CN116789618A - Biomass epoxy monomer, biomass self-repairing epoxy resin and preparation method - Google Patents
Biomass epoxy monomer, biomass self-repairing epoxy resin and preparation method Download PDFInfo
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- CN116789618A CN116789618A CN202310601640.7A CN202310601640A CN116789618A CN 116789618 A CN116789618 A CN 116789618A CN 202310601640 A CN202310601640 A CN 202310601640A CN 116789618 A CN116789618 A CN 116789618A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 128
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 90
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 90
- 239000004593 Epoxy Substances 0.000 title claims abstract description 57
- 239000000178 monomer Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 66
- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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 claims abstract description 31
- 229940016667 resveratrol Drugs 0.000 claims abstract description 31
- 235000021283 resveratrol Nutrition 0.000 claims abstract description 31
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 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 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
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- 238000001816 cooling Methods 0.000 description 21
- 238000010992 reflux Methods 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000007711 solidification Methods 0.000 description 11
- 230000008023 solidification Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 150000007529 inorganic bases Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
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- 239000003208 petroleum Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 2
- JHYKJJIJPWNOME-UHFFFAOYSA-N 1,4a,8-triazido-2,3,4,5,6,7-hexahydro-1H-naphthalene Chemical compound N(=[N+]=[N-])C12CCCC(=C2C(CCC1)N=[N+]=[N-])N=[N+]=[N-] JHYKJJIJPWNOME-UHFFFAOYSA-N 0.000 description 1
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses a biomass epoxy monomer, biomass self-repairing epoxy resin and a preparation method thereof, wherein biomass resveratrol and epichlorohydrin are used as raw materials, and the biomass epoxy monomer is prepared by heating reaction; and (3) solidifying the biomass epoxy monomer by citric acid to obtain the full bio-based epoxy resin. Compared with the prior art, the epoxy resin provided by the invention can be self-repaired efficiently under the condition of no catalyst, and has excellent thermal performance, high flexural modulus and strength and high tensile strength.
Description
Technical Field
The invention relates to a biomass epoxy monomer, biomass self-repairing epoxy resin and a preparation method thereof, belonging to the technical field of functional polymer materials.
Background
Epoxy resin is a thermosetting resin with the largest demand and excellent comprehensive performance, has good heat resistance, chemical resistance, mechanical property, cohesiveness, dimensional stability and electrical insulation, and is widely applied to the fields of electronics and electricity, aerospace, new energy, civil construction and the like as a coating, adhesive and high-performance composite resin matrix. However, more than 90% of the epoxy resins currently in commercial use are bisphenol a type epoxy resins, which are produced from non-renewable petroleum resources, and BPA is considered to be an endocrine disruptor and a toxic substance, and thus are prohibited by many countries for use in food packaging. The epoxy resin inevitably receives physical effects such as collision, scraping and the like in the use process, microcracks are generated inside the epoxy resin and spread to the surface to generate cracks, so that the service life of the epoxy resin is shortened, and the mechanical property of the epoxy resin is reduced. In recent years, researchers have proposed epoxy resin glass polymer materials based on reversible covalent bonds such as dynamic transesterification, disulfide interchange, siloxane interchange, hindered urea bonds, dynamic imine bonds, and the like, which provide possibilities for reprocessing and self-repairing of epoxy resins. In general, these epoxy resin glass polymers require the addition of catalysts such as zinc acetylacetonate, 1,5, 7-triazido bicyclo (4.4.0) dec-5-ene (TBD), and the like, which have certain toxicity, are expensive, have poor thermal stability, and have the problem of failure.
According to the research combined with the domestic and foreign high-performance bio-based epoxy resin, the vegetable oil-based epoxy resin has low epoxy group reactivity due to longer molecular flexible chain segments, and finally results in low crosslinking density and low heat resistance of the cured product. The lignin-derived epoxy resin has rigid groups such as benzene rings in a network structure, so that the thermal performance of the lignin-based epoxy resin can be effectively improved, but the self-repairing performance of the lignin-based epoxy resin is poor. Therefore, the current bio-based self-repairing epoxy resin cannot have high heat resistance, high mechanical property and good self-repairing property.
