CN111440293A - Method for selective ester aminolysis of epoxy grease by photocatalysis - Google Patents
Method for selective ester aminolysis of epoxy grease by photocatalysis Download PDFInfo
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- CN111440293A CN111440293A CN202010270925.3A CN202010270925A CN111440293A CN 111440293 A CN111440293 A CN 111440293A CN 202010270925 A CN202010270925 A CN 202010270925A CN 111440293 A CN111440293 A CN 111440293A
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- Prior art keywords
- epoxy
- photocatalytic
- aminolysis
- vegetable oil
- grease
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000004519 grease Substances 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000010644 ester aminolysis reaction Methods 0.000 title claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 title description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 24
- 239000008158 vegetable oil Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000002466 imines Chemical class 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims abstract description 10
- 235000019198 oils Nutrition 0.000 claims abstract description 10
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 claims abstract description 7
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940031016 ethyl linoleate Drugs 0.000 claims abstract description 4
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000007098 aminolysis reaction Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 claims description 3
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 claims description 3
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 claims description 3
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 3
- 241000221089 Jatropha Species 0.000 claims description 3
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 claims description 3
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 3
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims description 3
- 229940093471 ethyl oleate Drugs 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- VUSHVKUNOXWQTG-KHPPLWFESA-N methyl (Z)-2-oxooctadec-9-enoate Chemical compound O=C(C(=O)OC)CCCCCC\C=C/CCCCCCCC VUSHVKUNOXWQTG-KHPPLWFESA-N 0.000 claims description 3
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 3
- 229940117972 triolein Drugs 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 2
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 229930187593 rose bengal Natural products 0.000 claims description 2
- 229940081623 rose bengal Drugs 0.000 claims description 2
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 6
- 230000000269 nucleophilic effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- 229940125782 compound 2 Drugs 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
Abstract
The invention provides a method for selective ester aminolysis of photocatalytic epoxy grease, which comprises the following steps: epoxy vegetable oil is used as a raw material, and a target product is generated under the conditions of imine and a photocatalyst. Under the conditions of no solvent and no acid and alkali addition, imine is added into a reaction system to further aminolyze raw material epoxy vegetable oil, and a target product can be obtained under the photocatalytic condition. The reaction relates to the preparation of the natural vegetable oil to obtain the epoxy vegetable oil, and then synthesizes other substances, thereby exploring another novel way for the development and utilization of the natural oil. The reaction can be suitable for working with a large amount of grease, such as epoxidized vegetable oil, epoxidized ethyl linoleate and the like, and has single product and high conversion efficiency.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a method for selective ester aminolysis of photocatalytic epoxy grease.
Background
Vegetable oil and fat is a natural high molecular compound compounded by fatty acid and glycerin and widely distributed in nature. The oil and fat is also widely used in the fields of biological materials, high molecular materials, foods, cosmetics, heavy industrial raw materials and the like, is always main in the aspect of food application, and simultaneously improves the material performance by modifying the vegetable oil. In recent years, however, more and more people have used these oils to produce biofuels and chemical feedstocks. This is driven in part by the rapid rise in oil prices, the growing concern over the environmental impact of using petroleum, and the need to develop domestic renewable fuels and industrial raw materials. Vegetable oils can provide high value renewable fatty acids to chemical and health related industries, and a large variety of fatty acids exist in nature, many of which have potential industrial uses. The development and application of vegetable oil in emerging fields are receiving more and more extensive attention.
Epoxy resins are an important class of thermosetting resins, however, most of the epoxy resins are derived from non-renewable petroleum resources and have poor mechanical properties and are not easily degraded, so that the application of the epoxy resins is limited. Therefore, how to expand the raw materials for preparing epoxy resins becomes a hot spot of current research.
Disclosure of Invention
The invention aims to provide a method for preparing epoxy resin by using vegetable oil as a raw material, and the method expands a new application field for natural vegetable oil.
A method for selective ester aminolysis of photocatalytic epoxy grease comprises the following steps: epoxy vegetable oil is used as a raw material, and an epoxy resin polymer is generated under the conditions of imine and a photocatalyst, wherein the molecular formula of the epoxy resin polymer is as follows:
wherein R is1Represents a nucleophileThe group m, n represents the chain length of the grease and the position of epoxy.
