CN113816844A - Bio-based epoxy resin monomer and preparation method and application thereof - Google Patents
Bio-based epoxy resin monomer and preparation method and application thereof Download PDFInfo
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- CN113816844A CN113816844A CN202111186937.9A CN202111186937A CN113816844A CN 113816844 A CN113816844 A CN 113816844A CN 202111186937 A CN202111186937 A CN 202111186937A CN 113816844 A CN113816844 A CN 113816844A
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 91
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 91
- 239000000178 monomer Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 71
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 70
- 235000012141 vanillin Nutrition 0.000 claims description 70
- 239000004593 Epoxy Substances 0.000 claims description 46
- 229930185605 Bisphenol Natural products 0.000 claims description 36
- 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 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 8
- LUJMEECXHPYQOF-UHFFFAOYSA-N 3-hydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1 LUJMEECXHPYQOF-UHFFFAOYSA-N 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005882 aldol condensation reaction Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 230000005311 nuclear magnetism Effects 0.000 claims description 2
- BCGWQEUPMDMJNV-UHFFFAOYSA-N imipramine Chemical compound C1CC2=CC=CC=C2N(CCCN(C)C)C2=CC=CC=C21 BCGWQEUPMDMJNV-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 125000000468 ketone group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 33
- 239000012071 phase Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 150000002576 ketones Chemical group 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000013824 polyphenols Nutrition 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WLWIMKWZMGJRBS-UHFFFAOYSA-N Primin Natural products CCCCCC1=CC(=O)C=C(OC)C1=O WLWIMKWZMGJRBS-UHFFFAOYSA-N 0.000 description 3
- -1 carcinogenicity Chemical compound 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- XXPDBLUZJRXNNZ-UHFFFAOYSA-N promethazine hydrochloride Chemical compound Cl.C1=CC=C2N(CC(C)N(C)C)C3=CC=CC=C3SC2=C1 XXPDBLUZJRXNNZ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004402 polyphenol group Chemical group 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
-
- 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
- C08G59/40—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
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a bio-based epoxy resin monomer and a preparation method and application thereof, belonging to the field of high polymer materials. The invention also provides a bio-based epoxy resin material obtained by curing the bio-based epoxy resin monomer. The bio-based epoxy resin material prepared by the invention has the advantages of simple process, simple and convenient operation, easy implementation and the like, and can be prepared into different cross-linked epoxy resin materials by changing the equivalent weight of amine of a curing agent based on the special alpha, beta unsaturated ketone structure of a bio-based epoxy resin monomer.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an epoxy resin monomer based on vanillin, a preparation method thereof and application thereof in the field of epoxy resin preparation.
Background
Epoxy resin is a typical thermosetting resin, and is widely applied to the fields of coatings, adhesives, composite materials and the like due to excellent mechanical properties, good thermal stability and easy processability. Since the last 40 s, petroleum-based bisphenol a diglycidyl ether (DGEBA) has been the leading product of the epoxy industry, with usage levels exceeding 90%. The excessive use of fossil fuel reservoirs and the increase in greenhouse gas emissions pose serious environmental problems. Meanwhile, factors of DGEBA such as carcinogenicity, mutagenicity, reproductive toxicity and endocrine disturbance are attracting much attention. The development of a bio-based epoxy resin monomer and the application of the monomer in the epoxy resin industry are the key points of attention of researchers.
The bio-based epoxy resin monomer is obtained by synthesizing bio-based polyphenol by using bio-based phenol as a starting material, and glycidating the bio-based polyphenol, and the bio-based phenol developed at present mainly comprises guaiacol (eur. polym. j.2021,147,10), vanillin (ACS sustain. chem. eng.2021,9 (17)), 5768-5775 and the like. Patent No. CN202011561258.0 proposes bio-based bisphenol containing fluorene ring and guaiacol structure, and [ CN201911335986.7] proposes bio-based bisphenol containing guaiacol and [ CN202011152967.3] proposes bio-based bisphenol containing furan ring. Vanillin, also known as vanillin, is a compound containing both aldehyde groups and phenolic hydroxyl groups, and researchers have focused on the application of vanillin in the preparation of bio-based polyphenols due to its phenolic hydroxyl groups. However, vanillin has only one phenolic hydroxyl group, and is obtained by reacting vanillin as a raw material and other hydroxyl group-containing compounds for coupling (eur. polym. j.2020,140, 9). Although the above patents all report novel bio-based epoxy resin monomers, they are structurally simple, as in formula 1, essentially, a plurality of raw materials are synthesized into a bio-based phenol with polyphenol structure, and the middle part is changed, and this part does not affect the cross-linking structure of the epoxy resin.
