CN110591140A - Nano-porous polymer film material constructed by utilizing hydrogen bonds - Google Patents
Nano-porous polymer film material constructed by utilizing hydrogen bonds Download PDFInfo
- Publication number
- CN110591140A CN110591140A CN201910795246.5A CN201910795246A CN110591140A CN 110591140 A CN110591140 A CN 110591140A CN 201910795246 A CN201910795246 A CN 201910795246A CN 110591140 A CN110591140 A CN 110591140A
- Authority
- CN
- China
- Prior art keywords
- polymer film
- film material
- solvent
- molecule
- nano
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a nano porous polymer film material constructed by utilizing hydrogen bonds. The regular columnar phase structure can be assembled through the hydrogen bond supermolecule interaction of amino and carboxyl between two small molecules, and the nano porous polymer film can be prepared through photocrosslinking and solvent etching. The porous polymer film has good thermal stability, self-supporting property and solvent resistance. The pore size is about 1nm, the pore size distribution is uniform, the pore size requirement of the nanofiltration membrane is met, and the method can be applied to the preparation of the nanofiltration membrane and the seawater desalination. The preparation process is simple and easy to operate, and is convenient for further large-area preparation. Meanwhile, carboxyl distributed in the pore diameter can be further chemically modified, and is expected to be applied to the aspects of catalysis, nano templates and the like.
Description
Technical Field
The invention relates to a porous material, in particular to a nano porous polymer film material with uniform pore size distribution and the pore size of about 1nm, which is mainly applied to the aspects of nanofiltration membranes, seawater purification, catalysis, nano templates and the like and belongs to the field of material chemistry.
Background
With the development of economy and the increasing standard of living, the demand of people for water resource purity in life, business and agriculture is increasing, which presents a serious challenge to the development of water purification technology. The traditional water purification mainly utilizes a filter membrane with a porous structure to separate and remove impurities. Impurities such as sludge can be filtered by using a macroporous material, but for impurities such as ions and small molecules, a porous film material with a smaller pore diameter (about 1nm) is required. Polyimide films are widely used commercially at present as water treatment membranes. But it has the disadvantages of non-uniform pore size, large pore size, etc., which also limits its further application and development. Therefore, the preparation of thin film materials with uniform micropores of approximately 1nm is an important research goal.
The porous film material with the thickness of nearly 1nm is mainly divided into two systems: inorganic materials and polymers. The method for constructing the porous material by using the polymer is favored by more scientific researchers due to the characteristics of easy realization of large order degree and porosity, easy processing and easy modification, and the like compared with inorganic materials such as activated carbon, porous silicon and the like, the method can keep good hole shapes in organic solvents. Due to the limitation of self-assembly size of the block copolymer, the current construction of the porous film material with the thickness of about 1nm is mainly realized by means of self-assembly of small molecules.
The supramolecular assembly system is an aggregate system with a specific structure and function formed by intermolecular interaction between different compounds, and mainly comprises electrostatic interaction, hydrogen bond, hydrophobic interaction, van der waals force and the like. The hydrogen bond is acting force with directionality and moderate in strength, so that a supermolecular system constructed by utilizing the hydrogen bond is more beneficial to molecular orientation. Because the traditional small molecule assembly method cannot ensure the strength of the film, a polymer film material is required to be further prepared by crosslinking, and the stability of the polymer film material is improved. The porous structure of the porous film material is mainly realized by etching. By means of the dynamic characteristic of hydrogen bonds, the supermolecular assembly system can obtain the porous polymer film material by a simpler and more convenient solvent etching method.
Disclosure of Invention
The invention aims to develop a method for constructing a novel nano-porous polymer film material with uniform pore size distribution and about 1nm of pore size, the prepared nano-porous polymer film material can be applied to the fields of nanofiltration membranes, seawater purification and the like, and simultaneously carboxyl functional groups in the pore size can be further chemically modified, so that the nano-porous polymer film material is expected to be applied to the aspects of catalysis, nano templates and the like.
