CN116283835B - Biomass epoxy monomer, self-curing epoxy resin and preparation method thereof - Google Patents
Biomass epoxy monomer, self-curing epoxy resin and preparation method thereof Download PDFInfo
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- CN116283835B CN116283835B CN202310162654.3A CN202310162654A CN116283835B CN 116283835 B CN116283835 B CN 116283835B CN 202310162654 A CN202310162654 A CN 202310162654A CN 116283835 B CN116283835 B CN 116283835B
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
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- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
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Abstract
The invention discloses a biomass epoxy monomer, biomass self-curing epoxy resin and a preparation method thereof, wherein biomass tyramine and diphenolic acid are used as raw materials, and phenolic compounds are obtained through heating reaction; heating and reacting a phenol compound and epichlorohydrin to obtain an amide bond-containing biomass epoxy monomer; and solidifying the biomass epoxy monomer containing the amide bond to obtain the biomass epoxy resin. Compared with the prior art, the epoxy resin has excellent thermal performance, high flexural modulus and strength and high impact strength.
Description
Technical Field
The invention relates to a biomass epoxy monomer, biomass self-curing epoxy resin and a preparation method thereof, belonging to the technical field of functional polymer materials.
Background
The epoxy thermosetting resin has good chemical resistance, thermal stability, mechanical strength, cohesiveness, dimensional stability and electrical insulation, and is widely applied to various fields such as electrical engineering, electronic packaging, aerospace, new energy, rail transit and the like as a coating, an adhesive and a high-performance composite resin matrix. However, most of the epoxy resins are currently made from petroleum, a non-renewable resource, and the epoxy resin is crosslinked with a curing agent to form a high-strength thermosetting cured product. The curing agent is mainly amine, anhydride, latent curing agent, etc. In the mixing process of the epoxy resin and the curing agent, defects exist in the cured product due to non-uniformity of mixing or air bubbles and the like, and the defects are the weak points of the material, so that the premature failure of the material under the stress effect is directly caused. In addition, some epoxy resins or curing agents have relatively high viscosity, and some organic solvents are required to be added for dilution during blending, and volatilization of the organic solvents can pollute the atmosphere and harm human health.
Therefore, a novel self-curing epoxy resin is synthesized which is stable at normal temperature and undergoes self-crosslinking reaction under specific conditions, thereby minimizing defects of cured products caused by non-uniformity during mixing. To date, most of existing self-curing epoxy resins are not biomass resins, and meanwhile, imidazole, pyridine or amine catalysts are often added in the curing process of the existing self-curing epoxy resins to react with epoxy, so that the existing self-curing epoxy resins are not truly self-curing epoxy resins. And their flexural strength and impact strength are low. In short, the prior art does not have a biomass self-curing epoxy resin with high flexural and impact strength.
In view of the above, there is still a challenge to develop a biomass self-curing epoxy resin with high heat resistance, high flexural modulus and strength, and high impact strength.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a biomass epoxy monomer, a biomass self-curing epoxy resin with high heat resistance, high flexural modulus and strength and high impact strength and a preparation method thereof.
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:
(1) After heating and reacting tyramine and diphenolic acid, obtaining phenol compound;
(2) And heating and reacting the phenol compound and epichlorohydrin to obtain the biomass epoxy monomer.
The preparation method of the biomass self-curing epoxy resin comprises the following steps:
(1) After heating and reacting tyramine and diphenolic acid, obtaining phenol compound;
(2) Heating the phenol compound and epichlorohydrin for reaction to obtain a biomass epoxy monomer;
(3) And solidifying the biomass epoxy monomer to obtain the biomass self-solidifying epoxy resin.
In the step (1), the mol ratio of the tyramine to the diphenolic acid is 1: (0.5-1.5), preferably 1:1; the heating reaction temperature is 170-185 ℃ for 3-8 h, preferably 175-180 ℃ for 4-6 h.
In the step (2) of the present invention, the molar ratio of the phenol compound to epichlorohydrin is 1: (5-15), preferably 1:10.
