CN116283835A - A kind of biomass epoxy monomer, self-curing epoxy resin and preparation method thereof - Google Patents

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

A kind of biomass epoxy monomer, self-curing epoxy resin and preparation method thereof

technical field

The invention relates to a biomass epoxy monomer, a biomass self-curing epoxy resin and a preparation method thereof, belonging to the technical field of functional polymer materials.

Background technique

Epoxy thermosetting resins have good chemical resistance, thermal stability, mechanical strength, cohesiveness, dimensional stability and electrical insulation, and are widely used in electrical engineering, Electronic packaging, aerospace, new energy, rail transportation and many other fields. However, at present, most epoxy resins are made from non-renewable resource petroleum, and epoxy resins are cross-linked with curing agents to form high-strength thermosetting cured products. The types of curing agents mainly include amines, acid anhydrides and latent curing agents. During the mixing process of epoxy resin and curing agent, due to uneven mixing or air bubbles, there will be some defects in the cured product, and these defects are the weak points of the material, which directly lead to the failure of the material under stress. premature destruction. In addition, some epoxy resins or curing agents have relatively high viscosity. When blending, some organic solvents need to be added for dilution. The volatilization of these organic solvents will pollute the atmospheric environment and endanger human health.

Therefore, synthesizing a new type of self-curing epoxy resin, which can be stable at room temperature and undergoes its own cross-linking reaction under specific conditions, can minimize the cured product defects caused by inhomogeneity in the mixing process . So far, most of the existing self-curing epoxy resins are not biomass resins. At the same time, the current self-curing epoxy resins often add imidazole, pyridine or amine catalysts during the curing process to react with epoxy. Therefore, it is not A true self-curing epoxy resin. Also, their bending 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 summary, it is still challenging to develop a biomass self-curing epoxy resin with high heat resistance, high flexural modulus and strength, and high impact strength.

Contents of the invention

Aiming at the deficiencies of the prior art, the present 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 object, the technical scheme adopted in the present invention is:

A kind of biomass epoxy monomer, the preparation method of described biomass epoxy monomer comprises the steps:

(1) After heating and reacting tyramine and bisphenolic acid, a phenolic compound is obtained;

(2) heating and reacting the phenolic compound and epichlorohydrin to obtain a biomass epoxy monomer.

A kind of biomass self-curing epoxy resin, the preparation method of described biomass self-curing epoxy resin comprises the steps:

(1) After heating and reacting tyramine and bisphenolic acid, a phenolic compound is obtained;

(2) heating and reacting the phenolic compound and epichlorohydrin to obtain a biomass epoxy monomer;

(3) curing the biomass epoxy monomer to obtain a biomass self-curing epoxy resin.

In the step (1) of the present invention, the molar ratio of tyramine and bisphenolic acid is 1: (0.5-1.5), preferably 1:1; the temperature of the heating reaction is 170-185°C, and the time is 3-8h, preferably, The temperature of the heating reaction is 175-180° C., and the time is 4-6 hours.

In step (2) of the present invention, the molar ratio of phenolic compound and epichlorohydrin is 1: (5-15), preferably 1:10.

In the step (2) of the present invention, the heating reaction is carried out in an alcohol solvent. Preferably, the alcohol solvent is ethanol; the temperature of the heating reaction is 80-100°C, and the time is 1-2h. Preferably, the temperature of the heating reaction is 80-100°C. 90°C for 1.5-2 hours.

In step (2) of the present invention, the heating reaction is carried out in the presence of an inorganic base, preferably, the inorganic base is sodium hydroxide; the amount of the inorganic base is 1 to 1.5 times, preferably 1.1 to 1.2 times, the molar weight of the phenolic hydroxyl group in the phenolic compound , such as 1.1 times.

In the step (3) of the present invention, the biomass epoxy monomer is degassed and then solidified; the curing temperature is 160-220° C., and the curing time is 5-16 hours. Preferably, the curing is carried out in a stepwise heating manner, the holding time at each step temperature is not less than 1 h, and the temperature difference between adjacent steps does not exceed 30°C.