Formula 1 reports biobased bisphenols and biobased epoxy resin monomers
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of bio-based bisphenol containing vanillin, an epoxy resin monomer and an epoxy resin with a brand new structure, which can be started from vanillin of biological sources, is cheap and easy to obtain, can reduce the potential toxicity of the vanillin, has a unique alpha and beta unsaturated ketone structure of the epoxy resin monomer, and can prepare the epoxy resin with a brand new cross-linked structure.
The invention provides a bio-based bisphenol containing vanillin, which has a structural formula
The invention provides a preparation method of bio-based bisphenol containing vanillin, which comprises the following steps:
is prepared by the aldol condensation reaction of vanillin and m-hydroxyacetophenone under the catalysis of acid or alkali. The alkali can be sodium hydroxide or potassium hydroxide, and the acid is concentrated sulfuric acid.
The reaction equation is as follows:
the invention provides an epoxy resin monomer containing vanillin, which has a structural formula
The invention provides a preparation method of a bio-based epoxy resin monomer containing vanillin, which comprises the following steps:
the bio-based bisphenol shown in the formula (I) is reacted with epichlorohydrin under the catalysis of alkali to generate the bio-based bisphenol. The base can be potassium carbonate, dimethylaminopyridine, tetrabutylammonium bromide and triethylamine.
The invention provides a preparation method of bio-based epoxy resin containing vanillin, which comprises the following steps:
the bio-based epoxy resin monomer shown in the formula (II) is mixed with amine according to a certain proportion and is heated and cured.
A novel bio-based bisphenol and epoxy resin monomer structure is provided, in which the epoxy at two ends can be crosslinked with amine, and the middle group can also be crosslinked with amine, so that multi-crosslinking epoxy resin is generated, which has not been reported at present. The two-component coupling reaction is to find that the aldehyde group in the vanillin is subjected to aldol condensation reaction with another methyl ketone to obtain the chalcone with an alpha, beta unsaturated ketone structure, as shown in a formula 2, while in the selection of the ketone, the ketone with a phenolic hydroxyl group can be selected, and the chalcone is synthesized and has a bisphenol structure. In the process of crosslinking the epoxy resin monomer with amine, the intermediate alpha and beta unsaturated ketone is also crosslinked to obtain a brand-new and multi-crosslinked epoxy resin structure.
Formula 2 designs a bio-based epoxy resin monomer with an alpha, beta unsaturated ketone structure to be crosslinked with amine
Therefore, in the invention, the bio-based bisphenol containing a vanillin structure is prepared by taking vanillin and hydroxyacetophenone as raw materials through aldol condensation, the bio-based epoxy resin monomer is prepared through the glycidation of the bisphenol, and the bio-based epoxy resin monomer is crosslinked with fatty acid amine to prepare the bio-based epoxy resin (formula 3).
The bio-based epoxy resin material comprises bio-based epoxy resin monomers containing vanillin, wherein the ratio of the epoxy value of the bio-based epoxy resin monomers containing vanillin to the amine value of the diamine primine 1074 is 1:0.5 to 1: 2;
y is the mass of added internal standard tetrachloroethane, and Z is the peak area ratio of tetrachloroethane characteristic peak to epoxy characteristic peak in nuclear magnetism.
Preferably, the ratio of the epoxy value of the vanillin-containing bio-based epoxy resin monomer to the amine value of the diamine primine 1074 is from 1:0.5 to 1: 2.