In the step (2) of the invention, the heating reaction is carried out in an alcohol solvent, preferably ethanol; the heating reaction temperature is 80-100 ℃, the time is 1-2 h, and the preferable heating reaction temperature is 80-90 ℃ and the time is 1.5-2 h.
In the step (2) of the invention, the heating reaction is carried out in the presence of an inorganic base, preferably sodium hydroxide; the amount of the inorganic base to be used is 1 to 1.5 times, preferably 1.1 to 1.2 times, such as 1.1 times, the molar amount of the phenolic hydroxyl groups in the phenol compound.
In the step (3), the biomass epoxy monomer is defoamed and then solidified; the curing temperature is 160-220 ℃ 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 ℃.
Specifically, the biomass self-curing epoxy resin disclosed by the invention is prepared as follows:
(1) Mixing 100 parts of tyramine and 100 parts of diphenolic acid according to mole parts, stirring at 175-180 ℃ for reaction for 4-6 hours, and naturally cooling to room temperature to obtain phenolic compounds;
(2) Mixing 100 parts of phenol compound and 1000 parts of epichlorohydrin in ethanol in mol parts, then dropwise adding aqueous sodium hydroxide solution (1 mol/L, 1-1.5 times equivalent weight of each mol of phenolic hydroxyl group) into the mixture, reacting for 1-2 hours at 80-100 ℃, naturally cooling to room temperature, then mixing the mixture with dichloromethane, washing with deionized water, rotary evaporating (80 ℃ and 0.1 MPa) to remove the solvent, and obtaining biomass epoxy monomers through vacuum distillation (120 ℃);
(3) And (3) defoaming the biomass epoxy monomer obtained in the step (2), and curing to obtain the biomass self-curing epoxy resin.
The invention discloses application of tyramine, diphenolic acid and epichlorohydrin as raw materials in preparation of epoxy resin monomers or cured products; the application of the biomass epoxy monomer or the self-curing epoxy resin in preparing an epoxy resin material, in particular to the application of the self-curing epoxy resin material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes tyramine and diphenolic acid as raw materials to synthesize an epoxy resin containing amide bond, the tyramine and diphenolic acid adopted are biomass raw materials, and biomass self-curing epoxy resin is obtained by curing the biomass raw materials;
2. the biomass self-curing epoxy resin prepared by the invention has outstanding heat resistance and glass transition temperature (T) g ) 126℃and also has a high flexural modulus (4.67 GPa) and strength (188.3 MPa), and at the same time a high impact strength (21.80 KJ/m 2 No notch) and tensile strength (89.99 MPa), thereby providing a reliable basis for its application in the tip field.
Drawings
FIG. 1 is a synthetic reaction scheme and a chemical structural scheme of the phenol compound and the biomass epoxy monomer prepared in example 1 of the present invention.
FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum of phenol compound in example 1 of the present invention 1 H-NMR）。
FIG. 3 shows nuclear magnetic resonance spectrum of phenol compound in example 1 of the present invention 13 C-NMR）。
FIG. 4 shows the hydrogen nuclear magnetic resonance spectrum of the biomass epoxy monomer in example 1 of the present invention 1 H NMR）。
FIG. 5 shows the hydrogen nuclear magnetic resonance spectrum of the biomass epoxy monomer in example 1 of the present invention 13 C-NMR）。
Fig. 6 is a high resolution mass spectrum of biomass epoxy monomer prepared in example 1 of the present invention.
FIG. 7 is a thermal weight loss (TGA) curve of a biomass self-curing epoxy resin prepared in example 1 of the present invention, 10 ℃/min, nitrogen.
FIG. 8 is a dynamic thermo-mechanical analysis (DMA) curve of a biomass self-curing epoxy resin prepared in example 1 of the present invention, 10 ℃/min.
Fig. 9 is a bending stress-strain curve of the biomass self-curing epoxy resin prepared in example 1 of the present invention.
Fig. 10 is a tensile stress-strain curve of the biomass self-curing epoxy resin prepared in example 1 of the present invention.