The invention mainly aims at the problem that the existing polyimide film for seawater desalination does not have a uniform porous structure, and the like, and utilizes the design idea of a supramolecular assembly based on hydrogen bonds for reference, and utilizes photo-crosslinking and solvent etching to construct a nano porous polymer film material with uniform pore size distribution and the pore size of about 1 nm. The invention adopts a supermolecule compound with a columnar phase assembled by the mutual action of hydrogen bonds between a template molecule A and a ligand molecule B, further forms a polymer film with certain stability and a columnar phase structure through ultraviolet crosslinking, and washes away the template molecule A through solvent etching, thereby obtaining the nano porous polymer film material with uniform pore size distribution and the pore size of about 0.5-1.5 nm. Because the ultraviolet crosslinking method is adopted in the preparation process to tightly crosslink the small molecules, the nano porous polymer film material has certain thermal stability, self-supporting property and solvent resistance, and is expected to be applied to the aspects of nanofiltration membrane construction and water purification technology. Meanwhile, the carboxyl functional group in the pore diameter can be further chemically modified, and is expected to be applied to the aspects of catalysis, nano templates and the like, so that the application prospect of the nano template is greatly widened.
Specifically, as shown in fig. 1, the template molecule a is a molecule capable of forming a triple coordination hydrogen bond, and is capable of forming a hydrogen bond, and the molecule having a crosslinkable group at the molecular end is a ligand molecule B, and is compounded by using the hydrogen bond in a certain proportion, and a regular and uniform columnar phase structure is formed by self-assembly; then fixing the phase structure by a cross-linking method, and removing the template molecules by selective etching by using a solvent to obtain the porous film material with the aperture of about 1 nm.
The template molecule A is a melamine derivative, and the structure of the melamine derivative is shown as a formula I:
in the formula I, R1The linear alkyl is preferably a linear alkyl of C1-C20, more preferably a linear alkyl of C1-C12. The template molecule A has triple hydrogen bond sites and can be compounded with multiple ligands to form a columnar phase structure with symmetrical shape, and R is1Can improve the solubility of the template molecule A.
The structure of the ligand molecule B is shown as a formula II:
in the formula II, three R2Which may be identical or different, represent a functional group of a compound capable of photocrosslinking, preferably a group containing unsaturated double bonds, such as a methacrylate function (-OCOC (CH)3)＝CH2) Acrylate functional group (-OCOCH ═ CH)2) Vinyl (-CH ═ CH)2) Etc., or a derivative group thereof.
The crosslinking agent used in the preparation process is a common photocrosslinking initiator, such as (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, benzoin methyl ether, benzoin ethyl ether and the like.
The invention also provides a preparation method of the nano-porous polymer film material, which comprises the following steps:
1) dissolving and mixing a proper amount of template molecules A and ligand molecules B by using a proper solvent, adding a photocrosslinking agent, and stirring until the mixture is uniformly mixed;
2) standing at room temperature, slowly volatilizing the solvent, then placing in a vacuum drying oven to remove the residual solvent, and self-assembling to form a hydrogen bond compound with a columnar phase structure;
3) placing the hydrogen bond compound under ultraviolet light for curing and crosslinking, and fixing the columnar phase structure to obtain a polymer film with certain stability;
4) and further placing the polymer film in a solvent to etch and remove the template molecule A, and drying to obtain the nano porous polymer film material.
In the step 1), the molar ratio of the template molecule A to the ligand molecule B is generally 1: 3; the photocrosslinking agent is preferably 2,4, 6-trimethyl benzoyl-diphenyl phosphorus oxide, and the addition amount of the photocrosslinking agent can be 1-5% of the mass of the hydrogen bond complex.
In the step 1), the solvent is an aprotic solvent such as dichloromethane and chloroform.
Step 3) above for R2In the case of methacrylate functionality, crosslinking can be carried out for more than 24 hours under a 365nm UV lamp.
In the step 4), the solvent selected for etching is a polar solvent such as ethanol, methanol, dimethyl sulfoxide and the like.
In conclusion, the invention can assemble a regular columnar phase structure through the hydrogen bond supermolecule interaction of amino and carboxyl between two small molecules, and can simply and quickly prepare the nano porous polymer film material with the uniform aperture of nearly 1nm through further photocrosslinking and solvent etching. The prepared nano-porous polymer film material has good thermal stability, self-supporting property and solvent resistance. Compared with the prior art, the invention has the advantages that:
1) the preparation method of the nano porous polymer film material is simple and convenient by using the methods of hydrogen bond assembly, ultraviolet crosslinking and solvent etching. And the selected small molecules have simple structure, easily obtained raw materials and convenient synthesis, and are convenient for further large-scale production.