Specifically, the preparation of biomass self-curing epoxy resin of the present invention is as follows:

(1) In molar parts, mix 100 parts of tyramine and 100 parts of bisphenolic acid, then stir and react at 175-180°C for 4-6 hours, and naturally cool to room temperature to obtain a phenolic compound;

(2) In terms of molar parts, mix 100 parts of phenolic compound and 1000 parts of epichlorohydrin in ethanol, and then add dropwise sodium hydroxide aqueous solution (1mol/L, 1 to 1.5 times equivalent per mole of phenolic hydroxyl group) to the mixture , reacted at 80-100°C for 1-2h, cooled naturally to room temperature, then mixed the mixture with dichloromethane, washed with deionized water, and rotary evaporated (80°C, 0.1MPa) to remove the solvent, and vacuum distillation (120 ℃) obtain biomass epoxy monomer;

(3) The biomass epoxy monomer obtained in step (2) is defoamed, and then cured to obtain a biomass self-curing epoxy resin.

The invention discloses the application of tyramine, bisphenolic acid and epichlorohydrin as raw materials in the preparation of epoxy resin monomers or cured products; the above-mentioned biomass epoxy monomer or self-curing epoxy resin is used in the preparation of epoxy resin materials , especially the application of self-curing epoxy resin materials.

Compared with prior art, the beneficial effect that the present invention obtains is:

1. The present invention uses tyramine and bisphenolic acid as raw materials to synthesize an epoxy resin containing an amide bond. The tyramine and bisphenolic acid used are biomass raw materials, which are solidified to obtain biomass self-curing epoxy resin. resin;

2. The biomass self-curing epoxy resin prepared by the present invention has outstanding heat resistance, the glass transition temperature (T _g ) is 126°C, and it also has high flexural modulus (4.67GPa) and strength (188.3MPa), At the same time, it also has high impact strength (21.80KJ/m ² , no notch) and tensile strength (89.99MPa), which provides a reliable basis for its application in cutting-edge fields.

Description of drawings

Fig. 1 is the synthetic reaction formula and chemical structural formula of preparing phenolic compound and biomass epoxy monomer in Example 1 of the present invention.

Fig. 2 is the hydrogen nuclear magnetic resonance spectrum ( ¹ H-NMR) of the phenolic compound in Example 1 of the present invention.

Fig. 3 is the carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) of the phenolic compound in Example 1 of the present invention.

Fig. 4 is the hydrogen nuclear magnetic resonance spectrum ( ¹ H NMR) of the biomass epoxy monomer in Example 1 of the present invention.

Fig. 5 is the hydrogen nuclear magnetic resonance spectrum ( ¹³ C-NMR) of the biomass epoxy monomer in Example 1 of the present invention.

Fig. 6 is a high-resolution mass spectrum of the biomass epoxy monomer prepared in Example 1 of the present invention.

Fig. 7 is the thermogravimetric loss (TGA) curve of the biomass self-curing epoxy resin prepared in Example 1 of the present invention, 10°C/min, nitrogen.

Fig. 8 is the dynamic thermomechanical analysis (DMA) curve of the biomass self-curing epoxy resin prepared in Example 1 of the present invention, 10°C/min.

Fig. 9 is the bending stress-strain curve of the biomass self-curing epoxy resin prepared in Example 1 of the present invention.

Fig. 10 is the tensile stress-strain curve of the biomass self-curing epoxy resin prepared in Example 1 of the present invention.

Detailed ways

Refer to Fig. 1 for the preparation process of biomass self-curing epoxy resin disclosed by the present invention, specifically as follows:

(1) After heating and reacting tyramine and bisphenolic acid, a phenolic compound is obtained;

(2) heating and reacting the phenolic compound and epichlorohydrin to obtain an amide bond-containing biomass epoxy monomer;

(3) curing the amide bond-containing biomass epoxy monomer to obtain a biomass self-curing epoxy resin.

The technical solution of the present invention will be further described below in conjunction with the accompanying drawings and examples; all raw materials are commercially available, and the specific preparation operations and testing methods involved are all conventional methods in the field, using a universal testing machine (MTS CMT-4104) To test the mechanical properties, refer to ASTM-D882 for tensile test, refer to GBT2570-1995 for bending test, and refer to GBT2571-1995 for impact test. The molecular weight of the epoxy monomer was tested by high-resolution mass spectrometry (HRMS, MICRO TOF-Q III, ESI+). ^{The 1} H-NMR and ¹³ C-NMR spectra were measured using a nuclear magnetic resonance instrument (Bruker 400-600mhz), and the solvent was CDCl ₃ or DMSO-d6. The thermogravimetric analyzer (TGA, Discovery) was used to study the thermal stability of the resin under _N2 atmosphere, heating from room temperature to 800 °C at a heating rate of 10 °C/min.