In view of the above, there is still a challenge to develop a biomass-based catalyst-free self-repairing epoxy resin with high heat resistance and high mechanical strength.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the biomass self-repairing epoxy resin with high heat resistance and high mechanical strength and the preparation method thereof, and the epoxy resin disclosed by the invention can realize the self-repairing efficiency of more than 80% under the condition that a catalyst or an additive is not needed besides excellent heat resistance and mechanical properties, which is unexpected in the prior art, and effectively solves the problem that the existing self-repairing epoxy resin needs a catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the biomass epoxy monomer comprises the following steps: and heating resveratrol and epichlorohydrin to react to prepare the biomass epoxy monomer.
In the invention, the mol ratio of resveratrol to epichlorohydrin is 1: (10-20), preferably 1:20.
In the invention, the heating reaction is carried out in an alcohol solvent in the presence of inorganic base, and preferably, the alcohol solvent is ethanol; preferably, the ratio of the inorganic base to the alcohol solvent is 1 g:10-16 mL, preferably 1 g:12-14 mL. The mol ratio of resveratrol to inorganic base is 1:3-3.3; preferably, the inorganic base is sodium hydroxide; the dosage of the inorganic base is 1.1 times of the molar quantity of phenolic hydroxyl groups in resveratrol.
In the invention, resveratrol and epichlorohydrin are mixed, then inorganic alkali alcohol solution is dripped, and the biomass epoxy monomer is prepared by heating reaction; the dropping time of the sodium hydroxide alcohol solution is 0.5-2 h, preferably 1-1.5 h.
In the invention, the temperature of the heating reaction is 80-100 ℃, the time is 3-6 h, and the preferable temperature of the heating reaction is 80-90 ℃ and the time is 4-5 h.
The preparation method of the biomass self-repairing epoxy resin comprises the following steps: and the biomass epoxy monomer reacts with a biomass curing agent to obtain the biomass self-repairing epoxy resin.
In the present invention, the biomass curing agent is a biomass acid such as citric acid; preferably, the citric acid is dissolved in the solvent in advance and then mixed with the biomass epoxy monomer; preferably, the solvent is tetrahydrofuran.
In the invention, the biomass epoxy monomer and citric acid are prepolymerized at 80-100 ℃, and the prepolymer is solidified after degassing and soaking; the curing temperature is 110-150 ℃ and the curing time is 5-16 h. Preferably, the solidification is a step heating mode, the heat preservation time at each step temperature is not less than 1h, and the temperature difference between adjacent steps is not more than 30 ℃.
In the invention, the mol ratio of the biomass epoxy monomer to the biomass curing agent is 1: (0.5-1.5), preferably 1: (0.5-1).
The invention discloses application of biomass epoxy monomer or biomass self-repairing epoxy resin in preparation of an epoxy resin material. Compared with the prior art, the epoxy resin provided by the invention can be efficiently self-repaired under the condition of no catalyst or no additive, and has excellent thermal performance, high flexural modulus and strength and high tensile strength.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention synthesizes epoxy monomer by taking biomass resveratrol and epichlorohydrin as raw materials.
2. The biomass self-repairing epoxy resin prepared by the invention has outstanding heat resistance and glass transition temperature (T) g ) It also has a high flexural modulus (2.40 GPa) and strength (123.5 MPa) at 129 ℃, while it also has a high tensile strength (74.6 MPa) with a self-healing efficiency of 82.1%, thus providing a reliable basis for its application in the tip field.
Drawings
FIG. 1 is a schematic illustration of the synthesis of biomass epoxy monomers, the curing reaction and chemical structural formula of a biomass self-healing epoxy resin of the present invention;
FIG. 2 shows nuclear magnetic resonance hydrogen spectrum of biomass epoxy monomer of the present invention 1 H NMR）；
FIG. 3 shows nuclear magnetic resonance hydrogen spectrum of biomass epoxy monomer of the present invention 13 C-NMR）；
Fig. 4 is a high resolution mass spectrum of the biomass epoxy monomer of the present invention (key peaks:397.1653[M+H + ]，419.1472[M+Na + ]）；
FIG. 5 is a thermal weight loss (TGA) curve of a biomass self-healing epoxy resin of the present invention, 10 ℃/min, nitrogen;
FIG. 6 is a dynamic thermo-mechanical analysis (DMA) curve of the biomass self-healing epoxy resin of the present invention, 3 ℃/min;
FIG. 7 is a bending stress-strain curve of a biomass self-healing epoxy resin of the present invention;
FIG. 8 is a tensile stress-strain curve of the biomass self-healing epoxy resin of the present invention before and after self-healing;
fig. 9 is an electronic image of scratch repair of the biomass self-repairing epoxy resin of the present invention.
