CN115304745A - Compound epoxy resin based on resveratrol and isovanillin biology and preparation method thereof - Google Patents
Compound epoxy resin based on resveratrol and isovanillin biology and preparation method thereof Download PDFInfo
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- CN115304745A CN115304745A CN202211078662.1A CN202211078662A CN115304745A CN 115304745 A CN115304745 A CN 115304745A CN 202211078662 A CN202211078662 A CN 202211078662A CN 115304745 A CN115304745 A CN 115304745A
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- epoxy resin
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- isovanillin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 61
- JVTZFYYHCGSXJV-UHFFFAOYSA-N isovanillin Chemical compound COC1=CC=C(C=O)C=C1O JVTZFYYHCGSXJV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229940016667 resveratrol Drugs 0.000 title claims abstract description 26
- 235000021283 resveratrol Nutrition 0.000 title claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 30
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract 1
- 235000013350 formula milk Nutrition 0.000 description 36
- 230000008569 process Effects 0.000 description 24
- 239000000758 substrate Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000002861 polymer material Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 238000007142 ring opening reaction Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ICTMDIORIDZWQN-UHFFFAOYSA-M triethyl(phenyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)C1=CC=CC=C1 ICTMDIORIDZWQN-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 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 2
- 230000001788 irregular Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RZSJZEHKTBMMDZ-UHFFFAOYSA-N azanium;1,2,3-triethylbenzene;chloride Chemical compound [NH4+].[Cl-].CCC1=CC=CC(CC)=C1CC RZSJZEHKTBMMDZ-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004585 electronic sealant Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009933 reproductive health Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Images
Classifications
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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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- 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
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
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 bio-based material used in the invention mainly comprises bio-based resveratrol and bio-based isovanillin, the synthesis of epoxy monomers is simple, the conversion rate is high, the source is wide, the degree of greenization is high, and the biological safety 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 shows the characteristic of thermosetting, compared with a thermoplastic material, the thermosetting resin material has higher use temperature, can not melt and fuse, 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 million 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 large. 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 that the existing petrochemical products are over-exploited to cause resource shortage, but also that the preparation processes of acetone and phenol and strong acid for preparing bisphenol A are limited by petrochemical resources and other factors. In addition, bisphenol a has a large market share and a high research proportion in the aspects of polymers such as epoxy resin, polycarbonate and the like, but bisphenol a resins have negative influence on human reproductive health, are forbidden to be used as packaging materials of infant formula by the federal drug administration in the united states, and the corresponding forbidden fields are 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 of the bio-based material on the aspect of safety are widely developed, the biomass epoxy resin with relatively high safety is developed, the epoxy resin which replaces petroleum resources on the aspects of high performance, high biological safety and the like has a 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 meanwhile, the combustion pollution degree is severe, and the carbon content after heating is close to zero, so the carbon content is low, however, the research on preparing the bio-based carbon material based on the decomposition and 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 the compound shown in the formula A and the compound shown in the 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;
wherein the curing agent is shown in a formula C and/or a 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 a system, then adding isovanillin into the system, and carrying out heating 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-woven fabrics n-woven fabrics 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 double-biology-base 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 cleanness 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 isovanillin biology-based epoxy resin monomer shown in 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 biobased epoxy monomer shown in formula B.
FIG. 8 is the NMR carbon spectrum of the isovanillin biobased epoxy monomer shown in 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 polymer 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, triethyl phenyl ammonium chloride (0.29 g) and an aqueous solution of sodium hydroxide (2.06g, 5.0 mol/L) are continuously added into the system, the mixture is stirred and reacted at room temperature until the reaction is finished, after the reaction is finished, the reaction solution is extracted by ethyl acetate, layers are separated, an organic phase is dried by anhydrous magnesium sulfate, the filtration is carried out, the filtrate is concentrated, and a light yellow solid product, namely a compound of the formula A, is obtained by purifying through silica gel column chromatography, 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
Adding sodium hydroxide (32.17 g), potassium hydroxide (48.25 g) and deionized water (16 mL) into a 500mL flask in turn, heating the mixture to 160 ℃ within 10min, then adding isovanillin (96.5g, 0.635mol) into the system, and continuously reacting the reaction system 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 part example:
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 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 Relatively large absorption occurs compared with the raw material epoxy monomer,presumably due to the large number of hydroxyl groups formed in the process.
Example 4
Preparation of OSPBB/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 in 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 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 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 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 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 7
75% OYMB/25% preparation of OSBBB/NED Polymer
Weighing resveratrol bio-based epoxy resin monomer (0.0395 g, prepared in example 1) shown in formula A and isovanillin bio-based epoxy resin monomer (0.1261 g, prepared in example 2) shown in formula B 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 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 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 8
75% OYMB/25% preparation of OSBBB/NNED polymer
Weighing in a reaction flaskResveratrol bio-based epoxy resin monomer (0.0395 g, prepared in example 1) shown in formula A and isovanillin bio-based epoxy resin monomer (0.1261 g, prepared in example 2) shown in formula B were added with curing agent D (0.1593 g) at 25 deg.C, heated to about 60 deg.C, the sample was in a molten state, stirred rapidly to keep the materials fully molten, and mixed uniformly. 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 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 9
Preparation of OYMB/NED Polymer
The isovanillin bio-based epoxy resin monomer (0.109 g, prepared in example 2) shown in formula B was weighed in a reaction flask, 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, and the mixture was stirred rapidly to keep the material sufficiently molten and mixed uniformly. 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 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 The irregular graphene structure D is located at 1356cm -1 As shown in fig. 9.
Example 10
Preparation of OYMB/NNED polymers
The isovanillin bio-based epoxy resin monomer (0.109 g, prepared in example 2) shown in formula B is weighed in a reaction bottle, curing agent D (0.1356 g) is metered in at 25 ℃, the temperature is raised to about 60 ℃, the sample is in a molten state, the mixture is rapidly stirred to keep the materials fully molten, and the materials are uniformly mixed. 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 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. 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 The irregular graphene structure D is located at 1356cm -1 As shown in fig. 10.
Example 11
25% OYMB/75% preparation of OSBBB/NED 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 C (0.1245 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 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 12
25% preparation of OYMB/75% OSBBB/NNED 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 D (0.1486 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 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.
TABLE 1 thermal stability and residual carbon content at 700 ℃ of Biobased epoxy resins
As can be seen from Table 1, adding OSBBB to the OYMB/NED system favors 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 by 50 percent of OSPBBBB in terms of thermal performance 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 the present embodiment can be realized 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;
wherein the curing agent is shown in a formula C and/or a 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 preparing bio-based carbon material.
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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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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 |
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