Furthermore, the method for selective ester aminolysis of the photocatalytic epoxy grease comprises the step of mixing the epoxy vegetable oil, the imine and the photocatalyst in a molar ratio of (0.5-1.5) to (0.25-0.8) to (0.01-0.2).
Further, in the method for selective ester aminolysis of photocatalytic epoxy grease, the epoxy vegetable oil is: one or more of epoxidized soybean oil, epoxy linoleic acid ethyl ester or epoxy methyl oleate, epoxy ethyl oleate, epoxy methyl linoleate, epoxy ethyl linoleate, epoxy triolein, epoxy jatropha oil, epoxy tung oil and epoxy castor oil.
Further, in the method for selective ester aminolysis of photocatalytic epoxy grease, the imine is one of ethanolamine, ethylenediamine or propylenediamine.
Further, in the method for selective ester aminolysis of the photocatalytic epoxy grease, the photocatalyst is DCB and H2TPP、eosin Y、rose Bengal、Mes-Acr、4CzIPN、Ru(bpy)3 2+Or fac-Ir (ppy)3One of them.
Furthermore, the method for selective ester aminolysis of the photocatalytic epoxy grease comprises the step of mixing the epoxy vegetable oil, the imine and the photocatalyst in a molar ratio of (0.5-1.2) to (0.4-0.6) to (0.1-0.2).
Further, in the method for selective ester aminolysis of the photocatalytic epoxy grease, the imine is ethanolamine.
Further, the method for selective ester aminolysis of the photocatalysis epoxy grease comprises the steps that the photocatalyst is Ru (bpy)3 2+。
Further, according to the method for selective ester aminolysis of the photocatalytic epoxy grease, the whole reaction system is irradiated by white L ED light.
Further, according to the method for selective ester aminolysis of the photocatalytic epoxy grease, the target product can be obtained by performing the whole reaction system at room temperature for 8 hours under the protection of inert gas.
The invention also provides an epoxy resin polymer prepared by any one of the methods.
The invention provides a novel application approach of natural vegetable oil by a method of selective ester aminolysis of epoxy oil by photocatalysis. Specifically, in general, amino groups are introduced into the grease and are epoxy-opened, and after the amino groups are introduced, the epoxy can become substances such as alcohol and the like, and polymerization reaction can not be carried out any more. Moreover, epoxy can be subjected to ring-opening polymerization to obtain epoxy resin, and meanwhile, hydroxyl, amino and other polar groups with strong nucleophilicity are introduced into the epoxy resin molecules, so that the epoxy resin can be subjected to deep modification once again on the basis of the epoxy resin, and a polymer with better performance can be obtained. Such as: the epoxy resin and the amine introduced by the preparation method of the invention are used as sites for further polymerization crosslinking, so that the epoxy resin can be reacted with other components to obtain a polymer with higher strength or higher network crosslinking degree.
Has the advantages that:
1) according to the invention, the epoxy vegetable oil is used as a raw material for aminolysis to prepare the epoxy resin with more excellent performance, so that the method makes a great contribution to the exploration of the novel application field of the vegetable oil.
2) The preparation method of the invention selectively aminolyzes the epoxy group and the ester group under the conditions of no solvent and no acid and alkali addition: only the ester groups are aminolyzed, thereby obtaining a polymer with higher strength or a higher network crosslinking degree.
3) The preparation method provided by the invention can be used for modifying kilogram-grade epoxy grease, and is also suitable for: milligram scale, gram scale, kilogram scale reactions.
4) The preparation method provided by the invention can be directly used for epoxidized crude oil, and has no high requirement on the purity of the epoxy grease raw material, so that the preparation method is suitable for various substrates, such as: epoxy methyl oleate, epoxy ethyl oleate, epoxy methyl linoleate, epoxy ethyl linoleate, epoxy triolein and other pure oils; also: epoxidized soybean oil, epoxidized jatropha oil, epoxidized tung oil, epoxidized castor oil and other crude epoxy oils.
5) The reaction product is single, and the conversion efficiency is high.
6) The epoxy resin is widely applied to the field of materials such as adhesives, preservatives, coatings and the like due to simple synthesis method and excellent performance, and the biomass-based characteristic of the grease brings good characteristics for the biocompatibility and degradability of the materials.
7) This method ensures that the epoxy does not open and remains for further polymerization.
Drawings
FIG. 1 is a drawing of Compound 21HNMR(400MHz,CDCl3) A spectrogram;
FIG. 2 is a drawing of Compound 213CNMR(100MHz,CDCl3) A spectrogram;
FIG. 3 is a synthetic scheme of the process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a method for preparing epoxy resin by selective ester aminolysis of photocatalytic epoxy grease, which comprises the steps of taking epoxy vegetable oil as a raw material, adding imine and a photocatalyst, and carrying out a reaction under the irradiation of a white L ED lamp to obtain a target product, wherein the synthetic route is shown in figure 3. in the reaction, the epoxy soybean oil, ethanolamine, Ru (bpy)3 2+The molar ratio of (0.5-1.2) to (0.4-0.6) to (0.1-0.2).
In the above reaction, the reaction is carried out in a system without solvent or acid and alkali addition.
In the above reaction, the reaction was continuously irradiated for 8h under the protection of inert gas.
Example 2
This example provides a method for selective ester aminolysis of epoxy grease by photocatalysis, which comprises using epoxy linoleic acid ethyl ester (0.33g,1.0mmol), ethanolamine (2.53g,4.1mmol), Ru (bpy)3 2+(0.1mmol) is added into a 25m L dried round-bottom flask, under the conditions of no solvent and no acid and base addition, the reaction system is continuously irradiated for 8 hours under the protection of inert gas and a white L ED lamp, and the reaction progress is monitored by thin layer plate chromatography (T L C) in the process of the reaction.
And (2) carrying out post-reaction treatment, namely monitoring the reaction process in real time by using a thin-layer chromatography plate, stopping the reaction after 8 hours, pouring the reaction solvent into a 250m L separating funnel, extracting by using dichloromethane (3 × 10m L) and water (3 × 10m L), collecting a lower organic phase, drying by using anhydrous magnesium sulfate, filtering, concentrating, and carrying out column chromatography separation and purification by using 300-mesh 400-mesh silica gel, wherein the eluent ratio is petroleum ether/ethyl acetate (EtOAc/Petroleumether) ═ 1/5.
Structural identification of compound 2:
under the monitoring of Thin-layer Chromatography by Thin-layer L eye Chromatography:
(EtOAc/Petroleumether＝1/1):Rf＝0.075(UV)。
1HNMR(400MHz,CDCl3)ppm:0.88(s,3H),1.24-1.32(d,10H,J＝32.92Hz),1.45-1.51(t,7H,J＝24.96Hz),1.62(s,2H),1.73-1.76(t,2H,J＝12.32Hz),2.16-2.20(t,2H,J＝14.64Hz),2.96(s,2H),3.05-3.06(d,3H,J＝3.72Hz),3.38-3.39(d,2H,J＝3.96Hz),3.68(s,2H),6.17(s,1H).
13CNMR(100MHz,CDCl3)ppm:13.9,22.5,25.56,25.6,26.1,26.2,26.4,26.5,26.9,27.2,27.7,27.8,27.83,27.9,29.0,29.04,29.07,29.13,19.18,29.2,31.6,36.5,36.6,42.4,54.2,54.3,54.4,56.7,56.8,57.0,57.1,62.4,76.7,77.0,77.3,174.4.
FIG. 1 is a drawing of Compound 21HNMR(400MHz,CDCl3) A spectrogram; FIG. 2 is a drawing of Compound 213CNMR(100MHz,CDCl3) Spectra. As can be seen from FIGS. 1 and 2, the present invention provides a reliable method for preparing epoxy resin polymers from natural vegetable oils and fats.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for selective ester-based aminolysis of photocatalytic epoxy grease is characterized by comprising the following steps: the method comprises the following steps: epoxy vegetable oil is used as a raw material, and an epoxy resin polymer is generated under the conditions of imine and a photocatalyst, wherein the molecular formula of the epoxy resin polymer is as follows:
wherein R is1Represents nucleophilic group, and m and n represent chain length and epoxy position of grease.
2. The method for selective ester-based aminolysis of photocatalytic epoxy grease according to claim 1, characterized in that: the molar ratio of the epoxy vegetable oil to the imine to the photocatalyst is (0.5-1.5) to (0.25-0.8) to (0.01-0.2).
3. The method for selective ester-based aminolysis of photocatalytic epoxy grease according to claim 1, characterized in that: the epoxy vegetable oil is as follows: one or more of epoxidized soybean oil, epoxy linoleic acid ethyl ester or epoxy methyl oleate, epoxy ethyl oleate, epoxy methyl linoleate, epoxy ethyl linoleate, epoxy triolein, epoxy jatropha oil, epoxy tung oil and epoxy castor oil.
4. The method for selective ester-based aminolysis of photocatalytic epoxy grease according to claim 1, characterized in that: the imine is one of ethanolamine, ethylenediamine or propylenediamine.
5. The method for selective ester-based aminolysis of photocatalytic epoxy grease according to claim 1, characterized in that: the photocatalyst is DCB and H2TPP、eosin Y、rose Bengal、Mes-Acr、4CzIPN、Ru(bpy)3 2+Or fac-Ir (ppy)3One of them.
6. The method for selective ester-based aminolysis of photocatalytic epoxy grease according to claim 2, characterized in that: the molar ratio of the epoxy vegetable oil to the imine to the photocatalyst is (0.5-1.2) to (0.4-0.6) to (0.1-0.2).
7. The method for selective ester aminolysis of photocatalytic epoxy grease according to claim 4, characterized in that: the imine is ethanolamine.
8. The method for selective ester aminolysis of photocatalytic epoxy grease according to claim 5, characterized in that: the photocatalyst is Ru (bpy)3 2+。
9. The method for selective ester aminolysis of photocatalytic epoxy grease according to claim 1, wherein the whole reaction system is irradiated by white L ED light;
the whole reaction system is carried out for 8 hours at room temperature under the protection of inert gas, and then the target product can be obtained.
10. An epoxy resin polymer prepared according to the process of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010270925.3A CN111440293B (en) | 2020-04-08 | 2020-04-08 | Method for selective ester aminolysis of epoxy grease by photocatalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010270925.3A CN111440293B (en) | 2020-04-08 | 2020-04-08 | Method for selective ester aminolysis of epoxy grease by photocatalysis |
Publications (2)
| Publication Number | Publication Date |
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| CN111440293A true CN111440293A (en) | 2020-07-24 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810348A (en) * | 1956-09-04 | 1959-03-11 | Gen Mills Inc | Condensates of epoxy fatty acids or esters with polyamines |
| CN101845367A (en) * | 2009-07-01 | 2010-09-29 | 河南省科学院高新技术研究中心 | Hydroxylated tung oil and ester group-aminated preparation method thereof |
| US20110060076A1 (en) * | 2008-05-22 | 2011-03-10 | Hefner Jr Robert E | Epoxy resins derived from seed oil based alkanolamides and a process for preparing the same |
| CN102964856A (en) * | 2012-12-20 | 2013-03-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based solubilizing and toughening agent-modified epoxy asphalt material |
| CN110903606A (en) * | 2019-12-10 | 2020-03-24 | 安徽农业大学 | Plant oil-based composite material and preparation method thereof |
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2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810348A (en) * | 1956-09-04 | 1959-03-11 | Gen Mills Inc | Condensates of epoxy fatty acids or esters with polyamines |
| US20110060076A1 (en) * | 2008-05-22 | 2011-03-10 | Hefner Jr Robert E | Epoxy resins derived from seed oil based alkanolamides and a process for preparing the same |
| CN101845367A (en) * | 2009-07-01 | 2010-09-29 | 河南省科学院高新技术研究中心 | Hydroxylated tung oil and ester group-aminated preparation method thereof |
| CN102964856A (en) * | 2012-12-20 | 2013-03-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based solubilizing and toughening agent-modified epoxy asphalt material |
| CN110903606A (en) * | 2019-12-10 | 2020-03-24 | 安徽农业大学 | Plant oil-based composite material and preparation method thereof |
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