CN115304745B - Resveratrol and isovanillin based bio-based composite epoxy resin and preparation method thereof - Google Patents
Resveratrol and isovanillin based bio-based composite epoxy resin and preparation method thereof Download PDFInfo
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- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- 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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- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- 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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Abstract
The invention discloses a resveratrol and isovanillin based bio-based composite epoxy resin and a preparation method thereof, and the preparation method comprises the following steps: (1) Uniformly stirring and mixing the compound shown in the formula A and the compound shown in the formula B to obtain a biobased epoxy monomer compound; (2) And (2) mixing the bis-bio-based epoxy monomer compound obtained in the step (1) with a curing agent, melting and curing to obtain the epoxy resin composition. The biobased material used in the invention mainly comprises biobased resveratrol and biobased isovanillin, the synthesis of the epoxy monomer is simple, the conversion rate is high, the source is wide, the degree of greenization is high, and the biosecurity of the product is high. The invention uses the bio-based epoxy resin in the system as a raw material for the first time, prepares and realizes the corresponding composite bio-based epoxy resin material, realizes the construction of the carbon-based functional material, and is expected to become a novel bio-based high carbon-containing material.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a resveratrol and isovanillin based bio-based composite epoxy resin and a preparation method thereof.
Background
The epoxy resin is one of the most applied polymer materials at present, mainly has the characteristic of thermosetting, compared with a thermoplastic material, the thermosetting resin material has higher use temperature, does not generate melting and fusing phenomena, has better functions in the aspects of mechanical property, thermal property, corrosion resistance and the like, and has better application in the aspects of coatings, electronic sealants and the like, so the epoxy resin polymer material developed on the basis has better application value in the aspects of engineering plastics, engineering composite materials, surface layer protection and the like.
The global productivity of epoxy resin is about 500 ten thousand tons/year, wherein the basic variety is still mainly bisphenol A epoxy resin structure. The rapid development of the coating and paint industries in the world means that the market consumption of epoxy resins is high. The bisphenol A epoxy resin has excessive dependence and more obvious potential safety hazard in use, and recently, the substitution trend of some corresponding structures or raw materials is gradually formed in the aspects of bio-based substitution and the like.
The fundamental reason for the replacement of the bio-based epoxy resin is not only the resource shortage problem caused by the over-exploitation of the existing petrochemicals, but also the limitation of acetone and phenol for preparing bisphenol A, a strong acid preparation process and the like by petrochemical resources and other factors. In addition, the bisphenol A has a large market share, and the research proportion is high in the aspects of polymers such as epoxy resin, polycarbonate and the like, but bisphenol A resin has negative influence on human reproductive health, and is forbidden to be used as a packaging material of infant formula milk powder by the Federal drug administration in the United states, and the corresponding forbidden field is gradually widened. Meanwhile, the corresponding epoxy resin material has better wear resistance, but the granular particles generated in the long-term use process further enable the material to be easy to accumulate in the environment for a long time, so that possible secondary safety pollution can also occur.
The requirement for replacing the bio-based material and the consideration on the safety aspect of the bio-based material are widely developed, the biomass epoxy resin with relatively high safety is developed, the epoxy resin which replaces petroleum resources in the aspects of high performance, high biological safety and the like has a very good prospect in the future development process.
In addition, the traditional bisphenol a epoxy resin structure has poor effect in the aspect of thermal stability, and at the same time, the combustion pollution degree is severe, and the carbon content after heating is close to zero, so that the carbon content is low, however, the research on the preparation of the bio-based carbon material based on the decomposition carbonization process of the bio-based epoxy resin is less at present.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a resveratrol and isovanillin based bio-based composite epoxy resin and a preparation method thereof.
In order to solve the technical problems, the invention discloses a preparation method of a resveratrol and isovanillin based bio-based composite epoxy resin, which comprises the following steps:
(1) Uniformly stirring and mixing a compound shown as a formula A and a compound shown as a formula B to obtain a biobased epoxy monomer compound;
(2) Mixing the bis-bio-based epoxy monomer compound obtained in the step (1) with a curing agent, melting and curing to obtain the epoxy resin composition;
the curing agent is represented by formula C and/or formula D;
in the step (1), the preparation of the compound shown in the formula A specifically comprises the following steps: sequentially adding resveratrol, triethylbenzene ammonium chloride and epoxy chloropropane into a reaction bottle at room temperature, magnetically stirring, heating for reaction, and cooling to room temperature after the reaction is finished; and then adding triethyl phenyl ammonium chloride and an aqueous solution of sodium hydroxide into the system, stirring and reacting at room temperature, extracting a reaction solution after the reaction is finished, layering, drying an organic phase, filtering, concentrating, and purifying by silica gel column chromatography to obtain the catalyst.