2) The nano porous polymer film material has a porous structure with the pore size of about 1nm and uniform distribution, meets the pore size requirement of a nanofiltration membrane, and solves the problems of nonuniform pore size distribution and large pore size of the existing polyimide film.
3) The nano-porous polymer film material has good thermal stability, self-supporting property and solvent resistance, and provides possibility for further realizing the application of nano-filtration films, water purification technologies and the like.
4) The nano porous polymer film material of the invention is distributed with carboxyl functional groups in the pores, can be further chemically modified and is expected to be applied to the aspects of catalysis, nano templates and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a nanoporous polymer film according to the invention.
FIG. 2 is a differential scanning calorimetry trace of the hydrogen-bonding complex prepared in example 1.
FIG. 3 is a small angle X-ray scattering plot of the procedure for the nanoporous polymer thin film material prepared in example 1.
FIG. 4 is a temperature swing small angle X-ray scattering plot of the polymer film material prepared in example 1.
Detailed Description
The invention will be further described by means of specific embodiments, in conjunction with the accompanying drawings.
Example 1 Synthesis of template molecule A and ligand molecule B
Step 1: synthesis of template molecule A (2, 4-diamino-6-dodecylamino-1, 3, 5-triazine)
2.76g of 2-chloro-4, 6-diamino-1, 3, 5-triazine, 3.52g of dodecylamine, 1.60g of sodium bicarbonate and 100mL of 1, 4-dioxane are added into a 250mL dry flask and refluxed for 6h under the protection of argon. After the reaction, the reaction mixture was cooled to room temperature, poured into 200mL of ice water, and the precipitate was filtered and washed. Column separation (eluent: dichloromethane: methanol 10:1 by volume) afforded the product 3.30g, 59% yield.
Step 2: synthesis of ligand molecule B (3,4, 5-tris ((11- (methacryloyloxy) undecyl) oxy) benzoic acid)
A250 mL dry flask was charged with 2.45g of methyl 3,4, 5-trihydroxybenzoate, 10.0g of 11-bromo-1-undecanol, 11.0g of potassium carbonate, and 100mL of N, N-Dimethylformamide (DMF), and heated under reflux at 80 ℃ for 12 hours. After the reaction is finished, cooling to room temperature, filtering to remove potassium carbonate, and performing rotary evaporation on the reaction liquid to remove N, N-dimethylformamide. Column separation (eluent: dichloromethane: ethyl acetate 2:1 by volume) afforded compound 1 in 6.47g, 70% yield.
A250 mL dry flask was charged with 2.78g of Compound 1, 2.20g of potassium hydroxide, and 100mL of ethanol, and heated under reflux at 80 ℃ for 2 hours. After the reaction is finished, cooling to room temperature, and removing ethanol by rotary evaporation. 100mL of water was added, the pH adjusted to acidity with hydrochloric acid, filtered and dried to give 2.07g of Compound 2, 75% yield.
Into a 250mL dry flask were charged 900mg of Compound 2, 161mg of 4-dimethylaminopyridine, 1.47mg of 2, 6-di-tert-butyl-4-methylphenol, 660. mu.L of triethylamine, and 100mL of dichloromethane. 638 mu L of methacryloyl chloride is slowly dropped under the ice-bath condition, and after half an hour of ice-bath reaction, the stirring is continued for 24 hours at room temperature. After the reaction was complete, the dichloromethane was removed by rotary evaporation, and 10mL of water and 30mL of pyridine were added and refluxed for 2 h. After the reaction is finished, cooling to room temperature, slowly dropwise adding dilute hydrochloric acid, and adjusting the pH value to acidity. The mixture was extracted 3 times with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution. After drying and removal of the solvent by rotary evaporation, the ligand molecule b1.05g was obtained by column separation (eluent: dichloromethane: methanol 25:1 by volume) in 90% yield.
EXAMPLE 2 preparation of nanoporous Polymer film Material
2.50mg of the template molecule A and 22.5mg of the ligand molecule B synthesized in example 1 were weighed and dissolved in 1mL of chloroform, respectively. The two solutions were mixed and 0.2mg of photocrosslinker (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide was added. After stirring for 2h, the solvent was evaporated by standing. And then placing the mixture in a vacuum drying oven to remove residual solvent to obtain the hydrogen bond complex. And (3) placing the obtained hydrogen bond compound under an ultraviolet lamp of 365nm for crosslinking for 24h, so that the compound structure can be fixed, and the polymer film material can be obtained. And then, putting the polymer film material into 10mL of ethanol solvent for 48h, washing with ethanol for 3 times, and volatilizing until the solvent is removed by drying to obtain the nano-porous polymer film material.
