CN112142613B - Rosin-based small-molecule organic gel and cyclohexane gel formed by same - Google Patents
Rosin-based small-molecule organic gel and cyclohexane gel formed by same Download PDFInfo
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- CN112142613B CN112142613B CN202010999020.XA CN202010999020A CN112142613B CN 112142613 B CN112142613 B CN 112142613B CN 202010999020 A CN202010999020 A CN 202010999020A CN 112142613 B CN112142613 B CN 112142613B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C233/63—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
Abstract
The invention discloses a rosin-based micromolecular organic gel and a cyclohexane gel formed by the rosin-based micromolecular organic gel, and belongs to the field of rosin chemical utilization. The invention takes dehydroabietic acid and lysine ethyl ester hydrochloride as raw materials to carry out amidation reaction to obtain a rosin-based amphiphilic molecule, and simultaneously provides the structure of the rosin-based micromolecule gel and the gel performance in different organic solvents. The small molecular organic gel can lead cyclohexane to generate gelation and show good gelation capability. The invention promotes the development of rosin raw materials and products thereof, and explores a new way for the high value-added utilization of rosin.
Description
Technical Field
The invention relates to a rosin-based micromolecular organic gel and a cyclohexane gel formed by the rosin-based micromolecular organic gel, and belongs to the field of chemical utilization of rosin.
Background
As a typical soft material, the gel plays an important role in the fields of cosmetics, foods, drug sustained release, biological simulation, inorganic nano materials and the like. Common gelators include fatty acid derivatives, anthracenyl derivatives, amino acid-based gelators, diurea-type gelators, steroid derivatives, cyclodextrin derivatives, and the like. The research on the properties between the molecular structure of the gel and the physical and chemical properties of the gel and the design and synthesis of the small molecule gel with unique properties are one of the key points in the field of small molecule gels. By selecting proper reaction raw materials and through reasonable molecular design, a series of micromolecule gel systems with unique performance can be expected to be obtained.
Rosin is an important forestry resource in China, has the advantages of being renewable, good in environmental compatibility, easy to biodegrade and the like, and is widely applied to various fields of rubber, printing ink, pesticides, medicines, foods and other industries and lives. Rosin acid is a diterpenoid compound, and a tricyclic-linked rigid skeleton consisting of 20 carbon atoms has remarkable hydrophobic properties. If rosin is used as a main raw material to prepare the rosin-based micromolecule gel, an environment-friendly micromolecule gel system is expected to be developed. However, only reports on rosin-based small molecule hydrogel agents so far do not exist about efficient rosin-based organic gel agents and preparation methods thereof.
Disclosure of Invention
[ problem ] to
The rosin has the advantages of being renewable, biodegradable, multifunctional, easy to modify in structure and the like. Although rosin is widely used in the synthesis and application of amphiphilic molecules, no efficient rosin-based organic gelling agent and preparation method thereof exist so far.
[ solution ]
Aiming at the problems, the invention provides the rosin-based micromolecular organic gel, the rosin-based amphiphilic molecule is obtained by taking dehydroabietic acid and lysine ethyl ester hydrochloride as raw materials and carrying out amidation reaction, and the micromolecular organic gel can enable cyclohexane to be gelled and shows good gelling capacity.
The invention provides a rosin-based amphiphilic molecule, which has the following structural formula:
the invention provides a method for synthesizing the rosin-based amphiphilic molecule, and the synthetic route of the compound is as follows:
in one embodiment of the present invention, the method for synthesizing a rosin-based amphiphilic molecule comprises the steps of:
(1) purifying dehydroabietic acid;
(2) and carrying out amidation reaction on dehydroabietic acid and lysine ethyl ester hydrochloride to obtain the rosin-based amphiphilic molecule.
In one embodiment of the present invention, the step (1) of purifying dehydroabietic acid comprises: mixing, stirring and dissolving disproportionated rosin, ethanol and petroleum ether, fully stirring ethanolamine at the temperature of 60-80 ℃, separating out solid, cooling, and performing vacuum filtration; recrystallizing the obtained solid with an ethanol aqueous solution for 2-5 times to obtain pure dehydroabietic acid ethanolamine salt; dissolving the dehydroabietic acid ethanolamine salt by using an ethanol aqueous solution under a heating state, adding acetic acid for acidification, adding water for precipitating a solid, cooling, performing vacuum filtration, and drying to obtain a pure dehydroabietic acid product.