Example 1

(1) Preparation of phenolic compounds

Mix 6g of tyramine (CAS#: 51-67-2) and 12.52g of bisphenolic acid (CAS#: 126-00-1), then stir and react at 175°C for 4h, then cool naturally to room temperature to obtain phenolic compound , and the yield was 94%; its proton nuclear magnetic resonance spectrum ( ¹ H-NMR) and carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) are shown in Figure 2 and Figure 3, respectively.

(2) Preparation of amide bond-containing biomass epoxy monomer

At room temperature, mix 10g of phenolic compound and 16.10g of epichlorohydrin in 35mL of ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times the equivalent per mole of phenolic hydroxyl group) to the mixture, and after the addition is completed, heat at 80°C The mixture was reacted at lower temperature for 2 h, then naturally cooled to room temperature, the resulting mixture was mixed with 30 mL of dichloromethane, washed with 100 mL of deionized water, and then rotary evaporated (80° C., 0.1 MPa) to remove dichloromethane and most of the ethanol, and then Biomass epoxy monomer containing amide bonds was obtained by vacuum distillation (120°C), with a yield of 90%; Figure 4 is its hydrogen nuclear magnetic resonance spectrum ( ¹ H NMR); Figure 5 is its hydrogen nuclear magnetic resonance spectrum ( ¹³ C-NMR ); Figure 6 is its high-resolution mass spectrum.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for degassing (110°C, 10min, 0.1MPa), then put the mold into a blast drying oven, and follow the 160 ℃/2 h + 180 ℃/2 h+ 200 ℃/2 h + 220 ℃/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin, its thermal weight loss curve, dynamic Thermomechanical analysis (DMA) curves, bending stress-strain curves, and tensile stress-strain curves are shown in Figure 7, Figure 8, Figure 9, and Figure 10, respectively.

It can be seen that the above-mentioned biomass self-curing epoxy resin has a glass transition temperature (T _g ) of 126 °C and a T _d5% of 317 °C. Furthermore, the flexural modulus, flexural strength, and tensile strength of the above-mentioned biomass self-curing epoxy resin at room temperature are 4.67GPa, 188.3MPa, and 89.99MPa, respectively, and it also has high impact strength (21.80kJ/m ² ) , with outstanding mechanical properties.

The prior art uses the renewable bio-based compound honokiol as raw material to prepare bio-based epoxy resin DGEH through a one-step reaction. The flexural modulus of DGEH/DDS after curing is 3360 MPa, which is considered to be higher than that of the E51/DDS system. Value increased by 30%.

The glass transition temperature of the existing bisphenolic acid epoxy resin after self-curing is 70.84°C. The curing experiment was carried out with ordinary epoxy resin 128 and commercially available curing agent D230 at a mass ratio of 3:1, and the glass transition temperature was 88.83°C.

In the prior art, a self-curing biomass epoxy resin (EPEUGL) was designed and prepared using eugenol and glutaryl chloride as raw materials. The glass transition temperature (TgDMA) of C-EPEUGL is 94.6°C.

The prior art discloses a novel bio-based epoxy monomer containing active ester side groups. In the presence of a curing accelerator, the cured product has a bending strength of 105 MPa.

The prior art discloses a self-curing epoxy resin containing acid anhydride, pointing out that it has high modulus and strength, and under the promotion of a small amount of ethyl-4-methylimidazole, the tensile strength of the cured product is 42.5±3.6MPa .

In the prior art, epoxy resin BTE was prepared with isophthalamide as the initial raw material, and epoxy resin BFE was prepared with N ² , N ⁵ -bis(4-hydroxyphenyl)furan-2,5-dicarboxamide; two The curing peak of the DSC curve of this monomer is relatively small, which is similar to that of commercial bisphenol A epoxy. The performance of self-curing products is poor, and T _d5% is less than 200°C (10°C/min, nitrogen), which limits its use as a high-performance material. use.

The above shows that the biomass self-curing epoxy resin prepared by the present invention has excellent heat resistance and very good mechanical properties.