Detailed Description
The preparation process of the biomass self-curing epoxy resin disclosed by the invention is shown in fig. 1, and specifically comprises the following steps:
(1) After heating and reacting tyramine and diphenolic acid, obtaining phenol compound;
(2) Heating and reacting the phenol compound and epichlorohydrin to obtain an amide bond-containing biomass epoxy monomer;
(3) And curing the biomass epoxy monomer containing the amide bond to obtain the biomass self-curing epoxy resin.
The technical scheme of the invention is further described below with reference to the accompanying drawings and the examples; all materials are commercially available and the specific preparation operations and test methods involved are conventional in the art, using a universal tester (MTS CMT-4104) to test mechanical properties, tensile testing with reference to ASTM-D882, flexural testing with reference to GBT2570-1995, and impact testing with reference to GBT2571-1995. The molecular weight of the epoxy monomers was tested using high resolution mass spectrometry (HRMS, MICRO TOF-Q III, ESI+). Testing with nuclear magnetic resonance apparatus (Bruker 400-600 mhz) 1 H-NMR 13 C-NMR spectrum with CDCl as solvent 3 Or DMSO-d6. Investigation of the resin at N using a thermogravimetric analyzer (TGA, discovery) 2 Thermal stability under atmosphere, heating from room temperature to 800 ℃ at a heating rate of 10 ℃/min.
Example 1
(1) Preparation of phenol Compounds
6g of tyramine (CAS#: 51-67-2) and 12.52g of bis-tyramine were addedPhenolic acid (CAS#: 126-00-1) is mixed, then stirred and reacted for 4 hours at 175 ℃, and then naturally cooled to room temperature, so as to obtain phenolic compound with the yield of 94%; its nuclear magnetic resonance hydrogen spectrum 1 H-NMR) and nuclear magnetic resonance carbon spectrum 13 C-NMR) are shown in FIGS. 2 and 3, respectively.
(2) Preparation of biomass epoxy monomer containing amide bond
Mixing 10g of phenol compound and 16.10g of epichlorohydrin in 35mL of ethanol at room temperature, dropwise adding a sodium hydroxide aqueous solution (1 mol/L, 1.1 times equivalent of phenolic hydroxyl groups per mol) into the mixture, reacting for 2 hours at 80 ℃ after the dropwise addition is completed, then naturally cooling to room temperature, mixing the obtained mixture with 30mL of dichloromethane, washing with 100mL of deionized water, rotary evaporating (80 ℃ C., 0.1 MPa) to remove dichloromethane and most of ethanol, and carrying out vacuum distillation (120 ℃ C.) to obtain biomass epoxy monomer containing amide bonds, wherein the yield is 90%; FIG. 4 shows the nuclear magnetic resonance hydrogen spectrum [ ] 1 H NMR); FIG. 5 shows the nuclear magnetic resonance hydrogen spectrum [ ] 13 C-NMR); fig. 6 is a high resolution mass spectrum thereof.
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed into a mold, the mold is placed into a vacuum oven for defoaming (110 ℃,10min and 0.1 MPa), and then the mold is placed into a blast drying oven for curing according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin, wherein a thermal weight loss curve, a dynamic thermo-mechanical analysis (DMA) curve, a bending stress-strain curve and a tensile stress-strain curve of the biomass self-solidifying epoxy resin are respectively shown in fig. 7, 8, 9 and 10.
It can be seen that the glass transition temperature (T g ) 126 ℃, T d5% 317 ℃. Further, the flexural modulus, flexural strength and tensile strength of the biomass self-curing epoxy resin at normal temperature are 4.67GPa, 188.3MPa and 89.99MPa, respectively, and at the same time, the biomass self-curing epoxy resin also has high impact strength (21.80 kJ/m 2 ) Has outstanding mechanical properties.
In the prior art, renewable bio-based compounds and magnolol are used as raw materials, the bio-based epoxy resin DGEH is prepared through one-step reaction, the bending modulus of DGEH/DDS after solidification is 3360 MPa, and the bending modulus is considered to be improved by 30% compared with the corresponding value of an E51/DDS system.