Detailed Description
The preparation process of the biomass self-repairing epoxy resin disclosed by the invention is shown in fig. 1, and specifically comprises the following steps:
(1) Heating resveratrol and epichlorohydrin to react to prepare a biomass epoxy monomer;
(2) Solidifying the biomass epoxy monomer by citric acid to obtain biomass self-repairing epoxy resin; curing does not need to add any catalyst, accelerator and the like.
Specifically, the biomass self-repairing epoxy resin disclosed by the invention is prepared as follows:
(1) Mixing resveratrol and epichlorohydrin according to mole parts, then dropwise adding sodium hydroxide alcohol solution into the mixture, reacting for 3-6 hours at 80-100 ℃, naturally cooling to room temperature, filtering, then mixing filtrate with dichloromethane, washing with deionized water for times, rotary evaporating to remove solvent, and vacuum drying to obtain biomass epoxy monomer;
(2) According to parts by weight, dissolving citric acid in tetrahydrofuran, prepolymerizing biomass epoxy monomer and citric acid, and solidifying the prepolymer after degassing and soaking to obtain biomass self-repairing epoxy resin; no other raw materials or reagents need to be added in this step.
The biomass epoxy monomer is prepared by heating resveratrol and epichlorohydrin for reaction; then, solidifying the biomass epoxy monomer by citric acid to obtain biomass self-repairing epoxy resin; curing does not need to add any catalyst or accelerator. The technical scheme of the invention is further described below with reference to the accompanying drawings and the examples; all raw materials are commercially available, and the specific preparation operation and the testing method involved are conventional methods in the field, and the mechanical properties are tested by adopting a universal tester.
Example 1
(1) Preparation of biomass epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask provided with a reflux condenser pipe and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent of each mole of phenolic hydroxyl group) is added dropwise at 90 ℃ for 1h, then reflux reaction is carried out at 90 ℃ for 5h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted by methylene dichloride, the organic phase is washed 3 times by deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange oil, biomass epoxy monomer with 92 yield; FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum [ ] 1 H NMR); FIG. 3 shows the nuclear magnetic resonance hydrogen spectrum [ ] 13 C-NMR); fig. 4 is a high resolution mass spectrum thereof.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, poured into a beaker containing 10g of biomass epoxy monomer (the molar ratio of the biomass epoxy monomer to the citric acid is 1:0.8), pre-polymerized for 2 hours at 90 ℃, then defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling to room temperature to obtain the biomass self-repairing epoxy resin, wherein electronic images of a thermal weight loss curve, a dynamic thermal mechanical analysis (DMA) curve, a bending stress-strain curve, a tensile stress-strain curve and scratch repairing are respectively shown in fig. 5, 6, 7, 8 and 9.
The prepared bar was scratched (depth 66.45 μm) using a surgical knife, then placed in an oven at 180 ℃ for heat treatment for 10 minutes without applied pressure, and the repair of the scratch was photographed with a super depth microscope. Self-repair efficiency= (scratch initial width-scratch width after repair)/scratch initial width 100%.
It can be seen that the glass transition temperature (T g ) At 129 ℃, T d5% Is 285 ℃. Furthermore, the flexural modulus, flexural strength and tensile strength of the biomass self-repairing epoxy resin at normal temperature are respectively 2.40GPa, 123.5MPa and 74.3MPa, the biomass self-repairing epoxy resin has outstanding mechanical properties, meanwhile, the biomass self-repairing epoxy resin has good self-repairing performance, the scratch self-repairing efficiency is 82.1%, and the tensile strength can reach 81.9% of an original sample.