In one embodiment of the present invention, the step (1) of purifying dehydroabietic acid comprises: purification of dehydroabietic acid: putting 50g of ground disproportionated rosin, 5mL of ethanol and 250mL of petroleum ether into a clean 1000mL beaker, heating and stirring to completely dissolve the disproportionated rosin, keeping the temperature at 70 ℃ for 5min, adding ethanolamine (7.13g and 0.12mol), fully stirring for 20min to separate out a solid, naturally cooling to room temperature, and carrying out vacuum filtration. The obtained solid was recrystallized 3 times from ethanol/water (volume ratio 1:1) to obtain a relatively pure ethanolamine salt of dehydroabietic acid. Dissolving the ethanolamine salt with 100mL of ethanol/water (volume ratio of 1:1) solution under heating, acidifying with acetic acid (10.5g,0.18mol), precipitating white solid in the process, adding 10mL of water to fully precipitate, cooling to room temperature, vacuum filtering, and vacuum drying to obtain white dehydroabietic acid pure product.
In one embodiment of the present invention, the step (2) comprises the steps of: dissolving lysine ethyl ester hydrochloride in dichloromethane, sequentially adding triethylamine, 4-Dimethylaminopyridine (DMAP) and dehydroabietic acid, then adding HATU, and reacting for 4-6 h at 30-40 ℃; after the reaction is finished, dichloromethane is added for extraction for 1-2 times, and the organic layer is washed by deionized water for 4-5 times and then is treated by anhydrous Na2SO4Drying, suction filtering, taking filtrate, removing redundant solvent by rotary evaporation, and purifying by column chromatography to obtain the final product.
In one embodiment of the present invention, the step (2) includes the following specific steps: ethyl lysine hydrochloride (6.92g,0.028mol) was dissolved in methylene chloride, and triethylamine (20.23g,0.2mol), 4-Dimethylaminopyridine (DMAP) (0.12g,0.001mol) and dehydroabietic acid (15g,0.05mol) were added successively, followed by HATU (20.59g,0.054mol) and reacted at 35 ℃ for 5 hours. After the reaction is finished, dichloromethane is added for extraction for 1-2 times, and an organic layer is formedWashing with deionized water for 4-5 times, and adding anhydrous Na2SO4And (5) drying. And (4) carrying out suction filtration, taking filtrate, and removing redundant solvent by rotary evaporation. Purifying by column chromatography (eluent is mixed solvent of petroleum ether and ethyl acetate at volume ratio of 1:1) to obtain white solid as final product.
The invention provides an organic gel, which contains the rosin-based amphiphilic molecule.
The invention provides cyclohexane gel which contains the rosin-based amphiphilic molecule.
In one embodiment of the present invention, the preparation method of the cyclohexane gel comprises: and (2) placing the rosin-based amphiphilic molecules and cyclohexane in a reaction container, heating to a complete solvent, and cooling to obtain the cyclohexane gel.
In one embodiment of the invention, when preparing the cyclohexane gel, the rosin-based amphiphilic molecule is added in an amount of 2-5% (g/mL) of cyclohexane by mass volume fraction.
[ advantageous effects ]:
rosin acid and amino acid are used as raw materials to synthesize the rosin-based amphiphilic molecule. The compound is capable of gelling cyclohexane and is a very effective gelling agent for cyclohexane. The invention promotes the development of rosin raw materials and products thereof and explores a new way for the high added value utilization of rosin.
Drawings
FIG. 1 shows the molecular structure of a rosin-based amphiphilic molecule.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the rosin-based amphiphilic molecule.
Figure 3 is a photograph of a rosin-based amphiphile forming a cyclohexane gel with cyclohexane.
Fig. 4 is an SEM picture of a xerogel formed by rosin-based amphiphilic molecules in cyclohexane.