The glass transition temperature of the existing diphenolic acid epoxy resin after self-curing is 70.84 ℃, and a curing experiment is carried out by adopting common epoxy resin 128 and a commercially available curing agent D230 according to a mass ratio of 3:1, wherein the glass transition temperature is 88.83 ℃.
In the prior art, eugenol and glutaryl chloride are used as raw materials, a biomass epoxy resin (EPEUGL) with self-curing characteristic is designed and prepared, and the glass transition temperature (TgDMA) of C-EPEUGL is 94.6 ℃.
The prior art discloses a novel bio-based epoxy monomer containing active ester side groups, and the bending strength of a cured product is 105MPa in the presence of a curing accelerator.
The prior art discloses an anhydride-containing self-curing epoxy resin which is pointed out to have high modulus and strength, and the tensile strength of a cured product is 42.5+/-3.6 MPa under the promotion of a small amount of ethyl-4-methylimidazole.
In the prior art, the m-phthalamide is used as an initial raw material to prepare the epoxy resin BTE by adoptingN 2 ,N 5 -bis (4-hydroxyphenyl) furan-2, 5-dicarboxamide to prepare epoxy BFE; DSC curve curing peak of the two monomers is smaller, which is similar to commercial bisphenol A epoxy, self-curing material performance is poor, T d5% Are less than 200 c (10 c/min, nitrogen) and limit their use as high performance materials.
The biomass self-curing epoxy resin prepared by the invention has excellent heat resistance and very good mechanical properties.
Example 2
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and reacted for 5 hours under stirring at 175 ℃, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 80℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃at 0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 3
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and reacted for 5 hours under stirring at 175 ℃, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 90℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 4
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and reacted for 5 hours under stirring at 175 ℃, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 100℃for 1 hour, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 5
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and reacted for 6 hours under stirring at 175 ℃, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 80℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃at 0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 6
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and stirred at 175 ℃ for reaction for 4 hours, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 100℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 7
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and stirred at 180 ℃ for reaction for 4 hours, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 80℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃at 0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 8
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and stirred at 180 ℃ for reaction for 5 hours, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 80℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃at 0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 9
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and stirred at 180 ℃ for reaction for 5 hours, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 100℃for 1 hour, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
Example 10
(1) Preparation of phenol Compounds
6g of tyramine and 12.52g of diphenolic acid are mixed and stirred at 180 ℃ for reaction for 6 hours, and naturally cooled to room temperature, thus obtaining phenolic compound.
(2) Preparation of biomass epoxy monomer containing amide bond
10g of phenol compound and 16.10g of epichlorohydrin were mixed in ethanol, an aqueous sodium hydroxide solution (1 mol/L, 1.1 times equivalent per mol of phenolic hydroxyl group) was added dropwise to the mixture, reacted at 80℃for 2 hours, naturally cooled to room temperature, the mixture was mixed with methylene chloride, washed with deionized water, rotary evaporated (80℃at 0.1 MPa) to remove methylene chloride and most of ethanol, and an amide bond-containing biomass epoxy monomer was obtained by vacuum distillation (120 ℃).
(3) Preparation of biomass self-curing epoxy resin
10.0g of biomass epoxy monomer containing amide bonds is placed in a mold, the mold is placed in a vacuum oven for defoaming (10 min at 110 ℃), then the mold is placed in a blast drying oven, and the curing is carried out according to the process of 160 ℃/2 h +180 ℃/2 h +200 ℃/2 h +220 ℃/2 h; and after solidification, naturally cooling along with an oven to obtain the biomass self-solidifying epoxy resin.
The invention synthesizes the epoxy resin containing amide bond by taking tyramine and diphenolic acid as raw materials, the tyramine and diphenolic acid adopted are biomass raw materials, and the prepared biomass self-curing epoxy resin has outstanding heat resistance and glass transition temperature (T) g ) 126℃and also has a high flexural modulus (4.67 GPa) and strength (188.3 MPa), and at the same time a high impact strength (21.80 kJ/m 2 ) Compared with the prior art, the preparation method provided by the invention realizes the preparation of the biomass epoxy resin from the biomass raw material for the first time, and the resin has the capability of real self-curing, and particularly, the self-curing product has very excellent comprehensive performance, so that a reliable foundation is provided for the application of the self-curing product in the tip field.
