CN113999191A - Novel bio-based epoxy resin containing active ester side group and preparation method thereof - Google Patents
Novel bio-based epoxy resin containing active ester side group and preparation method thereof Download PDFInfo
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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
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Abstract
The invention provides a novel bio-based epoxy resin containing an active ester side group and a preparation method thereof, belonging to the technical field of material science. The preparation method comprises the steps of (1) obtaining an intermediate containing acetyl ester side groups through acetylation reaction by using biological-based raw materials of magnolol and acetic anhydride and sodium acetate as a catalyst; under the action of an oxidant, double bonds of the intermediate are epoxidized to obtain the acetyl ester side group-containing bio-based epoxy precursor. The bio-based epoxy resin having a high glass transition temperature is prepared by the reaction of the acetyl ester group and the epoxy group without adding any curing agent. Meanwhile, different reaction activities of the petroleum-based curing agent and the ester functional group with the epoxy group can be utilized to form in-situ self-growth phase separation and hydrogen bond action, so that the enhancement and intrinsic flame retardance of the epoxy resin are realized simultaneously. The simple strategy provides a new idea for solving the key problem that the heat resistance, strength and flame retardance of the epoxy resin are difficult to improve simultaneously.
Description
Technical Field
The invention belongs to the technical field of material science, relates to preparation of bio-based epoxy resin, and particularly relates to novel bio-based epoxy resin containing active ester side groups and a preparation method thereof.
Background
Epoxy thermosetting resins have good chemical resistance, thermal stability, mechanical strength, cohesiveness, dimensional stability and electrical insulation, so that epoxy thermosetting resins are widely applied to the fields of protective coatings, adhesives, buildings, high-performance composite materials, electrical engineering, electronic packaging and the like.
However, currently more than 90% of epoxy resins are bisphenol a type epoxy resins made from petroleum, a non-renewable resource. In addition, epoxy thermosetting resins are subject to tradeoffs between heat resistance, strength, and flame retardant properties. Flame retardant properties of epoxy resins are generally improved by introducing flame retardant elements by physical or chemical means, but this generally reduces the heat resistance and mechanical strength of the resin. In practical application, the epoxy resin with high heat resistance, high strength and flame retardance has very urgent requirements, so that the development and utilization of renewable resources for preparing the bio-based epoxy resin with high heat resistance, high strength and intrinsic flame retardance has important scientific and practical significance.
In recent years, significant advances have been made in biobased epoxy thermosetting resins. Various epoxy thermosetting resins have been synthesized from various biological sources. In particular, Epoxy thermoset resins are derived from Biobased monomeric phenols, whether bioconverted or synthesized with Biobased monomers, such as Chen, J, Nie X. Synthesis and Application of Polyoxide Cardanol Ether as Biobased polyol Reactive Diluent for Epoxy Resin [ J].ACS Sustainable Chemistry&Engineering, 2015,3,1164-1171 Cardanol, Fache, M, Austenite R.New vanillin-derived dioxymonomers for the synthesis of biobased themosets [ J]European Polymer Journal, 2015,67,527- & 538 Vanillin, Chen C, Lin C-M, the interaction of activated esters with epoxides for self-secure, highly flex, A2B2-and A3B3-type epoxy compounds[J]. Polymer Chemistry,2019,10,3983-]Nature Communications,2019,10,2107-2116 guaiacol, etc., play an important role in the development of high-performance bio-based epoxy thermosetting resins. However, it is difficult to improve the heat resistance, mechanical strength and flame retardant property of epoxy resin under the condition of maintaining high bio-based content in the above research methods.
So far, no document or patent report exists for preparing the self-curable bio-based epoxy resin containing the active ester side group from the design of the molecular structure. The introduction of the biphenyl structure can effectively improve the heat resistance, the mechanical property and the flame retardant property of the epoxy resin. Most importantly, the amine curing agent and the different reactivity of the ester functional group and the epoxy group can be utilized to form in-situ self-growth phase separation and hydrogen bond action, so that the strength and the flame retardant property are simultaneously improved.
Disclosure of Invention
In order to solve the existing problems, the invention discloses a preparation method of novel bio-based epoxy resin containing active ester side groups based on molecular structure design.
The technical scheme of the invention is as follows:
a novel bio-based epoxy resin containing active ester side groups has the following structure:
a preparation method of novel bio-based epoxy resin containing active ester side groups comprises the following steps:
(1) dissolving magnolol, acetic anhydride and sodium acetate in N, N-methylene acetamide, and reacting at 80-150 deg.C for 7-14 hr under nitrogen atmosphere; after the reaction is finished, washing the reaction solution with water, and drying to obtain an intermediate MGOE;
(2) dissolving the intermediate MGOE obtained in the step (1) in dichloromethane, stirring for 20-60 minutes, and then dropwise adding an epoxy reagent into the MGOE solution under an ice bath condition; after the dropwise addition, the temperature is kept at 20-40 ℃ for reaction 1-4 days; after the reaction, the reaction solution was filtered, and the obtained filtrates were each treated with Na2SO3Reduction of the solution, NaHCO3Sequentially washing with NaCl solution and drying to obtain a novel bio-based epoxy precursor MGOE-EP containing active ester side groups;
(3) uniformly mixing the biological epoxy precursor MGOE-EP obtained in the step (2) with an accelerant, casting in a mould after vacuum defoaming, and curing and forming to obtain a self-curing biological epoxy resin product;
(4) and (3) mixing the biological epoxy precursor MGOE-EP obtained in the step (2) with a petroleum-based curing agent, performing vacuum defoaming, pouring in a mold, and curing and molding to obtain a biological epoxy resin curing product.
Wherein the epoxidation reagent in the step (2) can be organic peroxy acid (m-chloroperoxybenzoic acid, peroxyacetic acid and trifluoroperoxyacetic acid), hydrogen peroxide or an acetone and ketone peroxide system, wherein the molar ratio of acetone to ketone peroxide is 1: 1.
wherein the accelerant in the step (3) is 4-dimethylamino pyridine, 2, 4, 6-tris (dimethylaminomethyl) phenol, pyridine, imidazole, dimethylcyclohexylamine, boron trifluoride amine complex or triethylamine.
The petroleum-based curing agent in the step (4) comprises polyamine and acid anhydride, and is selected from any one of ethylenediamine, isophorone diamine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, phenylketotetracarboxylic dianhydride, and trimellitic anhydride.
In the scheme of the invention, the bio-based epoxy resin with good thermal stability, mechanical strength and flame retardant property is obtained by adjusting the reaction parameters in each reaction step.
The invention further comprises the following optimized technical scheme:
in the optimized scheme, the preparation method of the curing product without adding the curing agent comprises the steps of uniformly mixing the bio-based epoxy resin MGOE-EP and the accelerant (0.1-3% of the MGOE-EP in mass ratio) at the temperature of 100-140 ℃, pouring the mixture into a mold after vacuum defoaming, firstly preserving the heat at the temperature of 100-165 ℃ for 3-7 hours, then preserving the heat at the temperature of 165-190 ℃ for 1-3 hours, then preserving the heat at the temperature of 190-230 ℃ for 1-5 hours, and finally curing at the temperature of 230-250 ℃ for 1-5 hours.
In the optimized scheme, the preparation method of the cured product needing to be added with the petroleum-based curing agent comprises the steps of adding the petroleum-based curing agent into the bio-based epoxy resin MGOE-EP at the temperature of 25-120 ℃, uniformly mixing, defoaming in vacuum, pouring the resin into a mold, preserving heat at 165 ℃ of 100-.
Compared with the prior art, the invention has the advantages that: the invention takes bio-based magnolol and acetic anhydride as raw materials to synthesize the self-curable bio-based epoxy monomer with double functional groups and four functional degrees, self-curing is carried out under the condition of not adding other curing agents, and the cured product is at 800 ℃ (N2Atmosphere) has a carbon residue rate of not less than 50 percent and a glass transition temperature of 205 ℃ at most, which are far higher than the petroleum-based bisphenol A epoxy resin with the largest use amount at present. In addition, common curing agents are selected to cure MGOE-EP in a grading way to form a novel epoxy thermosetting resin, and the formed in-situ phase separation and hydrogen bond interaction can be regulated and controlled by adjusting parameters (the molar ratio of the active ester to the curing agents). Thus, this strategy can simultaneously improve the heat resistance, strength, and flame retardant properties of epoxy resins. The bio-based epoxy resin prepared by the method has excellent heat resistance, mechanical strength and intrinsic flame retardant property, so that the resin has wide application prospect in a plurality of aspects such as automobile adhesives, electronic packaging materials, high-temperature salt spray corrosion resistant coatings, composite material matrixes and the like.
Drawings
FIG. 1 is a chemical shift diagram of a novel bio-based epoxy resin containing pendant active ester groups.
Detailed Description
The following provides specific embodiments of the novel bio-based epoxy monomer containing the active ester side group and the preparation method thereof. It is to be noted that: the following examples are intended only to illustrate the present invention in more detail, and do not narrow the scope of the present invention. Modifications and adaptations of the present invention are within the scope of the invention as claimed and are within the scope of the present invention.
The following further describes a specific embodiment of the present invention with reference to fig. 1 and the technical solution.
Example 1
(1) Synthesis of intermediate MGOE: 200mL of N, N-methylene acetamide, magnolol (10.0g,37.5mmol) and acetic anhydride (53.6g,525mmol) are added into a 500mL three-neck flask, and the mixture is magnetically stirred until the mixture is completely dissolved; introduction of N2Sodium acetate (0.2g) was added thereto, and after stirring for 30 minutes, the reaction temperature was maintained at 100 ℃ and the reaction was continued for 6 hours. After the reaction was completed, the reaction solution was washed with water and dried to obtain intermediate MGOE with a yield of 85%.
(2) Synthesizing a novel bio-based epoxy precursor MGOE-EP containing active ester side groups: dissolving the intermediate MGOE (7.0g and 20mmol) obtained in the step (1) in 10mL of dichloromethane, stirring for 20-60 minutes, and dropwise adding 3-m-chloroperoxybenzoic acid (40mmol dissolved in 130mL of dichloromethane) into the magnolol solution under the ice bath condition; after the dropwise addition, the temperature is kept at room temperature, and the reaction is carried out for 1 day; after the reaction, the reaction solution was filtered, and the obtained filtrates were each treated with Na2SO3Reduction of the solution, NaHCO3And NaCl aqueous solution are sequentially washed and dried to obtain the novel bio-based epoxy precursor MGOE-EP containing the active ester side group with the yield of 82 percent.
(3) MGOE-EP self-curing: 1g of MGOE-EP and 0.5 wt% of 4-dimethylaminopyridine are uniformly mixed, vacuum defoamed for 1 hour at 90 ℃, poured in a mold, and cured by the following steps: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The properties of the obtained self-curing bio-based epoxy resin are as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 354 ℃, and the carbon residue rate at 800 ℃ is 48 percent; the glass transition temperature is 184 ℃; the bending strength is 105 MPa; the flame retardant rating was vertical burn V-1 rating.
(4) Curing of MGOE-EP: 0.13g of curing agent diaminodiphenylmethane was mixed with 1g of MGOE-EP uniformly and the mixture was vacuum-cooled at 90 deg.CAfter defoaming for 1 hour, pouring in a mold, and carrying out a curing procedure: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 348 ℃, and the carbon residue rate at 800 ℃ is 47.7 percent; the glass transition temperature is 167 ℃; the bending strength is 125 MPa; the flame retardant rating was vertical burn V-1 rating.
(5) Curing of MGOE-EP: 0.16g of curing agent diaminodiphenyl sulfone and 1g of MGOE-EP are uniformly mixed, and after vacuum defoaming is carried out for 1 hour at the temperature of 90 ℃, pouring is carried out in a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 350 ℃, and the carbon residue rate at 800 ℃ is 48.2 percent; the glass transition temperature is 174 ℃; the bending strength is 138 MPa; the flame retardant rating was vertical burn V-0 rating.
(6) Curing of MGOE-EP: 0.26g of curing agent diaminodiphenylmethane and 1g of MGOE-EP are uniformly mixed, and after vacuum defoamation is carried out for 1 hour at 90 ℃, the mixture is poured into a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 342 ℃, and the carbon residue rate at 800 ℃ is 44.8 percent; the glass transition temperature is 164 ℃; the bending strength is 134 MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
(7) Curing of MGOE-EP: 0.32g of curing agent diaminodiphenyl sulfone and 1g of MGOE-EP are uniformly mixed, and after vacuum defoaming is carried out for 1 hour at the temperature of 90 ℃, pouring is carried out in a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 355 ℃, and the carbon residue rate at 800 ℃ is 46.5 percent; the glass transition temperature is 170 ℃; bending strength 151 MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
Example 2
(1) Synthesis of intermediate MGOE: 200mL of N, N-methylene acetyl was added to a 500mL three-necked flaskAmine, magnolol (10.0g,37.5mmol), acetic anhydride (53.6g,525mmol), stirring by magnetic force until completely dissolved; introduction of N2Sodium acetate (0.2g) was added thereto, and after stirring for 30 minutes, the reaction temperature was maintained at 130 ℃ and the reaction was continued for 12 hours. After the reaction was completed, the reaction solution was washed with water and dried to obtain intermediate MGOE with a yield of 95%.
(2) Synthesizing a novel bio-based epoxy precursor MGOE-EP containing active ester side groups: dissolving the intermediate MGOE (7.0g and 20mmol) obtained in the step (1) in 10mL of dichloromethane, stirring for 20-60 minutes, and dropwise adding 3-m-chloroperoxybenzoic acid (60mmol dissolved in 130mL of dichloromethane) into the magnolol solution under the ice bath condition; after the dropwise addition, the temperature is kept at room temperature, and the reaction is carried out for 1 day; after the reaction, the reaction solution was filtered, and the obtained filtrates were each treated with Na2SO3Reduction of the solution, NaHCO3And NaCl aqueous solution, and drying to obtain the novel bio-based epoxy precursor MGOE-EP containing the active ester side groups with the yield of 97 percent.
(3) MGOE-EP self-curing: 1g of MGOE-EP and 0.5 wt% of 4-dimethylaminopyridine are uniformly mixed, vacuum defoamed for 1 hour at 90 ℃, poured in a mold, and cured by the following steps: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The properties of the obtained self-curing bio-based epoxy resin are as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 364 ℃, and the carbon residue rate at 800 ℃ is 50.0 percent; the glass transition temperature is 205 ℃; bending strength 117 MPa; the flame retardant rating was vertical burn V-1 rating.
(4) MGOE-EP self-curing: 1g of MGOE-EP and 0.5 wt% of 2, 4, 6-tris (dimethylaminomethyl) phenol are uniformly mixed, vacuum defoamed for 1 hour at 90 ℃, poured in a mold, and cured by the following procedures: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The properties of the obtained self-curing bio-based epoxy resin are as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 360 ℃, and the carbon residue rate at 800 ℃ is 50.8 percent; the glass transition temperature is 201 ℃; the bending strength is 119 MPa; the flame retardant rating was vertical burn V-1 rating.
(5) MGOE-EP self-curing: 1g of MGOE-EP and 0.5 wt% of imidazoleUniformly mixing, defoaming in vacuum at 90 ℃ for 1 hour, and then pouring in a mold, wherein the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The properties of the obtained self-curing bio-based epoxy resin are as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 366 ℃, and the carbon residue rate at 800 ℃ is 51.8 percent; the glass transition temperature is 210 ℃; bending strength 122 MPa; the flame retardant rating was vertical burn V-1 rating.
(6) Curing of MGOE-EP: 0.13g of curing agent diaminodiphenylmethane and 1g of MGOE-EP are uniformly mixed, and after vacuum defoamation is carried out for 1 hour at 90 ℃, pouring is carried out in a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 356 ℃, and the carbon residue rate at 800 ℃ is 49.7 percent; the glass transition temperature is 177 ℃; the bending strength is 135 MPa; the flame retardant rating was vertical burn V-1 rating.
(7) Curing of MGOE-EP: 0.26g of curing agent diaminodiphenylmethane and 1g of MGOE-EP are uniformly mixed, and after vacuum defoamation is carried out for 1 hour at 90 ℃, the mixture is poured into a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 342 ℃, and the carbon residue rate at 800 ℃ is 45.6 percent; the glass transition temperature is 174 ℃; bending strength 154 MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
(8) Curing of MGOE-EP: 0.32g of curing agent diaminodiphenyl sulfone and 1g of MGOE-EP are uniformly mixed, and after vacuum defoaming is carried out for 1 hour at the temperature of 90 ℃, pouring is carried out in a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 355 ℃, and the carbon residue rate at 800 ℃ is 47.5 percent; the glass transition temperature is 190 ℃; bending strength is 159 MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
(9) Curing of MGOE-EP: will be provided with0.16g of curing agent diaminodiphenyl sulfone and 1g of MGOE-EP are uniformly mixed, and after vacuum defoaming is carried out for 1 hour at the temperature of 90 ℃, pouring is carried out in a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 356 ℃, and the carbon residue rate at 800 ℃ is 49.7 percent; the glass transition temperature is 186 ℃; the bending strength is 145 MPa; the flame retardant rating was vertical burn V-0 rating.
(10) Curing of MGOE-EP: 0.3g of curing agent phthalic anhydride, 1g of MGOE-EP and 0.5 wt% of 4-dimethylaminopyridine are uniformly mixed, and after vacuum defoamation for 1 hour at 90 ℃, the mixture is poured in a mould, wherein the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 335 ℃, and the carbon residue rate at 800 ℃ is 44.5 percent; the glass transition temperature is 160 ℃; the bending strength is 141 MPa; the flame retardant rating is the highest V-1 rating for vertical combustion.
(11) Curing of MGOE-EP: 0.2g curing agent tetrahydrophthalic anhydride, 1g MGOE-EP and 0.5 wt% 4-dimethylaminopyridine are mixed uniformly, and after vacuum defoamation for 1 hour at 90 ℃, the mixture is poured in a mould, and the curing procedure is as follows: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours, 200 ℃ for 2 hours and 240 ℃ for 2 hours. The performance of the bio-based epoxy resin MGOE-EP curing system is as follows: n is a radical of2In the atmosphere, the 5 percent thermal weight loss temperature is 333 ℃, and the carbon residue rate at 800 ℃ is 43.5 percent; the glass transition temperature is 152 ℃; the bending strength is 121 MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
Claims (7)
2. a preparation method of novel bio-based epoxy resin containing active ester side groups is characterized by comprising the following steps:
(1) dissolving magnolol, acetic anhydride and sodium acetate in N, N-methylene acetamide, and reacting at 80-150 deg.C for 7-14 hr under nitrogen atmosphere; after the reaction is finished, washing the reaction solution with water, and drying to obtain an intermediate MGOE; wherein the molar ratio of magnolol to acetic anhydride is 1:2-1: 10; the mass of the sodium acetate is 1-10% of that of the magnolol;
(2) carrying out epoxidation reaction on the intermediate MGOE obtained in the step (1) by adopting an epoxidation reagent; the reaction temperature is kept between 20 and 140 ℃, and the reaction time is 8 to 24 hours; after the reaction is finished, purifying and drying the reaction solution to obtain a novel self-curing bio-based epoxy precursor MGOE-EP containing an active ester side group;
(3) and (3) uniformly mixing the biological epoxy precursor MGOE-EP obtained in the step (2) with an accelerant and a petroleum-based curing agent respectively, performing vacuum defoaming, pouring in a mold, and curing and forming to obtain a self-curing biological epoxy resin product and a biological epoxy resin curing product respectively.
3. The preparation method according to claim 2, wherein in the step (2), the epoxidizing agent is organic peroxy acid, hydrogen peroxide or a system of acetone and ketone peroxide, wherein the molar ratio of acetone to ketone peroxide is 1: 1.
4. the method according to claim 3, wherein the organic peroxy acid is 3-m-chloroperoxybenzoic acid, peroxyacetic acid, peroxybenzoic acid, or trifluoroperoxyacetic acid.
5. The process according to any one of claims 2 to 4, wherein in the step (3), the accelerator is 4-dimethylaminopyridine, 2, 4, 6-tris (dimethylaminomethyl) phenol, pyridine, imidazole, dimethylcyclohexylamine, boron trifluoride amine complex or triethylamine; under the condition of 100-140 ℃, uniformly mixing the accelerant and the bio-based epoxy resin MGOE-EP according to the mass ratio of 0.1-3%, pouring the mixture into a mold after vacuum defoamation, firstly preserving heat at 100-165 ℃ for 3-7 hours, then preserving heat at 165-190 ℃ for 1-3 hours, then preserving heat at 190-230 ℃ for 1-5 hours, and finally curing at 230-250 ℃ for 1-5 hours.
6. The method as claimed in any one of claims 2 to 4, wherein in the step (3), the petroleum-based curing agent is polyamine or anhydride, the petroleum-based curing agent is added into the bio-based epoxy resin MGOE-EP at 25-120 ℃, after uniform mixing and vacuum defoaming, the resin is poured into a mold and is subjected to heat preservation at 165 ℃ for 3-7 hours at 100-.
7. The method according to claim 6, wherein the polyamine is ethylenediamine, isophoronediamine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine; the acid anhydride is phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, trimellitic anhydride.
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CN115368322A (en) * | 2022-08-30 | 2022-11-22 | 大连理工大学 | Preparation method of novel bio-based epoxy resin containing cyano structure |
CN116283835A (en) * | 2023-02-24 | 2023-06-23 | 苏州大学 | Biomass epoxy monomer, self-curing epoxy resin and preparation method thereof |
CN117003713A (en) * | 2023-07-14 | 2023-11-07 | 苏州大学 | Biomass epoxy monomer and biomass high-heat-resistance self-repairing epoxy resin |
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