CN113999191B - 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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- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
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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
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Abstract
The invention provides a novel bio-based epoxy resin containing active ester side groups and a preparation method thereof, belonging to the technical field of material science. Using magnolol and acetic anhydride as biological base raw materials, and using sodium acetate as a catalyst to obtain an intermediate containing acetyl ester side groups through an acetylation reaction; under the action of an oxidant, double bonds of the intermediate are epoxidized to obtain the bio-based epoxy precursor containing acetyl ester side groups. The bio-based epoxy resin having a high glass transition temperature is prepared by the reaction of acetyl groups and epoxy groups without adding any curing agent. Meanwhile, the different reactivity 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 bonding, so that the enhancement and the intrinsic flame retardance of the epoxy resin are realized at the same time. The simple strategy provides a new idea for solving the key problem that the heat resistance, the strength and the 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 in particular 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, adhesion, dimensional stability, and electrical insulation, and therefore are widely used in the fields of protective coatings, adhesives, construction, high-performance composite materials, electrical engineering, electronic packaging, and the like.
However, more than 90% of the current epoxy resins are bisphenol a type epoxy resins made from non-renewable resource petroleum. Furthermore, epoxy thermosets suffer from a tradeoff 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 is very urgent to be required, 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 have important scientific and practical significance.
In recent years, a great progress has been made in biobased epoxy thermosetting resins. Various epoxy thermosetting resins are synthesized from various biological sources. In particular, epoxy thermosets are derived from biobased monomeric phenols, whether bioconverted or synthesized with biobased monomers, e.g., chen, J, nie X. Synthesis and Application of Polyepoxide Cardanol Glycidyl Ether as Biobased Polyepoxide Reactive Diluent for Epoxy Resin [ J].ACS Sustainable Chemistry&Engineering, 2015,3,1164-1171. Cardanol, fache, M, auvergne R.New vanilin-derived diepoxy monomers for the synthesis of biobased thermosets [ J]European Polymer Journal, 2015,67,527-538 vanillin, chen C, lin C-M.the reaction of activated esters with epoxides for self-curable, high flexible, A 2 B 2 -and A 3 B 3 -type epoxy compounds[J]Polymer Chemistry,2019,10,3983-3995 eugenol, qi Y, wang J.Synthesis of an aromatic N-heterocycle derived from biomass and its use as a polymer feedstock [ J ]]Nature Communications,2019,10,2107-2116 guaiacol and the like 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 the epoxy resin at the same time under the condition of maintaining high bio-based content in the above-mentioned research method.
Up to now, no literature and patent report is made on the preparation of self-curable bio-based epoxy resin containing active ester side groups from the standpoint of molecular structural design. The introduction of the biphenyl structure can effectively improve the heat resistance, mechanical property and flame retardance of the epoxy resin. Most importantly, the different reactivity of amine curing agents and ester functional groups with epoxy groups can be utilized to form 'in situ' self-growth phase separation and hydrogen bonding to achieve the simultaneous improvement of strength and flame retardant properties.
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 from the point of 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 for 7-14 hours under the nitrogen atmosphere at the temperature of 80-150 ℃; washing the reaction liquid with water after the reaction is finished, 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 epoxidation reagent into the MGOE solution under ice bath conditions; after the dripping is completed, the temperature is kept at 20-40 ℃ and the reaction is carried out for 1-4 days; after completion of the reaction, the reaction mixture was filtered, and the obtained filtrates were each treated with Na 2 SO 3 Solution reduction of NaHCO 3 And NaCl solution are washed and dried in sequence to obtain a novel bio-based epoxy precursor MGOE-EP containing active ester side groups;
(3) Uniformly mixing the biobased epoxy precursor MGOE-EP obtained in the step (2) with an accelerator, performing vacuum defoaming, pouring in a mould, and performing curing molding to obtain a self-curing biobased epoxy resin product;
(4) Mixing the biobased epoxy precursor MGOE-EP obtained in the step (2) with a petroleum-based curing agent, vacuum defoaming, pouring in a mold, and curing and forming to obtain the biobased epoxy resin cured product.
Wherein the epoxidation reagent in the step (2) can be organic peroxyacid (m-chloroperoxybenzoic acid, peroxyacetic acid and trifluoroperoxyacetic acid), hydrogen peroxide or an acetone and ketone peroxide system, and the molar ratio of the acetone to the ketone peroxide is 1:1.
wherein the accelerator in the step (3) is 4-dimethylaminopyridine, 2.4.6-tris (dimethylaminomethyl) phenol, pyridine, imidazole, dimethylcyclohexylamine, boron trifluoride amine complex or triethylamine.
