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
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- 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
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- polymer
- peo
- hexanediamine
- monomer
- polyethylene oxide
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 17
- -1 polyoxyethylene Polymers 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 29
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 11
- OQQOAWVKVDAJOI-UHFFFAOYSA-N (2-dodecanoyloxy-3-hydroxypropyl) dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCC OQQOAWVKVDAJOI-UHFFFAOYSA-N 0.000 claims 1
- MSHNRHGYEBLPTK-UHFFFAOYSA-N CCCCCC.N#CO Chemical compound CCCCCC.N#CO MSHNRHGYEBLPTK-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- 238000012644 addition polymerization Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 12
- 239000000499 gel Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Images
Classifications
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- 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
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及用聚氧化乙烯制备具有亲油及亲水性透明有机凝胶的方法，包括以下步骤：1)聚合物单体合成：a用无水甲苯通过共沸法除掉PEO分子中的水分；b脱水后，在溶有PEO的甲苯溶液中加入1,6‑二异氰酸己烷、二月桂酸二丁基锡进行反应，反应后再滴加至正己烷溶液进行沉淀，过滤后得到聚合物单体；2)含有尿素结构的PEO聚合物合成：a聚合物单体、无水甲苯、1,6‑已烷二胺混合进行反应；滴加1,6‑已烷二胺反应，再滴加至正己烷溶液沉淀，并过滤后得到PEO聚合物；PEO聚合物以水或氯仿为溶剂制备透明凝胶。优点是：通过二步法实现PEO聚合物单体与1,6‑已烷二胺的加成聚合，最终合成了聚合物。
The invention relates to a method for preparing lipophilic and hydrophilic transparent organogels with polyethylene oxide, comprising the following steps: 1) synthesis of polymer monomers: a. using anhydrous toluene to remove water in PEO molecules by azeotropic method After b dehydration, in the toluene solution dissolved with PEO, add 1,6-diisocyanatohexane, dibutyltin dilaurate to react, and then dropwise to the n-hexane solution for precipitation after the reaction, and obtain the polymer after filtration Monomer; 2) Synthesis of PEO polymer containing urea structure: a polymer monomer, anhydrous toluene, 1,6-hexanediamine are mixed and reacted; 1,6-hexanediamine is added dropwise to react, and then dropwise Add to n-hexane solution for precipitation, and filter to obtain PEO polymer; PEO polymer uses water or chloroform as solvent to prepare transparent gel. The advantage is that the addition polymerization of PEO polymer monomer and 1,6-hexanediamine is realized by a two-step method, and the polymer is finally 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)
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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 |
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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》 * |
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