A bio-based bisphenol containing vanillin and a bio-based epoxy resin monomer containing vanillin are applied to adhesives and resins.
Advantageous effects
(1) According to the invention, vanillin which is of biological source is used as a raw material, so that the vanillin is cheap and easy to obtain, and the bio-based bisphenol with the structure of the formula I is prepared through a simple aldol condensation reaction.
(2) The epoxy resin monomer with the structure of formula II can be prepared by epoxidation reaction of bio-based bisphenol with the structure of formula I, and the epoxy resin monomer has an alpha and beta unsaturated ketone structure, can also be crosslinked with amine, and is a novel epoxy resin monomer structure.
(3) The bio-based epoxy resin material is obtained by crosslinking and curing a bio-based epoxy resin monomer with a structure of a formula II and fatty acid amine.
(4) The bio-based bisphenol with vanillin and the epoxy resin monomer have low toxicity and good biocompatibility.
(5) The method is simple, the bio-based bisphenol can be obtained by one-step reaction without a catalyst, the bio-based epoxy resin monomer can be obtained by one step, and the yield is high.
(6) The bio-based epoxy resin with different cross-linking structures can be prepared by changing the ratio of epoxy to amine for the first time.
Compared with the existing epoxy resin material, the epoxy resin material has the characteristics of greenness, no toxicity, good biocompatibility, novel structure, simple synthesis process, high yield and the like.
Drawings
Embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which
FIG. 1: method for producing bio-based bisphenols containing vanillin1H NMR chart
FIG. 2: method for producing bio-based bisphenols containing vanillin13C NMR chart
FIG. 3: method for preparing bio-based epoxy resin monomer containing vanillin1H NMR chart
FIG. 4: FTIR patterns of bio-based epoxy monomers containing vanillin
FIG. 5: epoxy value measurement of epoxy resin monomer in example 81H NMR chart
FIG. 6: FTIR chart of epoxy resin (epoxy: amine ═ 1:1) corresponding to epoxy resin monomer in example 9
FIG. 7: FTIR chart of epoxy resin corresponding to epoxy resin monomer in example 10 (epoxy: amine ═ 1:1.5)
FIG. 8: FTIR chart of epoxy resin (epoxy: amine ═ 1:2) corresponding to epoxy resin monomer in example 11
FIG. 9 shows the IR spectra (900 cm) of bio-based epoxy resin monomer and epoxy resin-1)
FIG. 1 shows a schematic view of a0 infrared spectrum (1650 cm) of bio-based epoxy resin monomer and epoxy resin-1)
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit and scope of the present invention.
The NMR spectra referred to in the examples were determined using a NMR spectrometer model Bruker Ascend TM-400 from Bruker, Inc. (Bruker), using deuterated chloroform (CDCl)3) And deuterated dimethyl sulfoxide (DMSO-d)6)。
The raw materials used in the following examples were all purchased from shanghai sahn chemical co.
The structural formula of the bio-based bisphenol containing vanillin in the invention is
The preparation method of the bio-based bisphenol containing vanillin comprises the following steps:
base catalysis: adding vanillin and m-hydroxyacetophenone into absolute ethanol at room temperature, stirring and mixing until dissolving, and then slowly dripping alkaline water solution under ice bath condition. And after the dropwise addition is finished, placing the reaction solution in an oil bath kettle at 50 ℃ for reaction for 12h, cooling to room temperature, adding dilute hydrochloric acid for acidification until the pH value is approximately equal to 2, extracting with ethyl acetate, drying, and purifying through a silica gel column to obtain yellow powder, namely the bio-based bisphenol containing vanillin.
The reaction equation is:
acid catalysis: under the ice-bath condition, vanillin and m-hydroxyacetophenone are added into absolute ethyl alcohol, stirred and mixed until dissolved, and concentrated sulfuric acid is slowly dropped under the ice-bath condition. And after the dropwise addition is finished, placing the reaction solution in a 60 ℃ oil bath kettle for reaction for 10 hours, pouring the reaction solution into a large amount of ice water, extracting with ethyl acetate, washing with a large amount of deionized water, drying, and purifying by a silica gel column to obtain yellow powder, namely the bio-based bisphenol containing vanillin.