Example 3 Performance testing of nanoporous Polymer film materials
About 3mg of the hydrogen bond complex sample prepared in the example 2 is taken, a differential scanning calorimeter is used for testing the thermal property, the temperature rising and reducing rates are both 10 ℃/min, and the experimental result is shown in figure 2. The experimental result shows that the compound has liquid crystallinity at room temperature. The samples in the process of preparing the nano-porous polymer film material in the example 2 are subjected to small-angle X-ray scattering tests, the experimental results are shown in FIG. 3, and the experimental results show that the columnar phase structures in the preparation process are all maintained. The polymer film material sample obtained by the preparation is subjected to a temperature-changing small-angle X-ray scattering test, and the experimental result is shown in figure 4, and the experimental result shows that the polymer film material sample obtained by the preparation has good thermal stability.
Example 4 self-supporting and solvent resistance testing of nanoporous Polymer film materials
The prepared nano porous polymer film material is clamped by tweezers to obtain a visible complete film. The nano-porous polymer film material is placed in common organic solvents (chloroform, dichloromethane, ethanol, methanol and the like) to present an original film state.
Claims (10)
1. A nano porous polymer film material is a supermolecular complex which is self-assembled into a columnar phase structure by the interaction of hydrogen bonds between a template molecule A and a ligand molecule B, then the phase structure is fixed by a cross-linking method, and the template molecule A is removed by selective etching of a solvent to obtain the nano porous polymer film, wherein the template molecule A is a molecule capable of forming a triple coordination hydrogen bond; the ligand molecule B is a molecule which can form hydrogen bonds with the template molecule A and the molecular end contains crosslinkable groups.
2. The nanoporous polymer film material of claim 1, wherein the template molecule a is a melamine derivative having the structure according to formula I:
in the formula I, R1Is straight chain alkyl.
3. The nanoporous polymeric film material of claim 2, wherein R is1Is straight-chain alkyl of C1-C20.
4. The nanoporous polymer film material of claim 1, wherein the ligand molecule B has the structure according to formula II:
in the formula II, three R2The same or different, represent functional groups that can undergo photocrosslinking.
5. The nanoporous polymeric film material of claim 4, wherein R is2Selected from methacrylate functional groups, acrylate functional groups, vinyl groups or derivatives thereof.
6. The nanoporous polymeric film material of claim 5, wherein R is2Is selected from-OCOC (CH)3)＝CH2、-OCOCH＝CH2and-CH ═ CH2。
7. The nanoporous polymer film material of claim 1, wherein the nanoporous polymer film material has a porous structure with a uniform distribution and pore sizes of 0.5-1.5 nm.
8. A method for preparing the nano-porous polymer film material of any one of claims 1 to 7, comprising the following steps:
1) dissolving and mixing the template molecule A and the ligand molecule B by using a solvent, adding a photocrosslinking agent, and stirring until the mixture is uniformly mixed;
2) standing at room temperature, slowly volatilizing the solvent, then placing in a vacuum drying oven to remove the residual solvent, and self-assembling to form a hydrogen bond compound with a columnar phase structure;
3) placing the hydrogen bond compound under ultraviolet light for curing and crosslinking, and fixing the columnar phase structure to obtain a polymer film with certain stability;
4) and further placing the polymer film in a solvent to etch and remove the template molecule A, and drying to obtain the nano porous polymer film material.
9. The method according to claim 8, wherein the molar ratio of the template molecule A to the ligand molecule B in step 1) is 1: 3; the added photocrosslinking agent is 2,4,6, -trimethyl benzoyl-diphenyl phosphorus oxide, and the adding amount of the photocrosslinking agent is 1-5% of the mass of the hydrogen bond complex.
10. The method according to claim 8, wherein the solvent used in step 1) is an aprotic solvent, and the solvent used in the etching in step 4) is a polar solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910795246.5A CN110591140A (en) | 2019-08-27 | 2019-08-27 | Nano-porous polymer film material constructed by utilizing hydrogen bonds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910795246.5A CN110591140A (en) | 2019-08-27 | 2019-08-27 | Nano-porous polymer film material constructed by utilizing hydrogen bonds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110591140A true CN110591140A (en) | 2019-12-20 |
Family
ID=68855780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910795246.5A Pending CN110591140A (en) | 2019-08-27 | 2019-08-27 | Nano-porous polymer film material constructed by utilizing hydrogen bonds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110591140A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847327B (en) * | 2005-01-14 | 2012-05-30 | 施乐公司 | Radiation curable inks containing curable gelator additives |
| CN106700087A (en) * | 2016-12-05 | 2017-05-24 | 江汉大学 | Triple hydrogen-bond supramolecular polymer and preparation method thereof |
-
2019
- 2019-08-27 CN CN201910795246.5A patent/CN110591140A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847327B (en) * | 2005-01-14 | 2012-05-30 | 施乐公司 | Radiation curable inks containing curable gelator additives |
| CN106700087A (en) * | 2016-12-05 | 2017-05-24 | 江汉大学 | Triple hydrogen-bond supramolecular polymer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| BEATRIZ FERINGAN ET.AL.: "Supramolecular Columnar Liquid Crystals Formedby Hydrogen Bonding between a Clicked Star-Shapeds-Triazineand Benzoic Acids", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| 张秀莲: "三聚氰胺与有机酸氢键自组装的研究", 《三聚氰胺与有机酸氢键自组装的研究》 * |
| 章俊: "《3D打印成型技术》", 31 May 2016, 南京师范大学出版社 * |
| 罗永明: "《中药化学成分提取分离技术与方法》", 31 January 2016, 上海科学技术出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105694051A (en) | Click chemistry based metal-organic framework cross-linking membrane and preparation method and application thereof | |
| CN112341652B (en) | Chiral azobenzene polymer film and preparation method and application thereof | |
| CN107892733B (en) | Heavy metal wastewater ion adsorption resin and preparation method thereof | |
| CN114292374B (en) | Fluorine-containing multi-structural-unit covalent organic framework material, preparation method thereof and oil-water separation application | |
| Fan et al. | Preparation of a novel mixed non-covalent and semi-covalent molecularly imprinted membrane with hierarchical pores for separation of genistein in Radix Puerariae Lobatae | |
| CN113698579B (en) | Porphyrin conjugated microporous polymer and its synthesis method and application | |
| CN105327626B (en) | A kind of composite nanometer filtering film and preparation method thereof | |
| CN113461912B (en) | Polycyclic aromatic skeleton polymer, and preparation method and application thereof | |
| CN110591140A (en) | Nano-porous polymer film material constructed by utilizing hydrogen bonds | |
| CN108424500B (en) | Polymethyl methacrylate-b-poly-o-nitrobenzyl ester block copolymer based on star silsesquioxane and preparation method thereof | |
| CN112341569B (en) | Azobenzene polymer and preparation method and application thereof | |
| CN104031179A (en) | 6-site monosubstituted-beta-cyclodextrin functional monomer and preparation method thereof | |
| CN113019137A (en) | Preparation and application of MXene @ COF composite film | |
| CN105396473A (en) | Preparation method of temperature/pH-responsive cellulose acetate membrane and application of membrane | |
| KR101759998B1 (en) | Ion-exchange polymer containing catechol group, preparation method and application thereof | |
| CN109384869B (en) | Fluorine-containing azobenzene amphiphilic polymer, visible light response polymer nanotube and preparation method thereof | |
| CN103980398B (en) | A kind of to be derivant or self-assembly that its analog is fluorescence chromophoric end groups and preparation method thereof | |
| JPWO2013069681A1 (en) | Vinyl chloride copolymer porous body and method for producing the same | |
| CN113634238B (en) | Flexible porous boron affinity copolymer adsorbent and preparation method and application thereof | |
| CN111793196B (en) | Tetra- (4-aldehyde- (1, 1-biphenyl)) methane-based conjugated organic microporous polymer and preparation method thereof | |
| CN110681875B (en) | Isosteviol metal gel and preparation method and application thereof | |
| CN112940162A (en) | Synthetic method of highly-ordered dendritic heterogeneous sugar-containing polymer containing multiple glycosyl groups | |
| CN107382898B (en) | Energetic material based on ANPZ energetic parent structure and synthetic method thereof | |
| CN111393551A (en) | Photoresponse polymer based on styryl pyrene dimer and preparation method thereof | |
| CN116396653B (en) | Method for preparing metal-organic polymer coating based on latticed supermolecular monomer |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191220 |
|
| WD01 | Invention patent application deemed withdrawn after publication |