CN112679726B - 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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- CN112679726B CN112679726B CN202011538771.8A CN202011538771A CN112679726B CN 112679726 B CN112679726 B CN 112679726B CN 202011538771 A CN202011538771 A CN 202011538771A CN 112679726 B CN112679726 B CN 112679726B
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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-diisocyanatohexane 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 polymer monomers, anhydrous toluene and 1,6-hexanediamine for reaction; adding 1,6-hexanediamine dropwise for reaction, adding n-hexane solution dropwise for precipitation, and filtering to obtain 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 was achieved by a two-step process, and the polymer was 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, and the like because of its very strong absorption ability to solvents. Particularly, with the development of the lithium ion battery industry, the all-solid-state battery has attracted attention due to its high energy density and light weight. 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 the 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 realize 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 azeotropic method with anhydrous toluene w =10000 moisture in a PEO molecule;
b, after dehydration, adding 1,6-diisocyanatohexane and dibutyltin dilaurate into a methylbenzene solution dissolved with PEO for reaction, dropwise adding the solution obtained after the reaction into a normal hexane solution for precipitation, and filtering to obtain a white solid polymer monomer;
2) Synthesis of PEO Polymer containing Urea Structure
a, mixing polymer monomers, 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-diisocyanatohexane and dibutyltin dilaurate into the toluene solution dissolved with the 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 then react for 12 hours at 80 ℃.
In the step 1) b, the addition amounts of 1,6-diisocyanatohexane and dibutyltin dilaurate are 1.31g and 013g respectively, and the obtained white solid polymer monomer is 13.85g; 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 and 1 the structure of the polymer was characterized by H NMR measurement at 1625cm, as seen from the infrared measurement -1 And 1720cm -1 Characteristic 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-NH-CO-NH-and-NH-CO-O-functional groups in the infrared test results of the polymer are respectively shown in1625cm -1 And 1716cm -1 It 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 schematic of 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; and (b) is in an inverted state.
FIG. 3 is a gel prepared with chloroform and PEO polymer.
Fig. 3 (a) is a normal state; and (b) is 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 lipophilic and hydrophilic transparent organogel by using polyethylene oxide is divided into the following two stages:
1) Synthesis of Polymer monomers
a removal of molecular weight M by azeotropy with 300mL of anhydrous toluene w Water in PEO molecules = 10000.
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, and 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 12h.
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:
1 H NMR(δ,CDCl 3 ,ppm)1.20-1.39(-CH 2 -CH 2 -CH 2 -NHCONH-CH 2 -CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -NHCOO-CH 2 -CH 2 -O-12H),1.40-1.54(-CH 2 -CH 2 -NHCONH-CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -NHCOO-CH 2 -CH 2 -O-,12H),3.14-3.18(-CH 2 -CH 2 -NHCONH-CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -NHCOO-CH 2 -CH 2 -,13H),(-NHCOO-CH 2 -CH 2 -O-,1190H),4.16-4.26(-NHCOO-CH 2 -CH 2 -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 M w ＝1.4×10 5 Molecular weight distribution of M w /M n PEO polymer of = 5.2. By infrared and 1 the structure of the polymer was characterized by H NMR measurement at 1625cm, as seen from the infrared measurement -1 And 1720cm -1 Characteristic absorption peaks belonging to NCO-and-NH-COO-functional groups, respectively, were clearly observed, indicating that the polymerized monomer (1) was successfully synthesized. And in the results of the infrared test of the polymer, -NH-CO-NH-and-NH-CO-O-functions the characteristic peaks of the clusters are shown at 1625cm, respectively -1 And 1716cm -1 It was confirmed that the polymer (3) was successfully synthesized, as shown in FIG. 1, since the polymer structure was also provided with affinityWater and an oleophilic moiety, so that the polymer forms a transparent organogel in both aqueous and chloroform solutions. 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 (1)
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 azeotropic method with anhydrous toluene w =10000 moisture in a PEO molecule;
b, after dehydration, adding 1,6-hexane diisocyanate and dibutyltin dilaurate into a methylbenzene solution dissolved with PEO for reaction, reacting for 8-12h at 50-60 ℃, 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 polymer monomers, anhydrous toluene and 1,6-hexanediamine for reaction;
mixing a polymer monomer, anhydrous toluene and 1,6-hexanediamine, and reacting at 80 ℃ for 12 hours;
b, continuously dripping the residual 1,6-hexanediamine, and continuously reacting;
c, dropwise adding the solution obtained after the reaction to a normal hexane solution for precipitation, and filtering to obtain a white solid with the molecular weight of M w ＝1.4×10 5 Molecular weight distribution of M w /M n PEO polymer of = 5.2;
d, preparing a transparent gel by using water or chloroform as a solvent by using the PEO polymer;
in the step 1) b, the addition amounts of 1,6-diisocyanatohexane and dibutyltin dilaurate were 1.31g and 0.13g, respectively, and 13.85g of a white solid polymer monomer was obtained; 13.85g of polymer monomer, 200ml of anhydrous toluene and 0.08g of 1,6-hexanediamine in the step 2) a; 0.05g of 1,6-hexanediamine remaining in step 2) b and 5.83g of PEO polymer obtained in step 2) c were added dropwise;
when the weight percentage concentration of the polymer is more than 4%, hydrogel is formed, and when the weight percentage concentration of the polymer is more than 2%, organogel taking chloroform as a developing solvent is formed.
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