In the step (1), the preparation of the compound shown in the formula B comprises the following specific steps: sequentially adding sodium hydroxide, potassium hydroxide and deionized water into a reaction bottle, heating the system, then adding the isovanillin into the system, and heating for reaction; after the reaction is finished, acidifying the system by using phosphoric acid until the pH value is =2 at room temperature, filtering, washing a solid part by using water, and drying to obtain an intermediate; then, sequentially adding the obtained intermediate, benzyltriethylammonium chloride and epichlorohydrin into a reaction bottle, heating for reaction, continuously adding benzyltriethylammonium chloride and an aqueous solution of sodium hydroxide into the system, and continuously reacting at room temperature; extracting reaction liquid after the reaction is finished, layering, washing an organic phase with water, layering, drying the organic phase, concentrating, and purifying by silica gel column chromatography to obtain the catalyst.
Specifically, in step (1), the molar ratio of epoxy groups in the compound represented by formula A to epoxy groups in the compound represented by formula B is n,0< -n < -100 >, preferably 0.3. Ltoreq. N.ltoreq.3.
Specifically, in the step (2), the molar ratio of the epoxy group in the bis-bio-based epoxy monomer composite to the NH in the curing agent is 2:1 to 4.
Wherein, the epoxy group in the biobased epoxy monomer compound is bonded with NH in the curing agent through C-N.
Specifically, in the step (2), the melting temperature is 50-75 ℃.
Specifically, in the step (2), the curing temperature is 65-95 ℃; the solidification temperature is greater than or equal to the melting temperature.
Specifically, in the step (2), the curing time is 2-5 h.
The resveratrol and isovanillin based bio-based composite epoxy resin prepared by the preparation method is also within the protection scope of the invention.
The application of the resveratrol and isovanillin based bio-based composite epoxy resin in preparing a bio-based carbon material is also within the protection scope of the invention.
Has the advantages that:
(1) The invention provides a preparation method of resveratrol and isovanillin-based composite bio-based epoxy resin, the green cleaning degree of an epoxy monomer is high, and the curing process is mild and efficient;
(2) The material prepared based on the bio-based epoxy monomer is further constructed by constructing a bio-based carbon base in an oxidation mode;
(3) The bio-based carbon prepared by the oxidation-based method has relatively high content, and is convenient for further expanding the application research of the biomass carbonized material.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a synthetic route of resveratrol bio-based epoxy resin monomer shown in formula A.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a resveratrol bio-based epoxy resin monomer shown in formula A.
FIG. 3 is the NMR carbon spectrum of resveratrol bio-based epoxy resin monomer shown in formula A.
FIG. 4 shows the synthesis route of the isovanillin biology base epoxy resin monomer shown in the formula B.
Fig. 5 is a nuclear magnetic resonance hydrogen spectrum of intermediate E shown in fig. 4.
Fig. 6 is a nuclear magnetic resonance carbon spectrum of intermediate E shown in fig. 4.
FIG. 7 shows the NMR spectrum of the isovanillin biology-based epoxy resin monomer shown in the formula B.
FIG. 8 shows the NMR spectrum of the isovanillin biology-based epoxy resin monomer shown in the formula B.
FIG. 9 is a Raman spectrum of a polymer material obtained in example 9; wherein the corresponding peak integral area ratio I G /I D ＝0.328。
FIG. 10 is a Raman spectrum of the polymeric material obtained in example 10; wherein the corresponding peak integral area ratio I G /I D ＝0.317。
FIG. 11 is a thermogravimetric plot of the polymeric materials obtained in examples 3 and 4.
FIG. 12 is a thermogravimetric plot of the polymeric materials obtained in examples 9 and 10.
FIG. 13 is a thermogravimetric plot of the polymeric materials obtained in examples 5 and 6.