With reference to the method, two groups of bio-based self-repairing epoxy resins are prepared according to the molar ratio of the biomass epoxy monomer to the citric acid of 1:1 and 1:0.6, wherein the glass transition temperature of the epoxy resin prepared according to the molar ratio of 1:1 is 104 ℃, the tensile strength is 58.8MPa, and the scratch self-repairing efficiency is 88.0%; the glass transition temperature of the epoxy resin prepared in the molar ratio of 1:0.6 is 146 ℃, the tensile strength is 52.8MPa, and the scratch self-repairing efficiency is 74.2%.
The prior literature reports that the full-bio-based self-repairing epoxy resin is prepared by taking biomass sulfate lignin and sebacic acid as raw materials and zinc acetylacetonate as a catalyst, wherein the tensile strength of Se-EP/Oz-L is 9.8MPa, the initial thermal decomposition temperature is 222 ℃, and the self-repairing efficiency is 77.4%.
The prior literature reports the preparation of bio-based self-healing epoxy resins starting from biomass rosin, fumaric acid and petroleum based 2,2- (1, 4-phenyl) -bis (4-mercapto-1, 3, 2-dioxaborane) (BDB) with a 20% C-FPAE tensile strength of 39.5MPa.
The prior literature reports that biomass menthane diamine is used as a raw material, a bio-based epoxy resin is prepared through one-step reaction, and adipic acid is used as a curing agent to prepare the full bio-based self-repairing epoxy resin, and EMDA-AA 1.0 Has a glass transition temperature of 72 ℃ (T) g DMA), the tensile strength was 57.4MPa.
The prior literature reports that biomass menthane diamine and tung oil-based triglycidyl ester are taken as raw materials to prepare the holotogenic productSelf-repairing epoxy resin based on matter, TOTGE-MDA 1.0 Has a glass transition temperature of 83 ℃ (T) g DMA), the tensile strength was 57.6MPa.
The prior art discloses a self-repairing epoxy resin prepared from N, N' -bis (tert-butyl) ethylenediamine, bisphenol A glycidyl ether type epoxy resin and hexamethylene diisocyanate, wherein the tensile strength is 22MPa, and the mechanical damage repairing efficiency is about 73%.
Compared with the prior art, the biomass self-repairing epoxy resin prepared by the invention has excellent heat resistance, outstanding mechanical properties and good self-repairing performance.
Example 2
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 60.802g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent per mol of phenolic hydroxyl group) is added dropwise at 90 ℃ for 1h, then reflux reaction is carried out at 90 ℃ for 5h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 3
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent per mol of phenolic hydroxyl group) is added dropwise at 100 ℃ for 1h, then reflux reaction is carried out at 100 ℃ for 3h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ C., -0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 4
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask provided with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent of each mole of phenolic hydroxyl group) is added dropwise at 80 ℃ for 1h, then reflux reaction is carried out at 80 ℃ for 5h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 5
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.257g of sodium hydroxide (1.0 equivalent per mol of phenolic hydroxyl group) is added dropwise at 90 ℃ for 1h, then reflux reaction is carried out at 90 ℃ for 5h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 6
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, 70mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent of each mole of phenolic hydroxyl group) is then added dropwise at 90 ℃ for 1h, then reflux reaction is carried out at 90 ℃ for 5h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 7
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent of each mole of phenolic hydroxyl group) is added dropwise at 90 ℃ for 1.5h, then reflux reaction is carried out at 90 ℃ for 5h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 8
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent of each mole of phenolic hydroxyl group) is added dropwise at 90 ℃ for 1.5h, then reflux reaction is carried out at 90 ℃ for 4h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 9
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.783g of sodium hydroxide (1.1 times equivalent per mol of phenolic hydroxyl group) is added dropwise at 90 ℃ for 1h, then reflux reaction is carried out at 90 ℃ for 4h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ and minus 0.1 MPa) is carried out, and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
Example 10
(1) Preparation of biomass resveratrol epoxy monomer
Under nitrogen atmosphere, 10g of resveratrol and 81.069g of epichlorohydrin are added into a three-neck flask equipped with a reflux condenser and a dropping funnel, then 80mL of ethanol containing 5.257g of sodium hydroxide (1.0 equivalent per mol of phenolic hydroxyl group) is added dropwise at 100 ℃ for 1h, then reflux reaction is carried out at 100 ℃ for 4h, natural cooling is carried out to room temperature, filtration is carried out, the filtrate is extracted with dichloromethane, the organic phase is washed 3 times with deionized water, reduced pressure concentration (80 ℃ C., -0.1 MPa), and drying is carried out in a vacuum oven at 90 ℃ for 12h, thus obtaining orange yellow oily matter.
