CN115449054B - Biological-based epoxy resin based on paeonol and preparation method and application thereof - Google Patents
Biological-based epoxy resin based on paeonol and preparation method and application thereof Download PDFInfo
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- CN115449054B CN115449054B CN202211285521.7A CN202211285521A CN115449054B CN 115449054 B CN115449054 B CN 115449054B CN 202211285521 A CN202211285521 A CN 202211285521A CN 115449054 B CN115449054 B CN 115449054B
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- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a bio-based epoxy resin based on paeonol, a preparation method and application thereof, and belongs to the technical field of bio-based epoxy resins. The invention also provides a bio-based epoxy resin material obtained by curing the bio-based epoxy resin monomer, which has the advantages of simple synthesis process, simple and convenient operation, high green degree, effective reduction of dependence on fossil resources and greater advantages compared with the existing petroleum-based epoxy resin. The bio-based epoxy resin obtained in the polymerization process has novel structure and excellent performance, and has the possibility of replacing the existing petroleum-based products.
Description
Technical Field
The invention belongs to the technical field of bio-based epoxy resin, and relates to a paeonol-based bio-based epoxy resin, and a preparation method and application thereof.
Background
Thermoset polymers have found wide application in various fields such as aerospace, electronics, high performance composites, and coatings. Epoxy resins (EP) have great potential applications due to their excellent dimensional stability, chemical resistance and balanced mechanical properties. However, most commercial epoxy resins are obtained from petroleum sources, and 90% of the epoxy resins are composed of bisphenol a diglycidyl ether (DGEBA) prepared from bisphenol a and Epichlorohydrin (ECH). Bisphenol A is mainly produced by using petroleum resources, so that the environmental problem is aggravated; in addition, bisphenol a-based resins have been banned by the U.S. federal drug administration as packaging materials for infant formulas due to their negative effects on health such as reproduction. Thus, the preparation of polymeric materials from biomass feedstocks is an important strategy for replacing petroleum resources, and the extensive development of high performance, biosafety thermosetting resins to replace the excessive use of petroleum resources is critical to maintaining sustainable development.
In recent years, various biomass-derived compounds have been used as raw materials for preparing renewable epoxy networks, such as vegetable oils, lignin, rosin, isosorbide, eugenol, and the like. The main biological sources of bio-based epoxy resin monomers studied at present are still based on a large number of benzene ring aromatic systems. Paeonol, also called paeonol, is a compound based on both aldehyde groups and phenolic hydroxyl groups, and researchers focus on the application of paeonol in preparation of biopolyphenols due to the phenolic hydroxyl groups. However, paeonol has only one phenolic hydroxyl group, and the bio-based bisphenol is prepared by chemical modification of paeonol serving as a raw material and other compounds.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the bio-based epoxy resin based on paeonol, which can be prepared from the paeonol of biological origin, is low in cost and easy to obtain, and can reduce the potential toxicity of the paeonol.
The invention also solves the technical problem of providing a preparation method of the paeonol-based bio-based epoxy resin.
In order to solve the first technical problem, the invention discloses a bio-based epoxy resin based on paeonol, which consists of a binary polymer formed by A and B or a binary polymer formed by A and C,
wherein, A, B, C's constitutional unit is respectively:
wherein, the binary polymer formed by A and B has a repeated structural unit shown in a formula I, and the binary polymer formed by A and C has a repeated structural unit shown in a formula II;
wherein m is more than or equal to 2, and n is more than or equal to 2.
Wherein, in the repeating structural units shown in the formula I, the structural units A and B are alternately connected, and the structural unit B is connected with at most 3 structural units A; in the repeating structural units represented by formula II, structural units A and C are alternately connected, and structural unit C is connected to at most 4 structural units A.
In order to solve the second technical problem, the invention discloses a preparation method of the paeonol-based bio-based epoxy resin, which comprises the steps of mixing paeonol-based bio-based epoxy resin monomer (BPEO) with an aminosilane curing agent, melting, injection molding and curing to obtain paeonol-based bio-based epoxy resin;
wherein, the structure of the paeonol-based bio-based epoxy resin monomer is shown as a formula III:
wherein the aminosilane curing agent comprises, but is not limited to, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and/or diethylenetriamine propyl trimethoxysilane;
specifically, the molar ratio of epoxy groups in the paeonol-based bio-based epoxy resin monomer to NH in the aminosilane-based curing agent is 1:0.6 to 2.