The reaction equation is:
the structural formula of the bio-based epoxy resin monomer containing vanillin in the invention is
The preparation method of the bio-based epoxy resin monomer containing vanillin comprises the following steps:
dissolving bio-based bisphenol containing vanillin in epichlorohydrin at room temperature, adding tetrabutylammonium bromide as a catalyst, reacting at 80 ℃ for 2h, cooling to room temperature, slowly dropwise adding a sodium hydroxide (40% wt.) aqueous solution, stirring at room temperature for 3h, extracting with ethyl acetate, washing with saturated salt water, drying, and spin-drying to obtain yellow powder, namely the bio-based epoxy resin monomer containing vanillin.
The reaction equation is:
in the following examples, various procedures and methods not described in detail are conventional methods well known in the art, and materials, reagents, devices, instruments, equipment and the like used in the following examples are commercially available unless otherwise specified.
Example 1:
in a 250mL reaction flask, vanillin (6.6g, 43) was added under room temperature conditions.2mmol,1.02eq.), m-hydroxyacetophenone (5.8g,42.4mmol,1.00eq.) was added to 100mL of absolute ethanol and mixed with stirring until dissolved. The reaction flask was then placed in an ice bath and 62.5mL of aqueous sodium hydroxide (16% wt.) solution was slowly added dropwise, the reaction turned from a pale pink to yellow with a small amount of white solid precipitating out. After the dropwise addition, the reaction solution is placed in an oil bath kettle at 50 ℃ for reaction for 12 hours, and the color of the reaction solution is changed from yellow to red and black. The reaction solution is cooled to 0 ℃, diluted hydrochloric acid is added to acidify until the pH value is approximately equal to 2, and the reaction solution changes from red black to yellow. The acidified reaction solution was extracted three times with 100mL of ethyl acetate and dried. The crude product was purified by silica gel column, petroleum ether/ethyl acetate 5: 1, then rinsing the product with pure ethyl acetate, and removing the solvent to obtain the vanillin-containing bio-based bisphenol as a yellowish solid with a yield of 52%.1H NMR(400MHz,DMSO-d6)δ9.78(s,1H),9.69(s,1H),7.72–7.57(m,3H),7.50(d,J＝2.0Hz,1H),7.47–7.43(m,3H),7.36(t,J＝7.9Hz,1H),7.26(dd,J＝8.2,2.0Hz,1H),7.04(ddd,J＝8.1,2.6,0.9Hz,1H),6.83(d,J＝8.1Hz,1H),3.87(s,3H).
Example 2:
in a 250mL reaction flask, vanillin (6.6g,43.2mmol,1.02eq.) and m-hydroxyacetophenone (5.8g,42.4mmol,1.00eq.) were added to 100mL absolute ethanol at room temperature and mixed with stirring until dissolved. The reaction flask was then placed in an ice bath and 62.5mL of aqueous potassium hydroxide (16% wt.) solution was slowly added dropwise, the reaction turned from a pale pink to yellow with a small amount of white solid precipitating out. After the dropwise addition, the reaction solution is placed in an oil bath kettle at 50 ℃ for reaction for 12 hours, and the color of the reaction solution is changed from yellow to red and black. The reaction solution is cooled to 0 ℃, diluted hydrochloric acid is added to acidify until the pH value is approximately equal to 2, and the reaction solution changes from red black to yellow. The acidified reaction solution was extracted three times with 100mL of ethyl acetate and dried. The crude product was purified by silica gel column, petroleum ether/ethyl acetate 5: 1, then rinsing the product with pure ethyl acetate, and removing the solvent to obtain the vanillin-containing bio-based bisphenol as a yellowish solid with a yield of 61%.1H NMR(400MHz,DMSO-d6)δ9.78(s,1H),9.69(s,1H),7.72–7.57(m,3H),7.50(d,J＝2.0Hz,1H),7.47–7.43(m,3H),7.36(t,J＝7.9Hz,1H),7.26(dd,J＝8.2,2.0Hz,1H),7.04(ddd,J＝8.1,2.6,0.9Hz,1H),6.83(d,J＝8.1Hz,1H),3.87(s,3H).
