.
Example 7.
Weighing 9.5mg of the first gelator and 0.5mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of cyclohexane, heating to 88 ℃ and carrying out intense ultrasound until the gelators are completely dissolved, naturally cooling to room temperature, and standing for 9h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to a gel-solution phase transition temperature of 103 ℃.
Organogels were formed in cyclohexane under the same conditions using the first gelator alone and were tested to have a gel-solution phase transition temperature of 73 ℃.
FIG. 4 is a transmission electron micrograph of the two-component organogel prepared above, showing that the supramolecular structure forming the organogel is a porous three-dimensional network system.
FIG. 5 is a scanning electron micrograph of the single-component organogel prepared as described above, showing that the supramolecular structure of the organogel is a typical ordered fiber structure.
Example 8.
Weighing 11.4mg of the first gelator and 0.6mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of cyclohexane, heating to 94 ℃, carrying out intense ultrasound until the gelators are completely dissolved in the cyclohexane, naturally cooling to room temperature, and standing for 10h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to have a gel-solution phase transition temperature of 106 ℃.
Organogels were formed in cyclohexane under the same conditions using the first gelator alone and were tested to have a gel-solution phase transition temperature of 78 ℃.
Example 9.
Weighing 13.3mg of the first gelator and 0.7mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of cyclohexane, heating at 89 ℃, strongly performing ultrasonic treatment until the gelators are completely dissolved, naturally cooling to room temperature, and standing for 8h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to have a gel-solution phase transition temperature of 108 ℃.
Organogels were formed in cyclohexane under the same conditions using the first gelator alone and were tested to have a gel-solution phase transition temperature of 81 ℃.
Example 10.
Weighing 15.2mg of the first gelator and 0.8mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of cyclohexane, heating at 88 ℃ and performing intense ultrasonic treatment until the gelators are completely dissolved, naturally cooling to room temperature, and standing for 7h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to have a gel-solution phase transition temperature of 110 ℃.
Organogels were formed in cyclohexane under the same conditions using the first gelator alone and were tested to have a gel-solution phase transition temperature of 84 ℃.
Example 11.
Weighing 17.1mg of the first gelator and 0.9mg of the second gelator into a screw-mouth vial with the diameter of 12mm, adding 1mL of cyclohexane, heating at 91 ℃ and performing intense ultrasonic treatment until the gelators are completely dissolved, naturally cooling to room temperature, and standing for 5h to form the stable organogel.
The vial was inverted in a vacuum oven and heated at a rate of 12 ℃/h to measure the organogel to have a gel-solution phase transition temperature of 110 ℃.
Organogels were formed in cyclohexane under the same conditions using the first gelator alone and were tested to have a gel-solution phase transition temperature of 86 ℃.
FIG. 3 is a graph showing the relationship between the gel-solution phase transition temperature and the concentration of the two-component organogel and the one-component organogel in examples 7 to 11. The spectrogram shows that the gel-solution phase transition temperature of the two-component organogel is obviously higher than that of the single-component organogel under different concentration conditions, which indicates that the thermal stability of the two-component organogel is far better than that of the single-component organogel.
Claims (7)
1. A high-thermal stability two-component organogel is prepared from the first gelatorN 1,N 3,N 5-tris (2-ethylhexyl) benzene-1, 3, 5-trimethylamide, a second gelator triethylamine hydrochloride and a low-polarity organic solvent, wherein the mass ratio of the first gelator to the second gelator in the mixed system is 10-100: 1, the total concentration range of the first gelator and the second gelator added into the low-polarity organic solvent is 5-30 mg/mL, and the low-polarity organic solvent is one of cyclohexane, toluene, xylene, dioxane, tetrahydrofuran, dichloromethane and chloroform.
2. The two-component organogel according to claim 1 wherein said low polarity organic solvent is cyclohexane or toluene.
3. The method of preparing the two-component organogel of claim 1, wherein the two-component organogel is formed by dissolving the first gelator and the second gelator in a low polarity organic solvent and allowing the two-component organogel to stand.
4. The process for the preparation of the two-component organogel according to claim 3, characterized in that the resting time is not less than 5 h.
5. The method for preparing the two-component organogel according to claim 4, wherein the standing time is 5 to 24 hours.
6. The two-component organogel according to claim 1, wherein the first gelator is prepared by stirring and reacting 2-ethylhexylamine, trimesoyl chloride and triethylamine as raw materials in chloroform as a solvent at 30-50 ℃ for 8-24 hours.