Example 2

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 175°C for 5h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 80°C for 2h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 3

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 175°C for 5h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10 g of phenolic compound and 16.10 g of epichlorohydrin in ethanol, add aqueous sodium hydroxide solution (1 mol/L, 1.1 equivalents per mole of phenolic hydroxyl group) dropwise to the mixture, react at 90 °C for 2 h, and cool naturally to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 4

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 175°C for 5h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 100°C for 1h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 5

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 175°C for 6h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 80°C for 2h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 6

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 175°C for 4h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add aqueous sodium hydroxide solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 100°C for 2h, and cool naturally to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 7

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 180°C for 4h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 80°C for 2h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 8

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 180°C for 5h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 80°C for 2h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 9

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 180°C for 5h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 100°C for 1h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

Example 10

(1) Preparation of phenolic compounds

6g of tyramine and 12.52g of bisphenolic acid were mixed, stirred and reacted at 180°C for 6h, and naturally cooled to room temperature to obtain a phenolic compound.

(2) Preparation of amide bond-containing biomass epoxy monomer

Mix 10g of phenolic compound and 16.10g of epichlorohydrin in ethanol, add dropwise sodium hydroxide aqueous solution (1mol/L, 1.1 times equivalent per mole of phenolic hydroxyl group) to the mixture, react at 80°C for 2h, and naturally cool to room temperature , the mixture was mixed with dichloromethane, washed with deionized water, rotary evaporated (80 °C, 0.1 MPa) to remove dichloromethane and most of the ethanol, and vacuum distillation (120 °C) to obtain amide bond-containing biomass epoxy monomers body.

(3) Preparation of biomass self-curing epoxy resin

Put 10.0g of amide bond-containing biomass epoxy monomer into the mold, put the mold into a vacuum oven for defoaming (10min at 110°C), then put the mold into a blast drying oven, and follow the steps of 160°C/2 h + 180 °C/2 h + 200 °C/2 h + 220 °C/2 h for curing; after curing, cool naturally with the oven to obtain biomass self-curing epoxy resin.

The present invention uses tyramine and bisphenolic acid as raw materials to synthesize an epoxy resin containing amide bonds. The tyramine and bisphenolic acid used are both biomass raw materials, and the prepared biomass self-curing epoxy resin has outstanding Heat resistance, the glass transition temperature (T _g ) is 126°C, it also has high flexural modulus (4.67GPa) and strength (188.3MPa), and it also has high impact strength (21.80kJ/m ² ) and tensile strength Tensile strength (89.99MPa), compared with the prior art, the present invention realizes the preparation of biomass epoxy resin from all biomass raw materials for the first time, and the resin has real self-curing ability, especially, the self-curing product has very excellent Comprehensive performance, thus providing a reliable basis for its application in cutting-edge fields.

Claims (10)

1. a biomass epoxy monomer, is characterized in that, the preparation method of described biomass epoxy monomer comprises the steps: (1) After heating and reacting tyramine and bisphenolic acid, a phenolic compound is obtained; (2) heating and reacting the phenolic compound with epichlorohydrin to obtain a biomass epoxy monomer. 2. The biomass epoxy monomer according to claim 1, characterized in that, in step (1), the molar ratio of tyramine to bisphenolic acid is 1: (0.5-1.5). 3 . The biomass epoxy monomer according to claim 1 , wherein in step (1), the heating reaction temperature is 170-185° C. and the time is 3-8 hours. 4. The biomass epoxy monomer according to claim 1, characterized in that, in step (2), the molar ratio of phenolic compound and epichlorohydrin is 1: (5-15). The biomass epoxy monomer according to claim 1, characterized in that, 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. 6 . The biomass epoxy monomer according to claim 1 , wherein in step (2), the temperature of the heating reaction is 80-100° C., and the time is 1-2 hours. 7. A biomass self-curing epoxy resin, characterized in that, the biomass epoxy monomer described in claim 1 is cured to obtain a biomass self-curing epoxy resin. 8 . The biomass self-curing epoxy resin according to claim 7 , wherein no catalyst and curing agent are added for curing; the curing temperature is 160-220° C. and the curing time is 5-16 hours. 9. The application of tyramine, bisphenolic acid and epichlorohydrin as raw materials in the preparation of biomass epoxy resin monomer or cured product. 10. the application of the biomass epoxy monomer described in claim 1 or the biomass self-curing epoxy resin described in claim 7 in the preparation of epoxy resin materials.

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