Example 3:
in a 250mL reaction flask, vanillin (13.2g,43.2mmol,1.02eq.) and m-hydroxyacetophenone (5.8g,42.4mmol,1.00eq.) were added to 40mL absolute ethanol at room temperature and mixed with stirring until dissolved. And then placing the reaction bottle in an ice bath, slowly dropwise adding 1.1mL of concentrated sulfuric acid, immediately changing the reaction liquid from colorless to red, gradually deepening the red to reddish black along with the dropwise addition of the sulfuric acid, and after the dropwise addition is finished, placing the reaction liquid in an oil bath kettle at 60 ℃ for reaction for 10 hours. The reaction solution was poured into 120mL of ice water, extracted with ethyl acetate, the organic phase was washed three times with water, dried and the crude product was purified by column chromatography, petroleum ether/ethyl acetate 5: 1, then washing the starting material with petroleum ether/ethyl acetate ═ 2: 1 flushing out the product, removing the solvent to obtain the bio-based bisphenol containing vanillin as a yellowish solid with a yield of 82%.1H NMR(400MHz,DMSO-d6)δ9.78(s,1H),9.69(s,1H),7.72–7.57(m,3H),7.50(d,J＝2.0Hz,1H),7.47–7.43(m,3H),7.36(t,J＝7.9Hz,1H),7.26(dd,J＝8.2,2.0Hz,1H),7.04(ddd,J＝8.1,2.6,0.9Hz,1H),6.83(d,J＝8.1Hz,1H),3.87(s,3H).
Example 4:
at room temperature, vanillin-containing bio-based bisphenol (1.62g,6mmol,1.0eq.) was dissolved in epichlorohydrin (12.71mL,159.6mmol,26.6eq.) to form a pale yellow reaction solution, tetrabutylammonium bromide (0.156g,0.51mmol,0.085eq.) was added as a catalyst, at which time the reaction solution changed from pale yellow to reddish black, and the reaction was carried out at 80 ℃ for 2 hours until the reaction solution changed from reddish black to yellow. The reaction solution was cooled to room temperature, and aqueous sodium hydroxide (40% wt.) (2.16mL) was slowly added dropwise, stirred at room temperature for 3 hours, extracted with 25mL ethyl acetate 3 times, washed with saturated brine, dried, and the solvent was removed under reduced pressure to give a vanillin-containing bio-based epoxy resin monomer as a yellow powder with a yield of 95%.1H NMR(400MHz,Chloroform-d)δ7.75(d,J＝15.6Hz,1H),7.61(d,J＝7.6Hz,1H),7.55(t,J＝2.1Hz,1H),7.45–7.33(m,2H),7.21(dd,J＝8.3,2.0Hz,1H),7.18–7.12(m,2H),6.95(d,J＝8.3Hz,1H),4.34(ddd,J＝11.7,8.7,3.1Hz,2H),4.19–3.96(m,2H),3.94(s,3H),3.40(ddt,J＝9.0,6.1,2.9Hz,2H),2.93(q,J＝4.1Hz,2H),2.78(ddd,J＝7.6,4.9,2.7Hz,2H).
Example 5:
at room temperature, vanillin-containing bio-based bisphenol (1.62g,6mmol,1.0eq.) was dissolved in epichlorohydrin (12.71mL,159.6mmol,26.6eq.) to form a light yellow reaction solution, potassium carbonate (0.071g,0.51mmol,0.085eq.) was added as a catalyst, at which time the reaction solution changed from light yellow to red-black, and the reaction was carried out at 80 ℃ for 2 hours until the reaction solution changed from red-black to yellow. The reaction solution was cooled to room temperature, and aqueous sodium hydroxide (40% wt.) (2.16mL) was slowly added dropwise, stirred at room temperature for 3h, extracted with 25mL ethyl acetate 3 times, washed with saturated brine, dried, and the solvent was removed under reduced pressure to give a vanillin-containing bio-based epoxy resin monomer as a yellow powder with a yield of 92%.1H NMR(400MHz,Chloroform-d)δ7.75(d,J＝15.6Hz,1H),7.61(d,J＝7.6Hz,1H),7.55(t,J＝2.1Hz,1H),7.45–7.33(m,2H),7.21(dd,J＝8.3,2.0Hz,1H),7.18–7.12(m,2H),6.95(d,J＝8.3Hz,1H),4.34(ddd,J＝11.7,8.7,3.1Hz,2H),4.19–3.96(m,2H),3.94(s,3H),3.40(ddt,J＝9.0,6.1,2.9Hz,2H),2.93(q,J＝4.1Hz,2H),2.78(ddd,J＝7.6,4.9,2.7Hz,2H).