Claims (7)
1. The preparation method of the biomass epoxy monomer is characterized by comprising the following steps of:
(1) After heating and reacting tyramine and diphenolic acid, obtaining phenol compound; the mol ratio of the tyramine to the diphenolic acid is 1:0.5-1.5;
(2) Heating and reacting the phenol compound with epichlorohydrin to obtain a biomass epoxy monomer; the mol ratio of the phenol compound to the epoxy chloropropane is 1:5-15; the temperature of the heating reaction is 80-100 ℃ and the time is 1-2 h.
2. The method for preparing biomass epoxy monomer according to claim 1, wherein: in the step (1), the temperature of the heating reaction is 170-185 ℃ and the time is 3-8 h.
3. The method for preparing biomass epoxy monomer according to claim 1, wherein: in step (2), the heating reaction is carried out in the presence of an inorganic base; the heating reaction is carried out in an alcohol solvent.
4. A biomass epoxy monomer prepared by the method for preparing a biomass epoxy monomer according to claim 1.
5. A method for preparing biomass self-curing epoxy resin, which is characterized in that biomass epoxy monomers in claim 4 are cured to obtain biomass self-curing epoxy resin; curing does not need to add a catalyst and a curing agent; the curing temperature is 160-220 ℃ and the curing time is 5-16 h.
6. The biomass self-curing epoxy resin prepared by the preparation method of biomass self-curing epoxy resin according to claim 5.
7. Use of the biomass epoxy monomer of claim 4 or the biomass self-curing epoxy resin of claim 6 in the preparation of an epoxy resin material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391651A (en) * | 1990-08-03 | 1995-02-21 | The Dow Chemical Company | Curable mixtures of mesogenic epoxy resins and mesogenic polyamines and cured compositions |
| CN113004494A (en) * | 2021-03-30 | 2021-06-22 | 金向红 | Modified epoxy resin, preparation method and emulsion preparation method thereof, and application of waterproof coating |
| CN113999417A (en) * | 2021-10-26 | 2022-02-01 | 华南理工大学 | Continuous fiber reinforced thermosetting resin-based high-thermal-conductivity composite material and preparation method thereof |
| CN113999191A (en) * | 2021-11-25 | 2022-02-01 | 大连理工大学 | Novel bio-based epoxy resin containing active ester side group and preparation method thereof |
| CN115160540A (en) * | 2022-08-09 | 2022-10-11 | 四川大学 | High-modulus high-activity epoxy resin and synthesis method and application thereof |
| CN115197173A (en) * | 2022-07-19 | 2022-10-18 | 南京工业大学 | Bio-based epoxy resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014152714A1 (en) * | 2013-03-14 | 2014-09-25 | Case Western Reserve University | Bisphenol polymer precursor replacements |
-
2023
- 2023-02-24 CN CN202310162654.3A patent/CN116283835B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391651A (en) * | 1990-08-03 | 1995-02-21 | The Dow Chemical Company | Curable mixtures of mesogenic epoxy resins and mesogenic polyamines and cured compositions |
| CN113004494A (en) * | 2021-03-30 | 2021-06-22 | 金向红 | Modified epoxy resin, preparation method and emulsion preparation method thereof, and application of waterproof coating |
| CN113999417A (en) * | 2021-10-26 | 2022-02-01 | 华南理工大学 | Continuous fiber reinforced thermosetting resin-based high-thermal-conductivity composite material and preparation method thereof |
| CN113999191A (en) * | 2021-11-25 | 2022-02-01 | 大连理工大学 | Novel bio-based epoxy resin containing active ester side group and preparation method thereof |
| CN115197173A (en) * | 2022-07-19 | 2022-10-18 | 南京工业大学 | Bio-based epoxy resin and preparation method thereof |
| CN115160540A (en) * | 2022-08-09 | 2022-10-11 | 四川大学 | High-modulus high-activity epoxy resin and synthesis method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 天津市合成材料工业研究所.环氧树脂与环氧化物.天津人民出版社,1974,第289-292页. * |
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