Detailed Description
[ example 1 ]
(1) Purification of dehydroabietic acid: putting 50g of ground disproportionated rosin, 5mL of ethanol and 250mL of petroleum ether into a clean 1000mL beaker, heating and stirring to completely dissolve the disproportionated rosin, keeping the temperature at 70 ℃ for 5min, adding ethanolamine (7.13g and 0.12mol), fully stirring for 20min to separate out a solid, naturally cooling to room temperature, and carrying out vacuum filtration. The obtained solid was recrystallized 3 times from ethanol/water (volume ratio 1:1) to obtain a relatively pure ethanolamine salt of dehydroabietic acid. Dissolving the ethanolamine salt with 100mL of ethanol/water (volume ratio of 1:1) solution under heating, acidifying with acetic acid (10.5g,0.18mol), precipitating white solid in the process, adding 10mL of water to fully precipitate, cooling to room temperature, vacuum filtering, and vacuum drying to obtain white dehydroabietic acid pure product.
(2) Synthesizing a rosin-based amphiphilic molecule: ethyl lysine hydrochloride (6.92g,0.028mol) was dissolved in 120mL of dichloromethane, triethylamine (20.23g,0.2mol), 4-Dimethylaminopyridine (DMAP) (0.12g,0.001mol) and dehydroabietic acid (15g,0.05mol) were added in this order, and HATU (20.59g,0.054mol) was added and reacted at 35 ℃ for 5 hours. After the reaction is finished, dichloromethane is added for extraction for 1-2 times, and the organic layer is washed by deionized water for 4-5 times and then is treated by anhydrous Na2SO4And (5) drying. And (4) carrying out suction filtration, taking filtrate, and removing redundant solvent by rotary evaporation. Purifying by column chromatography (eluent is mixed solvent of petroleum ether and ethyl acetate at volume ratio of 1:1) to obtain white solid with yield of 82.3%, and FIG. 1 shows molecular structure of synthesized rosinyl amphipathic molecule.
Rosin-based amphiphilic molecular structure and purity determination
Weighing a proper amount of the final product rosin-based surfactant, placing the rosin-based surfactant in a nuclear magnetic tube, and dissolving the rosin-based surfactant in a deuterated reagent DMSO. Performed at 25 ℃ with an Aduance III NMR spectrometer1H NMR measurement.1The resonance frequency of H is 400 MHz. As can be seen from the rosin-based hydrogen NMR spectrum in FIG. 2, the chemical shifts of each hydrogen match the target rosin-based surfactant, indicating that the final product was obtained. Meanwhile, the spectrogram has no impurity peak, which indicates that the product achieves high purity.
[ example 2 ] measurement of gelation behavior of rosin-based amphiphilic molecules.
0.025g of rosin-based amphiphilic molecule and 1mL of different solvents (the concentration of the corresponding solution is recorded as 2.5%, w/v) are weighed into a glass bottle, sealed, heated to be completely dissolved, cooled at room temperature and then observed in an inverted manner. The results are shown in table 1, the rosin-based amphiphilic molecule showed good gelling ability in the solvents cyclohexane and TEOS. Figure 3 is a photograph of a rosin-based amphiphile forming a cyclohexane gel with cyclohexane.
TABLE 1 gelation behavior of Compound 1 in various organic solvents (2.5%, w/v)
Note:[a]g-stable gel S-soluble I-insoluble
Determination of microstructure of rosin-based amphiphilic molecules:
and (3) freeze-drying the wet gel formed by 0.025g of rosin-based amphiphilic molecule and 1mL of cyclohexane, coating the wet gel on a conductive adhesive, adhering the conductive adhesive on a copper sample table, spraying gold on the sample, and observing the micro morphology of the xerogel under a field emission scanning electron microscope. The accelerating voltage is 5KV, and the emission current is 10 mA. It can be seen from fig. 4 that the gelling agent molecules aggregate in cyclohexane to form a fibrous network. The gelling agent molecules are assembled into an aggregation structure of a mesoscopic layer through hydrogen bond action and van der Waals action, and then are mutually cross-linked and wound to form a three-dimensional network structure, so that the organic solvent is gelled.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A compound having the formula:
2. a method for synthesizing the compound of claim 1, wherein the compound is synthesized by the following route:
3. the method of claim 2, wherein the method of synthesizing the compound comprises the steps of:
(1) purifying dehydroabietic acid;
(2) and carrying out amidation reaction on dehydroabietic acid and lysine ethyl ester hydrochloride to obtain the rosin-based amphiphilic molecule.