Example 6:
at room temperature, vanillin-containing bio-based bisphenol (1.62g,6mmol,1.0eq.) was dissolved in epichlorohydrin (12.71mL,159.6mmol,26.6eq.) to form a light yellow reaction solution, dimethylaminopyridine (0.062g,0.51mmol,0.085eq.) was added as a catalyst, whereupon the reaction solution changed from light yellow to red-black, and the reaction was carried out at 80 ℃ for 2 hours until the reaction solution changed from red-black to yellow. The reaction solution was cooled to room temperature, and aqueous sodium hydroxide (40% wt.) (2.16mL) was slowly added dropwise, stirred at room temperature for 3h, extracted with 25mL ethyl acetate 3 times, washed with saturated brine, dried, and the solvent was removed under reduced pressure to give a vanillin-containing bio-based epoxy resin monomer as a yellow powder with a yield of 93%.1H NMR(400MHz,Chloroform-d)δ7.75(d,J＝15.6Hz,1H),7.61(d,J＝7.6Hz,1H),7.55(t,J＝2.1Hz,1H),7.45–7.33(m,2H),7.21(dd,J＝8.3,2.0Hz,1H),7.18–7.12(m,2H),6.95(d,J＝8.3Hz,1H),4.34(ddd,J＝11.7,8.7,3.1Hz,2H),4.19–3.96(m,2H),3.94(s,3H),3.40(ddt,J＝9.0,6.1,2.9Hz,2H),2.93(q,J＝4.1Hz,2H),2.78(ddd,J＝7.6,4.9,2.7Hz,2H).
Example 7:
at room temperature, vanillin-containing bio-based bisphenol (1.62g,6mmol,1.0eq.) was dissolved in epichlorohydrin (12.71mL,159.6mmol,26.6eq.) to form a light yellow reaction solution, triethylamine (0.071mL,0.51mmol,0.085eq.) was added as a catalyst, at which time the reaction solution changed from light yellow to red-black, and the reaction was carried out at 80 ℃ for 2 hours until the reaction solution changed from red-black to yellow. The reaction solution was cooled to room temperature, and aqueous sodium hydroxide (40% wt.) (2.16mL) was slowly added dropwise, stirred at room temperature for 3h, extracted with 25mL ethyl acetate 3 times, washed with saturated brine, dried, and the solvent was removed under reduced pressure to give a vanillin-containing bio-based epoxy resin monomer as a yellow powder with a yield of 82%.1H NMR(400MHz,Chloroform-d)δ7.75(d,J＝15.6Hz,1H),7.61(d,J＝7.6Hz,1H),7.55(t,J＝2.1Hz,1H),7.45–7.33(m,2H),7.21(dd,J＝8.3,2.0Hz,1H),7.18–7.12(m,2H),6.95(d,J＝8.3Hz,1H),4.34(ddd,J＝11.7,8.7,3.1Hz,2H),4.19–3.96(m,2H),3.94(s,3H),3.40(ddt,J＝9.0,6.1,2.9Hz,2H),2.93(q,J＝4.1Hz,2H),2.78(ddd,J＝7.6,4.9,2.7Hz,2H).