(2) Preparation of biomass self-repairing epoxy resin
3.877g of citric acid is dissolved in 8mL of tetrahydrofuran, then poured into a beaker containing 10g of biomass epoxy monomer, prepolymerized at 90 ℃, defoamed in a vacuum oven (80 ℃,40min, -0.1 MPa), and then cured according to the process of 110 ℃/2 h +130 ℃/4 h +150 ℃/2 h; and after solidification, naturally cooling along with a hot press to obtain the biomass self-repairing epoxy resin.
The invention synthesizes the bio-based epoxy resin by taking resveratrol and epichlorohydrin as raw materials and takes biomass citric acid as a curing agent, and the prepared biomass-based self-repairing epoxy resin has outstanding heat resistance and T g The self-repairing efficiency is above 74% at the temperature of above 100 ℃ and the tensile strength of above 50MPa without catalyst; preferably, the biomass self-repairing epoxy resin prepared by the invention has a glass transition temperature (T g DMA) at 129 ℃, it also has a high flexural modulus (2.40 GPa) and strength (123.5 MPa), while it also has a high tensile strength (74.3 MPa) and good self-healing efficiency, with a scratch self-healing efficiency of 82.1% and a tensile strength healing efficiency of 81.9%. Compared with the prior art, the biomass epoxy resin is prepared from the full biomass raw material, and the resin can realize self-repairing under the condition of no catalyst, and has very excellent comprehensive performance, so that a reliable basis is provided for the application of the resin in the tip field.
Claims (10)
1. The preparation method of the biomass epoxy monomer is characterized by comprising the following steps of: and heating resveratrol and epichlorohydrin to react to prepare the biomass epoxy monomer.
2. The biomass epoxy monomer of claim 1, wherein: the mol ratio of resveratrol and epoxy chloropropane is 1:10-20.
3. The biomass epoxy monomer of claim 1, wherein: the heating reaction is carried out in an alcohol solvent in the presence of inorganic alkali; the temperature of the heating reaction is 80-100 ℃ and the time is 3-6 h.
4. A biomass epoxy monomer prepared from the biomass epoxy monomer of claim 1.
5. Use of the biomass epoxy monomer of claim 4 in the preparation of epoxy resins.
6. A preparation method of biomass self-repairing epoxy resin is characterized in that the biomass epoxy monomer described in claim 4 reacts with a biomass curing agent to obtain biomass self-repairing epoxy resin.
7. The method for preparing biomass self-repairing epoxy resin according to claim 6, wherein the method comprises the following steps: the biomass curing agent is a biomass acid; the reaction temperature is 110-150 ℃ and the reaction time is 6-12 h.
8. The method for preparing biomass self-repairing epoxy resin according to claim 7, wherein the method comprises the following steps: the biomass acid is citric acid; the mol ratio of the biomass epoxy monomer to the biomass curing agent is 1:0.5-1.5.
9. The biomass self-repairing epoxy resin prepared by the preparation method of biomass self-repairing epoxy resin according to claim 6.
10. Use of the biomass epoxy monomer of claim 4 or the biomass self-repairing epoxy resin of claim 9 in the preparation of an epoxy resin material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117551258A (en) * | 2024-01-10 | 2024-02-13 | 西南石油大学 | Biological source light response epoxy resin and preparation method thereof |
| CN117551258B (en) * | 2024-01-10 | 2024-03-15 | 西南石油大学 | Biological source light response epoxy resin and preparation method thereof |
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