4. The process according to claim 3, wherein the step (1) of purifying dehydroabietic acid is a step of: mixing, stirring and dissolving disproportionated rosin, ethanol and petroleum ether, fully stirring ethanolamine at the temperature of 60-80 ℃, separating out solid, cooling, and performing vacuum filtration; recrystallizing the obtained solid with an ethanol aqueous solution for 2-5 times to obtain pure dehydroabietic acid ethanolamine salt; dissolving the dehydroabietic acid ethanolamine salt by using an ethanol aqueous solution under a heating state, adding acetic acid for acidification, adding water for precipitating a solid, cooling, performing vacuum filtration, and drying to obtain a pure dehydroabietic acid product.
5. The method of claim 3, wherein the step (2) comprises the steps of: dissolving lysine ethyl ester hydrochloride in dichloromethane, sequentially adding triethylamine, 4-dimethylaminopyridine and dehydroabietic acid, then adding HATU, and reacting for 4-6 h at 30-40 ℃; after the reaction is finished, dichloromethane is added for extraction for 1-2 times, and the organic layer is washed by deionized water for 4-5 times and then is treated by anhydrous Na2SO4Drying, suction filtering, taking filtrate, removing redundant solvent by rotary evaporation, and purifying by column chromatography to obtain the final product.
6. The method as claimed in claim 5, wherein the eluent used for the column chromatography purification is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 1: 1.
7. An organic gelator comprising a compound according to claim 1.
8. A cyclohexane gel comprising the compound according to claim 1.
9. A process for preparing the cyclohexane gel of claim 8, wherein the process comprises: placing the compound of claim 1 and cyclohexane in a reaction vessel, heating to completely dissolve, and cooling to obtain a cyclohexane gel.
10. The method according to claim 9, wherein the compound according to claim 1 is added in an amount of 2 to 5% by mass in terms of volume fraction of cyclohexane in the preparation of cyclohexane gel.
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| US2772972A (en) * | 1954-08-20 | 1956-12-04 | Gen Aniline & Film Corp | Positive diazotype printing plates |
| CN105797644A (en) * | 2016-04-20 | 2016-07-27 | 江南大学 | Light-response intelligent foam formed through dehydroabietic acid surfactant |
| CN107308883A (en) * | 2017-06-26 | 2017-11-03 | 江南大学 | A kind of stable foam formed by abietyl amino acid surfactant |
| CN108675934A (en) * | 2018-05-10 | 2018-10-19 | 江南大学 | A kind of worm micella formed by abietyl Gemini surface active agent |
| CN109627191A (en) * | 2019-01-04 | 2019-04-16 | 江南大学 | A kind of supramolecular hydrogel of abietyl micro-molecular hydrogel agent and its formation |
| CN110404472A (en) * | 2019-08-09 | 2019-11-05 | 福州大学 | A kind of rosin-based Gemini surface active agent and preparation method thereof |
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Patent Citations (6)
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| US2772972A (en) * | 1954-08-20 | 1956-12-04 | Gen Aniline & Film Corp | Positive diazotype printing plates |
| CN105797644A (en) * | 2016-04-20 | 2016-07-27 | 江南大学 | Light-response intelligent foam formed through dehydroabietic acid surfactant |
| CN107308883A (en) * | 2017-06-26 | 2017-11-03 | 江南大学 | A kind of stable foam formed by abietyl amino acid surfactant |
| CN108675934A (en) * | 2018-05-10 | 2018-10-19 | 江南大学 | A kind of worm micella formed by abietyl Gemini surface active agent |
| CN109627191A (en) * | 2019-01-04 | 2019-04-16 | 江南大学 | A kind of supramolecular hydrogel of abietyl micro-molecular hydrogel agent and its formation |
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