Example 8:
to be provided with1The method is characterized in that the absolute epoxy value of the bio-based epoxy resin monomer is determined by adding internal standard tetrachloroethane. The epoxy resin monomer X g (X ═ 0.0213) obtained in example 4 was weighed first, and internal tetrachloroethane Y g (Y ═ 0.0233) was weighed and combined, and then 0.6mL of deuterated chloroform was added and dissolved. As shown in fig. 5, the characteristic peak of tetrachloroethane is 6.0ppm, the characteristic peak of epoxy is 3.0ppm, there are three peaks, and the peak area ratio is Z (Z ═ 2.76) according to the characteristic peak of tetrachloroethane and one of the epoxy, then the epoxy value of X g of the bio-based epoxy resin monomer can be determined by the following formula:
according to the nuclear magnetic internal standard method, the formula is as follows, wherein Y is the mass of the added internal standard tetrachloroethane, and Z is the peak area ratio of the tetrachloroethane characteristic peak to the epoxy characteristic peak in nuclear magnetic, 0.213g of bio-based epoxy resin monomer (example 4) contains 0.95mmol of epoxy, so 0.224g of bio-based epoxy resin monomer contains 1.0mmol of epoxy.
According to the information of the purchase (brand name COROA), the following are indicated: since 1g of the dimeric amine Priamine 1074 contained 3.7mmol of amine in terms of amine number, 0.27g of the dimeric amine Priamine 1074 contained 1mmol of amine.
Example 9:
vacuumizing and stirring 0.224g of bio-based epoxy resin monomer at 100 ℃ for degassing for 0.5h, then adding 0.27g of diamine Priamine 1074 (epoxy: amine is 1:1), continuously vacuumizing at 100 ℃ until the mixture is uniformly mixed into a homogeneous phase, immediately pouring the homogeneous phase into a mold while the homogeneous phase is hot, heating and curing the homogeneous phase in an oven at 120 ℃ for 24h, and taking out the bio-based epoxy resin material (1:1) containing vanillin after the mold is cooled to room temperature. The structure is characterized by infrared, as shown in fig. 6.
Example 10:
0.224g of bio-based epoxy resin monomer is vacuumized, stirred and degassed at 100 ℃ for 0.5h, then 0.405g of diamine primine 1074 is added (epoxy: amine is 1:1.5), the mixture is continuously vacuumized at 100 ℃ until the mixture is uniformly mixed into a homogeneous phase, the homogeneous phase is immediately poured into a mold while the mixture is hot, the mixture is heated and cured in an oven at 120 ℃ for 24h, and the bio-based epoxy resin material (1:1.5) containing vanillin is taken out after the mold is cooled to room temperature. The structure is characterized by infrared, as shown in fig. 7.
Example 11:
vacuumizing and stirring 0.224g of bio-based epoxy resin monomer at 100 ℃ for degassing for 0.5h, then adding 0.54g of diamine Priamine 1074 (epoxy: amine is 1:2), continuously vacuumizing at 100 ℃ until the mixture is uniformly mixed into a homogeneous phase, immediately pouring the homogeneous phase into a mold while the homogeneous phase is hot, heating and curing the homogeneous phase in an oven at 120 ℃ for 24h, and taking out the bio-based epoxy resin material (1:2) containing vanillin after the mold is cooled to room temperature. The structure is characterized by infrared, as shown in fig. 8.
Example 12:
epoxy adhesive applications. Vacuumizing and stirring 0.224g of bio-based epoxy resin monomer at 100 ℃ for degassing for 0.5h, then adding 0.27g of diamine Priamine 1074 (epoxy: amine is 1:1), continuously vacuumizing at 100 ℃ until the mixture is uniformly mixed into a homogeneous phase, immediately coating the homogeneous phase on a metal block while hot, sticking the metal block on another metal block after the homogeneous coating, pressing the metal block to be stuck, putting the metal block into a 120 ℃ oven for curing for 24h, taking out the metal block, and cooling the metal block to room temperature to obtain the completely stuck metal block. According to the infrared spectrum of fig. 9, the peak of epoxy is about 900. In FIG. 9 the first line is bio-based epoxy monomer, the second line is epoxy (1:1), the third line is epoxy (1:1.5), and the fourth line is epoxy (1: 2). Referring to fig. 9, the top mcha is the infrared spectrum of the bio-based epoxy resin monomer, and has a distinct peak around 900, which is an epoxy group. The second is epoxy with amine 1:1, the disappearance of the epoxy peak proves that the epoxy and the amine react completely, and the third and fourth are respectively 1:1.5 and 1:2, and an infrared spectrum of the epoxy resin of 1:1.5 and 1: no epoxy peak was found in the epoxy resin of 2, confirming complete crosslinking of the epoxy with the amine.