FIG. 14 is an IR spectrum of the polymer materials obtained in examples 3 to 12.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Raw materials synthesis part example:
example 1
At room temperature, sequentially adding resveratrol (1.0 g), triethyl phenyl ammonium chloride (0.29 g) and epichlorohydrin (12.0 g) into a 100mL three-mouth reaction bottle, and magnetically and uniformly stirring to obtain a mixture; stirring the obtained mixture at 80 ℃ for reacting for 2h, and cooling the reaction liquid to room temperature after the reaction is finished; then, continuously adding triethylphenyl ammonium chloride (0.29 g) and a sodium hydroxide aqueous solution (2.06g, 5.0 mol/L) into the system, stirring and reacting at room temperature until the reaction is finished, extracting the reaction solution with ethyl acetate after the reaction is finished, layering, drying an organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtrate, and purifying by silica gel column chromatography to obtain a light yellow solid product, namely a compound in the formula A, of 1.6g, wherein the yield is 92%; the synthesis route of the compound of the formula A is shown in figure 1, the nuclear magnetic resonance hydrogen spectrum of the compound of the formula A is shown in figure 2, and the nuclear magnetic resonance carbon spectrum is shown in figure 3.
Example 2
Sodium hydroxide (32.17 g), potassium hydroxide (48.25 g) and deionized water (16 mL) were added to a 500mL flask in this order, then the mixture was heated to 160 ℃ over 10min, followed by addition of isovanillin (96.5g, 0.635 mol) to the system, and the reaction system was allowed to continue to react at 160 ℃ for 4h; after the reaction was completed, the reaction mixture was transferred to a beaker, acidified with phosphoric acid until pH =2 at room temperature, filtered, and the resulting precipitate was washed with water and finally dried to obtain solid intermediate E92 g with a yield of 86.2%; the synthesis route of the intermediate E is shown in FIG. 4, the nuclear magnetic resonance hydrogen spectrum of the intermediate E is shown in FIG. 5, and the nuclear magnetic resonance carbon spectrum is shown in FIG. 6.
Intermediate E (2.52 g), benzyltriethylammonium chloride (TEACC, 0.34 g), epichlorohydrin (13.8 g) were added to a flask (250 mL) and the mixture was reacted by magnetic stirring at 80 ℃ for 4.5h, followed by addition of another TEACC (0.34 g) and aqueous sodium hydroxide (2.4 g,5.0 mol/L) and reaction at room temperature for 1.5h; after the reaction was completed, the mixture was extracted with ethyl acetate three times, and the layers were separated, the combined organic phase was washed with water three times, and the layers were separated, and the organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated, and the mixture was purified by silica gel column chromatography using PE/EA as an eluent, to obtain 3.0g of a white solid compound of formula B with a yield of 71.3%; the NMR spectrum of the compound of formula B is shown in FIG. 7, and the NMR spectrum is shown in FIG. 8.
Polymerization section examples:
example 3
Preparation of OSBBB/NED Polymer
Weighing resveratrol bio-based epoxy resin monomer (0.1586 g, prepared in example 1) shown in formula A in a reaction bottle, metering curing agent C (0.1334 g) at 25 ℃, heating to about 60 ℃, keeping the sample in a molten state, rapidly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 75 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate was analyzed to determine the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Equal strength stretching vibration) disappears, indicating that the epoxy group and the amino group of the epoxy resin are completely polymerized, and 3434cm is generated due to the ring opening process of the epoxy -1 The greater absorption relative to the starting epoxy monomer is inferred to be due to the large number of hydroxyl groups formed in the process.
Example 4
Preparation of OSPBBBB/NNED Polymer
Weighing resveratrol bio-based epoxy resin monomer (0.1586 g, prepared in example 1) shown in formula A in a reaction bottle, metering and adding curing agent D (0.1593 g) at 25 ℃, heating to about 60 ℃, enabling a sample to be in a molten state, rapidly stirring to keep the materials to be fully molten, and uniformly mixing. Then gradually raising the temperature to 70 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate shows that the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Equal strength stretching vibration) disappears, indicating that the epoxy group and the amino group of the epoxy resin are completely polymerized, and 3434cm is generated due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process.
Example 5
50% OSBBB/50% preparation of OYMB/NED Polymer
Weighing a resveratrol bio-based epoxy resin monomer (0.0793 g, prepared in example 1) shown in formula A and an isovanillin bio-based epoxy resin monomer (0.0841 g, prepared in example 2) shown in formula B in a reaction bottle, metering a curing agent C (0.1334 g) at 25 ℃, heating to about 60 ℃, keeping a sample in a molten state, rapidly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 80 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate shows that the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process.