Specifically, the melting temperature is 45-65 ℃ until the solid is completely melted; the curing temperature is 70-90 ℃ and the curing time is 1-3 h.
The preparation method of the paeonol-based bio-based epoxy resin monomer comprises the following steps:
s1: dissolving paeonol and boron tribromide in dichloromethane to perform a first reaction to obtain 2, 4-dihydroxyacetophenone;
s2: mixing epichlorohydrin, a phase transfer catalyst and the 2, 4-dihydroxyacetophenone obtained in the step S1 for a second reaction; and after the second reaction is finished, cooling to room temperature, and adding an alkaline solution into the system for a third reaction to obtain the catalyst.
Wherein the structure of the 2, 4-dihydroxyacetophenone is as follows:
specifically, in step S1, the 2, 4-dihydroxyacetophenone is prepared according to other prior art, and may also be prepared according to the following preparation method: rapidly adding boron tribromide into a paeonol-based ultra-dry dichloromethane solution at the temperature of minus 60 ℃ for stirring, then slowly enabling the reaction solution to reach the room temperature, and stirring for reaction at the room temperature; after the reaction was completed, the reaction system was cooled to 0℃and NH was slowly added 4 Cl performs quenching reaction. Removing dichloromethane in vacuum, adding ethyl acetate into the reactant for extraction, separating liquid, washing an organic phase by water and brine in sequence, and separating an organic layer; finally, the organic layer is dried by anhydrous sodium sulfate, the solvent is removed in vacuum, and the organic layer is separated and purified by column chromatography.
Specifically, in step S1, the molar ratio of paeonol to boron tribromide is 1:0.5 to 5; the mass volume ratio of paeonol to dichloromethane is 1: 10-20 g/mL.
Wherein the dichloromethane is ultra-dry dichloromethane.
Specifically, in step S1, the reaction temperature is room temperature, and the reaction time is 50-70 h, preferably 60h.
Specifically, in step S2, the phase transfer catalyst is tetraethylammonium bromide; the alkaline solution is any one or the combination of a plurality of potassium carbonate solution, sodium hydroxide solution and potassium hydroxide solution; the mass concentration of alkali in the alkaline solution is 20% -50%.
Wherein, the alkaline solution, the solvent is water, and the solute is alkali.
Specifically, in the step S2, the molar ratio of the 2, 4-dihydroxyacetophenone, epichlorohydrin to the phase transfer catalyst is 1: 20-30: 0.2 to 0.5; the molar ratio of the alkali to the epichlorohydrin in the alkaline solution is 1-1.5: 1, preferably 1:1.
specifically, in the step S2, the second reaction is carried out at a temperature of 70-90 ℃, preferably 80 ℃ for 3-5 hours, preferably 4 hours; the third reaction is carried out at room temperature for 0.5-1 h, preferably 0.5h.
In the step S2, the second reaction and the third reaction are performed under stirring, and the stirring speed is 800-1000 rpm.
In the step S2, after the third reaction is finished, the reaction solution is diluted with water, extracted with ethyl acetate, separated, dried to obtain an organic phase, filtered, the filtrate is decompressed and distilled to remove the solvent, and the filtrate is separated and purified by column chromatography to obtain BPEO.
The application of the paeonol-based bio-based epoxy resin as a precursor in preparing the thermosetting epoxy resin is also within the protection scope of the invention.
The beneficial effects are that:
(1) Compared with the prior art, the bio-based epoxy resin based on the natural paeonol compound can be used as a precursor of the thermosetting epoxy resin, the natural paeonol compound from a bio-based source is directly adopted as a raw material, the preparation method is simple and efficient, the operation is simple and convenient, the control is good, the mass production can be realized by utilizing the existing chemical equipment, and the dependence of the existing petroleum-based epoxy resin on petrochemical resources and the pollution of the petroleum-based epoxy resin on the environment can be reduced.
(2) Since paeonol is the main active ingredient of root bark of Paeonia suffruticosa of Paeoniaceae and root bark or whole grass of Cynanchum paniculatum of Cynanchum of Asclepiadaceae, the development of bio-based epoxy resin products based on paeonol can promote the development of bio-based materials, has important significance for promoting the sustainable development of the fields of the whole polymer materials and the like, is a bio-based, green and environment-friendly product, and has dual effects of saving petroleum resources and protecting the environment.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a reaction scheme for preparing epoxy resin monomer BPEO according to the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the epoxy resin monomer BPEO.
FIG. 3 is a nuclear magnetic resonance carbon spectrum of the epoxy resin monomer BPEO.
Fig. 4 is a high resolution mass spectrum of epoxy monomer BPEO.
Fig. 5 is a fourier infrared spectrum of epoxy monomer BPEO.
FIG. 6 is a TGA plot of epoxy monomer BPEO.
FIG. 7 is a Fourier infrared spectrum of the epoxy resin polymer obtained in example 3.
FIG. 8 is a TGA graph of the epoxy resin polymer obtained in example 3.
Fig. 9 is a fourier infrared spectrum of the epoxy resin polymer obtained in example 4.
FIG. 10 is a TGA graph of the epoxy resin polymer obtained in example 4.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
The preparation method of the 2, 4-dihydroxyacetophenone comprises the following steps: paeonol (24 g,144 mmol) was added to a 1000mL round bottom flask, ultra-dry dichloromethane (400 mL) was added and dissolved with stirring at-60℃and BBr was then added rapidly to the system 3 (28.8 mL,298.89 mmol) and then the reaction mixture was allowed to slowly reach room temperature, and the reaction was stirred at room temperature for 60 hours. After the reaction was completed, the reaction system was cooled to 0℃and NH was slowly added 4 Cl performs quenching reaction. Dichloromethane was removed in vacuo, ethyl acetate was then added to the reaction mixture to extract, the organic phase was separated, washed with water and brine sequentially, and the organic layer was separated; finally, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed in vacuo, and the target product was purified by silica gel column chromatography using a PE/ea=6/1 system as eluent to give 2, 4-dihydroxyacetophenone (19.9 g) as a white solid in 90.8% yield.
The synthetic route of the compound 2, 4-dihydroxyacetophenone is shown in figure 1, and the nuclear magnetic resonance hydrogen spectrum data are shown as follows:
1 H NMR(400MHz,Chloroform-d)δ12.69(s,1H),7.73-7.57(m,1H),6.46-6.31(m,2H),2.57(s,3H).
example 2
Preparation of paeonol-based bio-based epoxy monomer (BPEO): epichlorohydrin (73.3 g,792 mmol), tetraethylammonium bromide (1.6 g,7.88 mmol) and 2, 4-dihydroxyacetophenone (6 g,39.43 mmol) were added to a 500mL round bottom flask at room temperature, and after mixing, the mixture was stirred at 80℃for 4 hours, and after completion of the reaction of the starting materials by TLC plate, heating was stopped and the reaction solution was cooled to room temperature; then, a NaOH solution (40% by mass of sodium hydroxide in the solution, 31.7g,792 mmol) was slowly added to the reaction mixture, and the reaction was completed after 0.5h at room temperature as measured by TLC plate. After the reaction is finished, adding water into the reaction liquid to dilute, extracting with ethyl acetate for three times, separating liquid, organically drying and removing water, filtering, decompressing and rotationally evaporating filtrate to remove solvent to obtain a crude product, separating and purifying the crude product by silica gel chromatographic column chromatography, and selecting a PE/EA=3/1 system as an eluent to obtain 8.5g of white solid BPEO with the yield of 81.5%.
The synthesis route of the BPEO is shown in fig. 1, the nmr hydrogen spectrum of the BPEO is shown in fig. 2, the nmr carbon spectrum of the BPEO is shown in fig. 3, the high resolution mass spectrum of the BPEO is shown in fig. 4, and specific nmr hydrogen spectrum, carbon spectrum and mass spectrum data are shown as follows:
1 H NMR(400MHz,Chloroform-d)δ7.82(d,J＝8.6Hz,1H),6.69-6.37(m,2H),4.34(ddt,J＝16.3,11.0,2.7Hz,2H),3.96(td,J＝10.8,9.8,5.4Hz,2H),3.39(ddq,J＝21.8,6.3,3.0Hz,2H),2.94(dt,J＝9.1,4.5Hz,2H),2.78-2.72(m,2H),2.62(s,3H).
13 C NMR(101MHz,Chloroform-d)δ197.60,163.15,159.72,132.77,121.82,106.30,100.03,69.62,69.03,49.89,44.59,31.96.
HRMS(ESI-TOF)m/z Calcd for[M+H] + :265.1071,[M+Na] + :287.089；Found[M+H] + :265.1070,[M+Na] + :287.0893.
the fourier infrared spectrum of BPEO is shown in fig. 5, which is known from the figure: ethylene oxide characteristicsPeak 862cm -1 And 906cm -1 The formation indicated that the epoxide group had been successfully introduced into 2, 4-dihydroxyacetophenone, indicating successful preparation of BPEO monomer.
The TGA profile of BPEO is shown in fig. 6, as known from the figure: the initial decomposition temperature was 241℃and the maximum decomposition temperature was 342 ℃.
Example 3
BPEO (1.32 g,5 mmol) was weighed into a reaction flask, and under nitrogen atmosphere, curative N- (2-aminoethyl) -3-aminopropyl trimethoxysilane (1.1 g,4.99 mmol) was metered in at 25℃and heated to 45℃while stirring rapidly for 5min to ensure sufficient melting of the material, mixing homogeneously and heating to 80℃for curing. Solidifying for 2h at the temperature, and cooling to obtain the light yellow clear epoxy resin polymer. As shown in FIG. 7, the infrared peak (862 cm -1 And 906cm -1 Equal-intensity stretching vibration) is passed, indicating that the epoxy groups and amine groups of the epoxy resin have been completely polymerized.
Polymer infrared data attribution: 1029cm -1 Vibrating carbon-oxygen bond in fatty ether bond C-O-C; 1265cm -1 Vibrating carbon-oxygen bond in aromatic ether bond C-O-C; 1662cm -1 Stretching vibration of c=o bond in acetophenone; 823cm -1 The left and right peaks are the stretching vibration of=c-H bond on the benzene ring; 3422cm -1 The broad absorption peak at this point is the peak formed by the ring opening of the ethylene oxide leading to the appearance of OH groups.
The thermal gravimetric data analysis of the obtained epoxy resin polymer under nitrogen is shown in fig. 8, the initial decomposition temperature is 290 ℃, and the maximum decomposition temperature is 409.6 ℃, which shows that the obtained material has good heat resistance.
Example 4
BPEO (1.32 g,5 mmol) is weighed in a reaction bottle, a curing agent of diethylenetriamine propyl trimethoxy silane (0.995 g,3.75 mmol) is metered and added at 25 ℃ under the nitrogen atmosphere, the temperature is raised to 45 ℃ to be fully melted, the mixture is uniformly mixed, the temperature is raised to 80 ℃ to be cured for 2 hours, and the yellowish clear epoxy resin polymer is obtained after cooling. By applying infrared data to the obtained epoxy resin polymerAs shown in FIG. 9, the infrared peak of ethylene oxide (862 cm -1 And 906cm -1 Equal-intensity stretching vibration) is passed, indicating that the epoxy groups and amine groups of the epoxy resin have been completely polymerized.
Polymer infrared data attribution: 1028cm -1 Vibrating carbon-oxygen bond in C-O-C which is aliphatic ether bond; 1264cm -1 Is carbon oxygen bond vibration in aromatic ether bond C-O-C; 1662cm -1 Is the stretching vibration of C=O bond in acetophenone; 824cm -1 The left and right peaks are on benzene ring=c-stretching vibration of H-bond; 3421cm -1 The broad absorption peak at this point is the peak formed by the ring opening of the ethylene oxide leading to the appearance of OH groups.
Analysis of thermogravimetric data of the obtained epoxy resin polymer under nitrogen, as shown in fig. 10, shows that the initial decomposition temperature is 298 ℃ and the maximum decomposition temperature is 399 ℃, which shows that the obtained material has good heat resistance.
The invention provides a paeonol-based bio-based epoxy resin, a preparation method and an application thought and a method thereof, and particularly the method and the way for realizing the technical scheme are a plurality of preferred embodiments of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (11)
1. A paeonol-based bio-based epoxy resin is characterized by comprising a binary polymer formed by A and B or a binary polymer formed by A and C,
wherein, A, B, C's constitutional unit is respectively:
wherein, the binary polymer formed by A and B has a repeated structural unit shown in a formula I, and the binary polymer formed by A and C has a repeated structural unit shown in a formula II;
wherein m is more than or equal to 2, and n is more than or equal to 2.
2. The preparation method of the paeonol-based bio-based epoxy resin, which is characterized in that paeonol-based bio-based epoxy resin monomers and an aminosilane curing agent are mixed, melted, injection molded and cured to obtain the paeonol-based bio-based epoxy resin;
wherein, the structure of the paeonol-based bio-based epoxy resin monomer is shown as a formula III:
3. the preparation method according to claim 2, wherein the aminosilane curing agent is N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and/or diethylenetriamine propyl trimethoxysilane; the molar ratio of epoxy groups in the paeonol-based bio-based epoxy resin monomer to NH in the aminosilane curing agent is 1:0.6 to 2.
4. The method according to claim 2, wherein the melting temperature is 45 to 65 ℃; the curing temperature is 70-90 ℃ and the curing time is 1-3 h.
5. The preparation method according to claim 2, wherein the preparation method of the paeonol-based bio-based epoxy resin monomer comprises the steps of:
s1: dissolving paeonol and boron tribromide in dichloromethane to perform a first reaction to obtain 2, 4-dihydroxyacetophenone;
s2: epichlorohydrin is reacted with mixing the phase transfer catalyst with the 2, 4-dihydroxyacetophenone obtained in the step S1 to carry out a second reaction; and after the second reaction is finished, cooling to room temperature, and adding an alkaline solution into the system for a third reaction to obtain the catalyst.
6. The method according to claim 5, wherein in the step S1, the molar ratio of paeonol to boron tribromide is 1:0.5 to 5; the mass volume ratio of paeonol to dichloromethane is 1: 10-20 g/mL.
7. The method according to claim 5, wherein in the step S1, the first reaction is performed at room temperature for 50 to 70 hours.
8. The method according to claim 5, wherein in step S2, the phase transfer catalyst is tetraethylammonium bromide; the alkaline solution is any one or the combination of a plurality of potassium carbonate solution, sodium hydroxide solution and potassium hydroxide solution; the mass concentration of alkali in the alkaline solution is 20% -50%.
9. The method according to claim 5, wherein in the step S2, the molar ratio of the 2, 4-dihydroxyacetophenone, epichlorohydrin to the phase transfer catalyst is 1: 20-30: 0.2 to 0.5; the molar ratio of the alkali to the epichlorohydrin in the alkaline solution is 1-1.5: 1.
10. the preparation method according to claim 5, wherein in the step S2, the second reaction is performed at a temperature of 70-90 ℃ for 3-5 hours; the third reaction is carried out at room temperature for 0.5-1 h.
11. Use of the paeonol-based biobased epoxy resin of claim 1 as a precursor for the preparation of a thermally curable epoxy resin.
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| CN109734684A (en) * | 2018-12-20 | 2019-05-10 | 中国科学院宁波材料技术与工程研究所 | A kind of biology base fire retarding epoxide resin presoma and its preparation method and application based on natural phenolic monomer |
| CN112457472A (en) * | 2020-11-25 | 2021-03-09 | 广东工业大学 | Low-viscosity bio-based magnolol epoxy resin and preparation method thereof |
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| CN109734684A (en) * | 2018-12-20 | 2019-05-10 | 中国科学院宁波材料技术与工程研究所 | A kind of biology base fire retarding epoxide resin presoma and its preparation method and application based on natural phenolic monomer |
| CN112457472A (en) * | 2020-11-25 | 2021-03-09 | 广东工业大学 | Low-viscosity bio-based magnolol epoxy resin and preparation method thereof |
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