In addition, according to FIG. 10, the first line is bio-based epoxy monomer, the second line is epoxy (1:1), the third line is epoxy (1:1.5), and the fourth line is epoxy (1: 2). 1650 or so is the carbonyl peak of the unsaturated ketone, the strong absorption peak clearly seen in the bio-based epoxy resin monomer, whereas in epoxy: amine 1:1 and 1: the peak of carbonyl absorption was still observed at 1.5, which is shown to be in the range of 1: at 1.5 the amine has not reacted with the carbonyl group but preferentially with the double bond of the unsaturated ketone, which follows the 1, 4-addition mechanism. The double bond peak is blocked from visual observation by the peak of the benzene ring around 1600. In the presence of an epoxy: amine 1: the carbonyl peak disappears at 2, and a weak peak appears around 1630 to the right of the original carbonyl peak, which is a peak of C ═ N, thus proving that the carbonyl reacts with amine to form imine. In summary, 1: 1-time amine cross-linking with epoxy, 1:1.5, 1, 4-addition, 1:2, reacting with carbonyl to form imine, and performing infrared characterization on a brand new crosslinking structure to prove the preparation of the novel epoxy resin.
Claims (9)
1. A vanillin-containing bio-based bisphenol characterized by the structural formula:
2. a method of producing a vanillin-containing bio-based bisphenol of claim 1,
is prepared by the aldol condensation reaction of vanillin and m-hydroxyacetophenone under the catalysis of acid or alkali.
3. The method according to claim 2, wherein the alkali is sodium hydroxide or potassium hydroxide, and the acid is concentrated sulfuric acid.
4. A bio-based epoxy resin monomer containing vanillin is characterized in that the structural formula is
5. The preparation method of the vanillin-containing bio-based epoxy resin monomer as claimed in claim 4, wherein the vanillin-containing bio-based epoxy resin monomer is prepared by reacting the bio-based bisphenol represented by the formula (I) with epichlorohydrin under the catalysis of alkali.
6. The method according to claim 5, wherein the base is selected from the group consisting of potassium carbonate, dimethylaminopyridine, tetrabutylammonium bromide and triethylamine.
7. A bio-based epoxy resin material comprising the bio-based epoxy resin monomer containing vanillin of claim 4, characterized in that: the ratio of epoxy value of the vanillin-containing bio-based epoxy resin monomer to amine value of the diamine pramine 1074 of claim 5 or 6 is from 1:0.5 to 1: 2;
y is the mass of added internal standard tetrachloroethane, and Z is the peak area ratio of tetrachloroethane characteristic peak to epoxy characteristic peak in nuclear magnetism.
8. The bio-based epoxy material of a bio-based epoxy monomer containing vanillin of claim 7, wherein: the ratio of epoxy value of the vanillin-containing bio-based epoxy resin monomer to amine value of the diamine pramine 1074 of claim 5 or 6 is 1:1 or 1:1.5 or 1: 2.
9. A bio-based bisphenol containing vanillin and a bio-based epoxy resin monomer containing vanillin are applied to adhesives and resins.
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| CN114853587A (en) * | 2022-04-25 | 2022-08-05 | 南京工业大学 | Bio-based bisphenol, bio-based epoxy resin monomer and preparation method of resin thereof |
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| WO2023136620A1 (en) * | 2022-01-12 | 2023-07-20 | 건국대학교 산학협력단 | Chemically degradable epoxy compound, method for preparing same, epoxy composite material comprising same, and decomposition method thereof |
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Application publication date: 20211221 |