Example 6
50% OSBBB/50% preparation of OYMB/NNED polymer
Weighing resveratrol bio-based epoxy resin monomer (0.0793 g, prepared in example 1) shown in formula A and isovanillin bio-based epoxy resin monomer (0.0841 g, prepared in example 2) shown in formula B in a reaction bottle, metering curing agent D (0.1593 g) at 25 ℃, heating to about 60 ℃, keeping the sample in a molten state, rapidly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 80 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate shows that the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process.
Example 7
75% OYMB/25% preparation of OSBBB/NED Polymer
Weighing a resveratrol bio-based epoxy resin monomer (0.0395 g, prepared in example 1) shown in formula A and an isovanillin bio-based epoxy resin monomer (0.1261 g, prepared in example 2) shown in formula B in a reaction bottle, metering a curing agent C (0.1334 g) at 25 ℃, heating to about 60 ℃, keeping a sample in a molten state, rapidly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 90 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate was analyzed to determine the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption relative to the starting epoxy monomer is inferred to be due to the large number of hydroxyl groups formed in the process.
Example 8
75% OYMB/25% preparation of OSBBB/NNED polymer
Weighing a resveratrol bio-based epoxy resin monomer (0.0395 g, prepared in example 1) shown in formula A and an isovanillin bio-based epoxy resin monomer (0.1261 g, prepared in example 2) shown in formula B in a reaction bottle, metering a curing agent D (0.1593 g) at 25 ℃, heating to about 60 ℃, keeping a sample in a molten state, quickly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 80 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate was analyzed to determine the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process.
Example 9
Preparation of OYMB/NED Polymer
Weighing the isoaroma shown as the formula B in a reaction bottleLanolin bio-based epoxy resin monomer (0.109 g, prepared in example 2), curing agent C (0.086 g) was metered in at 25 deg.C, the temperature was raised to about 60 deg.C, the sample was in a molten state, the mixture was stirred rapidly to keep the material well molten and mixed well. Then gradually raising the temperature to 95 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate shows that the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process. Under the air, the sample is horizontally placed at 45 degrees, then the sample is ignited for 5s, the fire source is removed, the self-combustion of the epoxy resin is maintained until the epoxy resin is extinguished, the residual carbon is directly used for Raman testing, and the graphene G is located at 1590cm according to the analysis rule -1 Irregular graphene structure D at 1356cm -1 As shown in fig. 9.
Example 10
Preparation of OYMB/NNED polymers
The isovanillin biobased epoxy resin monomer (0.109 g, prepared in example 2) of formula B was weighed into a reaction flask, curing agent D (0.1356 g) was metered in at 25 deg.C, the temperature was raised to about 60 deg.C, the sample was in a molten state, stirred rapidly to keep the material well molten, and mixed well. Then gradually raising the temperature to 85 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate was analyzed to determine the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Equal strength stretching vibration) disappears, indicating that the epoxy group and the amino group of the epoxy resin are completely polymerized, and 3434cm is generated due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process. Under the air, the sample is horizontally placed at 45 degrees, then the sample is ignited for 5s, the fire source is removed, the self-combustion of the epoxy resin is maintained until the epoxy resin is extinguished, the residual carbon is directly used for Raman testing, and the graphene G is located at 1590cm according to the analysis rule -1 Is not regularThe graphene structure D is located at 1356cm -1 As shown in fig. 10.
Example 11
25% OYMB/75% preparation of OSBBB/NED Polymer
Weighing a resveratrol bio-based epoxy resin monomer (0.111 g, prepared in example 1) shown in formula A and an isovanillin bio-based epoxy resin monomer (0.0392 g, prepared in example 2) shown in formula B in a reaction bottle, metering a curing agent C (0.1245 g) at 25 ℃, heating to about 60 ℃, keeping a sample in a molten state, quickly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 80 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate shows that the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process.