7. The two-component organogel of claim 6, wherein the molar ratio of 2-ethylhexylamine, trimesoyl chloride, and triethylamine is 3-10: 1: 3-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710841241.2A CN107551962B (en) | 2017-09-18 | 2017-09-18 | High-thermal-stability two-component organogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710841241.2A CN107551962B (en) | 2017-09-18 | 2017-09-18 | High-thermal-stability two-component organogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107551962A CN107551962A (en) | 2018-01-09 |
| CN107551962B true CN107551962B (en) | 2020-06-02 |
Family
ID=60980199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710841241.2A Active CN107551962B (en) | 2017-09-18 | 2017-09-18 | High-thermal-stability two-component organogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107551962B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516927B (en) * | 2018-11-19 | 2021-09-14 | 中北大学 | Supramolecular gel with adjustable gel factor and structural morphology |
| CN110575795B (en) * | 2019-10-06 | 2021-11-16 | 中北大学 | High-thermal-stability supermolecule organogel and preparation thereof |
| CN112354492B (en) * | 2020-10-30 | 2023-11-03 | 中北大学 | Organogel composition and preparation method thereof |
| CN112316861A (en) * | 2020-10-30 | 2021-02-05 | 中北大学 | Double-component organic gel composition and application thereof |
| CN112745241A (en) * | 2020-12-31 | 2021-05-04 | 中北大学 | Compound for detecting normal hexane or cyclohexane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2254127A1 (en) * | 2009-05-20 | 2010-11-24 | Nexans | Organogel for electrical cable insulating layer |
| CN105189449A (en) * | 2013-03-15 | 2015-12-23 | 特罗菲克斯制药股份有限公司 | Non-peptide BDNF neurotrophin mimetics |
-
2017
- 2017-09-18 CN CN201710841241.2A patent/CN107551962B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2254127A1 (en) * | 2009-05-20 | 2010-11-24 | Nexans | Organogel for electrical cable insulating layer |
| CN105189449A (en) * | 2013-03-15 | 2015-12-23 | 特罗菲克斯制药股份有限公司 | Non-peptide BDNF neurotrophin mimetics |
Non-Patent Citations (2)
| Title |
|---|
| Phase Behavior and Mesophase Structures of 1,3,5-Benzene- and 1,3,5-Cyclohexanetricarboxamides: Towards an Understanding of the Losing Order at the Transition into the Isotropic Phase;Andreas Timme，et al.;《Chemistry A European Journal》;20120531;第18卷;第8329-8339页 * |
| Tailoring Supramolecular Nanofibers for Air Filtration Applications;Daniel Weiss et al;《Applied Materials & Interfaces》;20160516;第8卷;第14885-14892页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107551962A (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107551962B (en) | High-thermal-stability two-component organogel and preparation method thereof | |
| CN110605098B (en) | Non-reversible covalent organic framework for efficiently and selectively recovering gold and preparation method thereof | |
| CN104478847A (en) | Acetal-substituted glucosamide, preparation method and method for preparing supramolecular gel | |
| CN107459583B (en) | Highly hyperbranched cationic polysaccharide derivative containing dendritic polyamide-amine group and preparation method thereof | |
| Liu et al. | Structure–property relationship of a class of efficient organogelators and their multistimuli responsiveness | |
| CN110575795B (en) | High-thermal-stability supermolecule organogel and preparation thereof | |
| CN104826562A (en) | Preparation method of supramolecular copolymerization column five-aromatic hydrocarbon gel | |
| CN103071806B (en) | Preparation method of water-soluble nanoparticles | |
| CN107674074B (en) | Preparation method and application of amphiphilic naphthalimide gelator | |
| JP2020019846A (en) | Cellulose derivative, heavy metal removal material containing the same, and heavy metal removing method using the same | |
| KR101079237B1 (en) | Compound having self-assembling property and preparing method thereof, and method for preparing nano structure using the same | |
| JP2020019845A (en) | Cellulose derivative, heavy metal removal material containing the same, and heavy metal removing method using the same | |
| WO2020027091A1 (en) | Cellulose derivative, heavy metal removing material using same, and heavy metal removing method using same | |
| CN110845507B (en) | Glycoluril-derivatized anthracene-group-containing molecular clip and preparation method and application thereof | |
| CN113603610B (en) | Naphthalene hydrazide organic gel factor and preparation method and application thereof | |
| CN112142613B (en) | Rosin-based small-molecule organic gel and cyclohexane gel formed by same | |
| CN105294721A (en) | Synthetic method and micrometer wire preparation method of perylene bisimide derivative | |
| US8461381B2 (en) | Preparation of organic compounds for enhanced reactivity | |
| CN108359456A (en) | A kind of preparation method of the leaded full-inorganic perovskite quantum dot fluorescence powder with petal-shaped pattern | |
| CN110681875B (en) | Isosteviol metal gel and preparation method and application thereof | |
| Huang et al. | A β-d-glucose pentaacetate derivative as an efficient phase selective gelator for oil spill recovery | |
| CN108129354B (en) | Gelling agent, gel composition and gel preparation method | |
| JP4424838B2 (en) | Analysis method for quaternary ammonium salts | |
| CN110526862A (en) | Molecule clathrate compound and the preparation method and application thereof | |
| CN107118214B (en) | A kind of synthetic method of compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |