CN112679726A - Method for preparing lipophilic and hydrophilic transparent organic gel by using polyoxyethylene - Google Patents
Method for preparing lipophilic and hydrophilic transparent organic gel by using polyoxyethylene Download PDFInfo
- Publication number
- CN112679726A CN112679726A CN202011538771.8A CN202011538771A CN112679726A CN 112679726 A CN112679726 A CN 112679726A CN 202011538771 A CN202011538771 A CN 202011538771A CN 112679726 A CN112679726 A CN 112679726A
- Authority
- CN
- China
- Prior art keywords
- peo
- polymer
- hexanediamine
- reaction
- polymer monomer
- 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.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for preparing a lipophilic and hydrophilic transparent organic gel by using polyethylene oxide, which comprises the following steps: 1) polymer monomer synthesis: a, removing water in PEO molecules by an azeotropic method by using anhydrous toluene; b, after dehydration, adding 1, 6-hexane diisocyanate and dibutyltin dilaurate into a methylbenzene solution dissolved with PEO for reaction, dropwise adding the mixture into a normal hexane solution for precipitation after the reaction, and filtering to obtain a polymer monomer; 2) synthesis of PEO polymers containing urea structure: a, mixing a polymer monomer, anhydrous toluene and 1, 6-hexanediamine for reaction; dropwise adding 1, 6-hexanediamine for reaction, dropwise adding the mixture to a normal hexane solution for precipitation, and filtering to obtain a PEO polymer; PEO polymers were prepared as clear gels using water or chloroform as solvents. The advantages are that: the addition polymerization of PEO polymer monomer and 1, 6-hexanediamine is realized by a two-step method, and finally the polymer is synthesized.
Description
Technical Field
The invention belongs to the field of preparation of organogels, and particularly relates to a method for preparing a lipophilic and hydrophilic transparent organogel by using polyethylene oxide (PEO).
Background
Polyethylene oxide (PEO) is expected to be applied to the fields of solid electrolytes, sensors, inks, etc. because of its very strong absorption capacity for solvents. Particularly, with the development of the lithium ion battery industry, the all-solid-state battery is receiving attention due to its characteristics of high energy density, light weight, and the like. In recent years, the development of PEO as a solid electrolyte has been a focus of attention. Because PEO molecules are nontoxic, the hydrogel is often applied to the fields of cosmetics, drug delivery and the like.
Gels are classified into physical gels formed by the interaction between macromolecules and chemical gels, which are gels formed by the formation of organic macromolecules through chemical bonds. In general, PEO molecules have water solubility and are difficult to directly form hydrogel, so that hydrogen bonds capable of increasing intermolecular interaction force are required to be added to the main chain of the PEO molecules in order for the PEO molecules to form gel.
In order to increase intermolecular interaction, polymer monomer (1) was prepared by the reaction of PEO having a molecular weight of 10000 with 1, 6-diisocyanatohexane, and the synthesized polymer monomer was prepared as polymer (3) containing a urea structure by addition polymerization with 1, 6-hexanediamine. Since the molecular weight of the monomer exceeds 10000, the monomer hardly participates in polymerization, resulting in that chain extension becomes very difficult.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a transparent organogel with oleophylic property and hydrophilic property by using polyethylene oxide, wherein PEO monomer with large molecular weight and 1, 6-hexanediamine are subjected to addition polymerization, and PEO high polymer molecules after polymerization form the transparent organogel in aqueous solution and chloroform solution, and the transparent organogel has oleophylic property and hydrophilic property.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing a transparent organogel having lipophilic and hydrophilic properties from polyethylene oxide, comprising the steps of:
1) synthesis of Polymer monomers
a removal of the molecular weight M by azeotropy with anhydrous toluenew10000 of moisture in a PEO molecule;
b, after dehydration, adding 1, 6-hexane diisocyanate and dibutyltin dilaurate into a toluene solution dissolved with PEO for reaction, dropwise adding the solution obtained after the reaction into a n-hexane solution for precipitation, and filtering to obtain a white solid polymer monomer;
2) synthesis of PEO Polymer containing Urea Structure
a, mixing a polymer monomer, anhydrous toluene and 1, 6-hexanediamine for reaction;
b, continuously dropwise adding the residual 1, 6-hexanediamine, and continuously reacting;
c, dropwise adding the solution obtained after the reaction into a normal hexane solution for precipitation, and filtering to obtain a white solid PEO polymer;
d PEO polymer is used as a solvent to prepare transparent gel by using water or chloroform.
Adding 1, 6-hexane diisocyanate and dibutyltin dilaurate into the toluene solution dissolved with PEO in the step 1), and reacting for 8-12h at 50-60 ℃.
In the step 2), the polymer monomer, the anhydrous toluene and the 1, 6-hexanediamine are mixed and react for 12 hours at 80 ℃.
In the step 1) b, the addition amounts of 1, 6-diisocyanatohexane and dibutyltin dilaurate were 1.31g and 013g, respectively, and the amount of the obtained white solid polymer monomer was 13.85 g; 13.85g of polymer monomer, 200ml of anhydrous toluene and 0.08g of 1, 6-hexanediamine in the step 2) a; 0.05g of the remaining 1, 6-hexanediamine and 5.83g of the PEO polymer obtained in step 2) c as a white solid were added dropwise.
Compared with the prior art, the invention has the beneficial effects that:
the invention realizes the addition polymerization of PEO polymer monomer and 1, 6-hexanediamine by adding 1, 6-hexanediamine through a two-step method, and finally synthesizes the polymer. By infrared and1the structure of the polymer was characterized by H NMR measurement at 1625cm, as seen from the infrared measurement-1And 1720cm-1Characteristic absorption peaks belonging to NCO-and-NH-COO-functional groups, respectively, were clearly observed, indicating that the polymerized monomer (1) was successfully synthesized. And the characteristic peaks of the-NH-CO-NH-and-NH-CO-O-functional groups in the infrared test results of the polymer are shown at 1625cm-1And 1716cm-1It was demonstrated that polymer (3) was successfully synthesized, and since the polymer structure had both hydrophilic and lipophilic moieties, it formed transparent organogels in both aqueous and chloroform solutions.
Drawings
FIG. 1 is a scheme showing the synthesis of polymer monomers and the synthesis of PEO polymers containing urea structures.
FIG. 2 is a gel prepared with water and PEO polymer.
FIG. 2 (a) shows a normal state; (b) in an inverted state.
FIG. 3 is a gel prepared with chloroform and PEO polymer.
Fig. 3 (a) is a normal state; (b) in an inverted state.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example one
Referring to fig. 1, the method for preparing the lipophilic and hydrophilic transparent organogel by using polyethylene oxide is divided into the following two stages:
1) synthesis of Polymer monomers
a using 300mL anhydrous nailBenzene removal of molecular weight M by azeotropic Processw10000 moisture in PEO molecules.
b after dehydration, 1.31g of 1, 6-diisocyanatohexane and 0.13g of dibutyltin dilaurate were added to a toluene solution in which PEO was dissolved, the mixture was reacted at 50 ℃ for 12 hours, and then an n-hexane solution was added dropwise to precipitate, and the mixture was filtered to obtain 13.85g of a white solid polymer monomer.
2) Synthesis of PEO Polymer containing Urea Structure
a three-necked flask was charged with 13.85g of polymer monomer, 200mL of anhydrous toluene, and 0.08g of 1, 6-hexanediamine.
b reacting at 80 deg.C for 12h, adding 0.05g 1, 6-hexanediamine dropwise, and reacting for 12 h.
c precipitation by dropwise addition of an n-hexane solution and filtration gave 5.83g of PEO polymer as a white solid.
d PEO polymer as white solid was used to prepare a clear gel in water or chloroform as solvent, see FIGS. 2 and 3.
Structural characterization of PEO polymers
Test results of nuclear magnetism:
1H NMR(δ,CDCl3,ppm)1.20-1.39(-CH2-CH2-CH2-NHCONH-CH2-CH2-CH2-and-CH2-CH2-CH2-NHCOO-CH2-CH2-O-12H),1.40-1.54(-CH2-CH2-NHCONH-CH2-CH2-and-CH2-CH2-CH2-NHCOO-CH2-CH2-O-,12H),3.14-3.18(-CH2-CH2-NHCONH-CH2-CH2-and-CH2-CH2-CH2-NHCOO-CH2-CH2-,13H),(-NHCOO-CH2-CH2-O-,1190H),4.16-4.26(-NHCOO-CH2-CH2-O-,4H),4.64-3.53(-CONH-,-COONH-,5H)。
and (3) infrared test results:
FT-IR(cm-1)2878,1716,1625,1577,1467,1414,1360,1342,1280,1241,1146,1096,1060,961,947,842,736,660。
the invention realizes the addition polymerization of PEO polymer monomer and 1, 6-hexanediamine by adding 1, 6-hexanediamine through a two-step method, and finally synthesizes the molecular weight Mw＝1.4×105Molecular weight distribution of Mw/MnPEO polymer ═ 5.2. By infrared and1the structure of the polymer was characterized by H NMR measurement at 1625cm, as seen from the infrared measurement-1And 1720cm-1Characteristic absorption peaks belonging to NCO-and-NH-COO-functional groups, respectively, were clearly observed, indicating that the polymerized monomer (1) was successfully synthesized. And the characteristic peaks of the-NH-CO-NH-and-NH-CO-O-functional groups in the infrared test results of the polymer are shown at 1625cm-1And 1716cm-1It was demonstrated that polymer (3) was successfully synthesized, and that it forms transparent organogels in both aqueous and chloroform solutions, since the polymer structure has both hydrophilic and lipophilic moieties, see fig. 1. As can be seen from fig. 2, when the weight percentage concentration of the polymer is more than 4%, a hydrogel is formed, and when the weight percentage concentration of the polymer is more than 2%, an organogel using chloroform as a developing solvent is formed, see fig. 3. This indicates that the PEO polymer is relatively easier to form organogels.
Claims (4)
1. The method for preparing the lipophilic and hydrophilic transparent organogel by using the polyethylene oxide is characterized by comprising the following steps:
1) synthesis of Polymer monomers
a removal of the molecular weight M by azeotropy with anhydrous toluenew10000 of moisture in a PEO molecule;
b, after dehydration, adding 1, 6-hexane diisocyanate and dibutyltin dilaurate into a toluene solution dissolved with PEO for reaction, dropwise adding the solution obtained after the reaction into a n-hexane solution for precipitation, and filtering to obtain a white solid polymer monomer;
2) synthesis of PEO Polymer containing Urea Structure
a, mixing a polymer monomer, anhydrous toluene and 1, 6-hexanediamine for reaction;
b, continuously dropwise adding the residual 1, 6-hexanediamine, and continuously reacting;
c, dropwise adding the solution obtained after the reaction into a normal hexane solution for precipitation, and filtering to obtain a white solid PEO polymer;
d PEO polymer is used as a solvent to prepare transparent gel by using water or chloroform.
2. The method for preparing a transparent organogel having lipophilic and hydrophilic properties using polyethylene oxide according to claim 1, wherein 1, 6-diisocyanatohexane and dibutyltin dilaurate are added to the solution of PEO dissolved in the step 1) and reacted at 50-60 ℃ for 8-12 h.
3. The method for preparing lipophilic and hydrophilic transparent organogel using polyethylene oxide according to claim 1, wherein the polymer monomer, the anhydrous toluene and the 1, 6-hexanediamine are mixed and reacted at 80 ℃ for 12h in step 2).
4. The method for preparing a transparent organogel having lipophilic and hydrophilic properties using polyethylene oxide according to claim 1, wherein 1, 6-diisocyanatohexane and dibutyltin dilaurate are added in the step 1) b in an amount of 1.31g and 013g, respectively, and the amount of the obtained polymer monomer as a white solid is 13.85 g; 13.85g of polymer monomer, 200ml of anhydrous toluene and 0.08g of 1, 6-hexanediamine in the step 2) a; 0.05g of the remaining 1, 6-hexanediamine and 5.83g of the PEO polymer obtained in step 2) c as a white solid were added dropwise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011538771.8A CN112679726B (en) | 2020-12-23 | 2020-12-23 | Method for preparing lipophilic and hydrophilic transparent organic gel by using polyoxyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011538771.8A CN112679726B (en) | 2020-12-23 | 2020-12-23 | Method for preparing lipophilic and hydrophilic transparent organic gel by using polyoxyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112679726A true CN112679726A (en) | 2021-04-20 |
| CN112679726B CN112679726B (en) | 2023-03-17 |
Family
ID=75451156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011538771.8A Active CN112679726B (en) | 2020-12-23 | 2020-12-23 | Method for preparing lipophilic and hydrophilic transparent organic gel by using polyoxyethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112679726B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5634943A (en) * | 1990-07-12 | 1997-06-03 | University Of Miami | Injectable polyethylene oxide gel implant and method for production |
| CN103524697A (en) * | 2013-10-28 | 2014-01-22 | 苏州大学 | Polyurethaneurea hydrogel and preparation methods therefor |
| CN103539919A (en) * | 2013-10-28 | 2014-01-29 | 苏州大学 | Application of polyurethane urea hydrogel with shape memory function |
-
2020
- 2020-12-23 CN CN202011538771.8A patent/CN112679726B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5634943A (en) * | 1990-07-12 | 1997-06-03 | University Of Miami | Injectable polyethylene oxide gel implant and method for production |
| CN103524697A (en) * | 2013-10-28 | 2014-01-22 | 苏州大学 | Polyurethaneurea hydrogel and preparation methods therefor |
| CN103539919A (en) * | 2013-10-28 | 2014-01-29 | 苏州大学 | Application of polyurethane urea hydrogel with shape memory function |
Non-Patent Citations (2)
| Title |
|---|
| VINICIUS H BONATTINI等: "One-step formation of polyurea gel as a multifunctional approach for biological and environmental applications" * |
| 乔从德: "聚乙二醇基智能水凝胶的研究进展", 《高分子通报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112679726B (en) | 2023-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110437456B (en) | Self-healing polymer and preparation method and application thereof | |
| CN101218705B (en) | Solid polymer electrolyte for lithium ion battery and lithium ion battery | |
| EP1393394B1 (en) | Conductive polyamine-based electrolyte | |
| KR102184530B1 (en) | A crosslinked-type copolymer, a polymer membrane comprising the same, an anion exchange membrane comprising the polymer membrane, a fuel cell comprising the anion exchange membrane, and a method for manufacturing the crosslinked-type copolymer | |
| CN102206342B (en) | Electric conduction polymer and synthesis method thereof and electroactive electrode with surface covered with electric conduction polymer | |
| US7517615B2 (en) | Gel electrolyte, process for producing the same, and use thereof | |
| WO2012129805A1 (en) | Conductive polymer, synthesis method thereof, and electroactive electrode covered with said conductive polymer | |
| CN111354975B (en) | Triblock hybrid polymer electrolyte, and preparation method and application thereof | |
| CN112239543B (en) | Cross-linked comb-shaped polymer electrolyte, and preparation method and application thereof | |
| CN113621131A (en) | Polyelectrolyte material, preparation method thereof and polyelectrolyte membrane | |
| KR0176017B1 (en) | Water soluble conductive polyaniline composites | |
| EP1853644B1 (en) | Copolymer of propylene or ethylene oxide and of an oxirane bearing an ionic group | |
| CN115232465A (en) | Preparation method of tough self-repairing material capable of realizing self-repairing in seawater | |
| KR101720049B1 (en) | Solid polymer electrolytes comprising polymer crosslinked tannic acid derivative for secondary lithium battery | |
| CN112679726B (en) | Method for preparing lipophilic and hydrophilic transparent organic gel by using polyoxyethylene | |
| He et al. | Electroactive polymer with oligoanilines in the main chain and azo chromophores in the side chain: synthesis, characterization and dielectric properties | |
| KR101295678B1 (en) | Polysiloxane resin containing single-ion conductor and a film for lithium secondary battery using the same | |
| CN103887084A (en) | TiO2 hybridization polymer gel electrolyte and preparation method and application thereof | |
| CN108047668B (en) | polylactic acid fiber fused polypyrrole material and preparation method thereof | |
| CN112820938A (en) | Ion gel electrolyte with semi-interpenetrating network structure and preparation method and application thereof | |
| CN116285298A (en) | Ketone-based solid polymer electrolyte and preparation method and application thereof | |
| CN108598535B (en) | Polyacrylonitrile and ionic liquid composite anion exchange membrane for fuel cell and preparation method thereof | |
| Chen et al. | Self-healing and mechanically robust poly (thiourea-disulfide) elastomers based on three types of synergistic dynamic bonding | |
| CN105199091A (en) | Polyion liquid acid-base indicator suitable for non-polar solvent and preparation method thereof | |
| CN100354338C (en) | A process for the preparation of polyaniline salt |
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 |