Example 12
25% preparation of OYMB/75% OSBBB/NNED Polymer
Weighing resveratrol bio-based epoxy resin monomer (0.111 g, prepared in example 1) shown in formula A and isovanillin bio-based epoxy resin monomer (0.0392 g, prepared in example 2) shown in formula B in a reaction bottle, metering curing agent D (0.1486 g) at 25 ℃, heating to about 60 ℃, keeping the sample in a molten state, rapidly stirring to keep the materials fully molten, and uniformly mixing. Then gradually raising the temperature to 80 ℃ to start curing, and then maintaining the temperature for 2 hours to obtain a transparent light yellow polymer material. As shown in FIG. 14, the infrared data of the epoxy substrate was analyzed to determine the infrared peaks (860 cm and 910 cm) of ethylene oxide in the original epoxy substrate -1 Constant-strength stretching vibration) disappears, indicating that the epoxy group and the amine group of the epoxy resin are completely polymerized, and 3434cm is obtained due to the ring opening process of the epoxy -1 The greater absorption occurs relative to the starting epoxy monomer, presumably due to the large number of hydroxyl groups formed in the process.
TABLE 1 thermal stability and residual carbon content at 700 ℃ of Biobased epoxy resins
From Table 1, it can be seen that adding OSBBB to the OYMB/NED system benefits T as a whole d30 And T max And R 700 The thermal stability and the char yield of the material are improved; although the char-forming performance of the OSBBB/NED system is similar to that of OYMB/NED, R can still be made by effective compounding 700 The improvement is about 7% (example 7vs example 9); in addition, the T of OYMB/NNED can be improved in terms of thermal performance by 50 percent of OSPBBBB max About 40 ℃ C, T d30 Increasing to above 400 ℃ (example 6vs example 10).
Table 2 examples 3-6 combustion carbon structure morphology
The invention provides a thought and a method based on resveratrol and isovanillin bio-based composite epoxy resin and a preparation method thereof, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in this embodiment can be implemented by the prior art.
Claims (8)
1. A preparation method of a bio-based composite epoxy resin based on resveratrol and isovanillin is characterized by comprising the following steps:
(1) Uniformly stirring and mixing a compound shown as a formula A and a compound shown as a formula B to obtain a biobased epoxy monomer compound;
(2) Mixing the biobased epoxy monomer compound obtained in the step (1) with a curing agent, melting and curing to obtain the product;
the curing agent is represented by formula C and/or formula D;
2. the production method according to claim 1, characterized in that in step (1), the molar ratio of epoxy groups in the compound represented by formula a to epoxy groups in the compound represented by formula B is n, 0-n-woven fabric.
3. The method according to claim 1, wherein in the step (2), the molar ratio of the epoxy group in the bis-biobased epoxy monomer composite to the NH in the curing agent is 2:1 to 4.
4. The method according to claim 1, wherein the melting temperature in the step (2) is 50 to 75 ℃.
5. The preparation method according to claim 1, wherein in the step (2), the curing is carried out at a curing temperature of 65-95 ℃; the solidification temperature is greater than or equal to the melting temperature.
6. The method according to claim 1, wherein in the step (2), the curing is carried out for 2 to 5 hours.
7. The resveratrol and isovanillin based bio-based composite epoxy resin prepared by the preparation method of any one of claims 1-6.
8. The use of the resveratrol and isovanillin based bio-based composite epoxy resin of claim 7 in the preparation of bio-based carbon materials.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211078662.1A CN115304745B (en) | 2022-09-05 | 2022-09-05 | Resveratrol and isovanillin based bio-based composite epoxy resin and preparation method thereof |
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| CN202211078662.1A CN115304745B (en) | 2022-09-05 | 2022-09-05 | Resveratrol and isovanillin based bio-based composite epoxy resin and preparation method thereof |
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| CN113292703A (en) * | 2021-05-28 | 2021-08-24 | 南京工业大学 | Phosphorus-free full-bio-based flame-retardant epoxy resin with excellent thermal and mechanical properties and green preparation method thereof |
| CN114395110A (en) * | 2022-01-30 | 2022-04-26 | 南京工业大学 | All-bio-based cyano epoxy resin and green preparation method thereof |
| CN114456128A (en) * | 2022-02-25 | 2022-05-10 | 南京工业大学 | Application of novel isovanillin epoxy resin monomer in preparation of silicon-containing polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113292703A (en) * | 2021-05-28 | 2021-08-24 | 南京工业大学 | Phosphorus-free full-bio-based flame-retardant epoxy resin with excellent thermal and mechanical properties and green preparation method thereof |
| CN114395110A (en) * | 2022-01-30 | 2022-04-26 | 南京工业大学 | All-bio-based cyano epoxy resin and green preparation method thereof |
| CN114456128A (en) * | 2022-02-25 | 2022-05-10 | 南京工业大学 | Application of novel isovanillin epoxy resin monomer in preparation of silicon-containing polymer |
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