Wherein the petroleum-based curing agent in the step (4) comprises polyamine and anhydride, and is selected from any one of ethylenediamine, isophorone diamine, m-xylylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride and trimellitic anhydride.
In the scheme, 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 an optimized scheme, the preparation method of the cured product without adding the curing agent comprises the steps of uniformly mixing the bio-based epoxy resin MGOE-EP and the accelerator (0.1-3% of the mass ratio of the MGOE-EP) at 100-140 ℃, pouring the mixture into a mold after vacuum defoaming, 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.
In an optimized scheme, the preparation method of the cured product 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, vacuum defoaming, pouring the resin into a mold, preserving heat for 3-7 hours at the temperature of 100-165 ℃, preserving heat for 1-3 hours at the temperature of 165-190 ℃, preserving heat for 1-5 hours at the temperature of 190-230 ℃, and finally curing for 1-5 hours at the temperature of 230-250 ℃.
Compared with the prior art, the invention has the advantages that: the invention synthesizes difunctional tetrafunctional self-curable biobased epoxy monomer by taking biobased magnolol and acetic anhydride as raw materials, and carries out self-curing under the condition of no need of adding other curing agents, and the cured product is prepared by the method of the invention under the temperature of 800 ℃ (N 2 Atmosphere), the carbon residue rate is not lower than 50%, the glass transition temperature can reach 205 ℃ at the highest, and the values are far higher than those of the prior artThe greatest amount of petroleum-based bisphenol a type epoxy resin. In addition, the common curing agent is selected to carry out fractional curing on the MGOE-EP to form the 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 agent). Thus, this strategy can simultaneously improve the heat resistance, strength, and flame retardant properties of the epoxy resin. 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 prospects in various 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 a specific embodiment of a novel bio-based epoxy monomer containing an active ester side group and a preparation method thereof. It is necessary to point out that: the following examples are provided only to illustrate the present invention in more detail and are not intended to limit the scope of the invention. Modifications and adaptations can be made without departing from the spirit of the invention and are within the scope of the invention as claimed.
The following describes the 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-methyleneacetamides, magnolol (10.0 g,37.5 mmol) and acetic anhydride (53.6 g,525 mmol) are firstly added into a 500mL three-neck flask, and magnetically stirred, and after the mixture is completely dissolved; introducing N 2 Sodium acetate (0.2 g) was added thereto, and after stirring for 30 minutes, the reaction temperature was kept at 100℃and the reaction was continued for 6 hours. After the reaction, the reaction solution was washed with water and dried to obtain intermediate MGOE in 85% yield.
(2) Synthesis of novel biobased epoxy precursor MGOE-EP containing pendant active ester groups: intermediate MGOE (7.0 g,20 mmol) obtained in step (1) was dissolved in 10mL of dichloromethane and after stirring for 20-60 min 3-m-chloroperoxybenzoic acid (40 mmol in 130mL of di)Methyl chloride) is dropwise added into magnolol solution under ice bath condition; after the dripping is completed, the temperature is kept at room temperature, and the reaction is carried out for 1 day; after completion of the reaction, the reaction mixture was filtered, and the obtained filtrates were each treated with Na 2 SO 3 Solution reduction of NaHCO 3 And NaCl aqueous solution are washed and dried in sequence to obtain the novel bio-based epoxy precursor MGOE-EP containing the active ester side group, and the yield is 82%.
(3) MGOE-EP self-curing: 1g of MGOE-EP and 0.5wt% of 4-dimethylaminopyridine were uniformly mixed and vacuum defoamed at 90℃for 1 hour, and then poured into a mold, and the curing procedure was: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The properties of the resulting self-curing biobased epoxy resin were: n (N) 2 Under the atmosphere, the 5% thermal weight loss temperature is 354 ℃, and the carbon residue rate at 800 ℃ is 48%; the glass transition temperature is 184 ℃; bending strength 105MPa; the flame retardant grade is V-1 grade of vertical burning.
(4) MGOE-EP curing: uniformly mixing 0.13g of curing agent diaminodiphenylmethane with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture, wherein 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 biobased epoxy MGOE-EP curing system is: n (N) 2 Under the atmosphere, the 5% thermal weight loss temperature is 348 ℃, and the carbon residue rate at 800 ℃ is 47.7%; the glass transition temperature is 167 ℃; bending strength 125MPa; the flame retardant grade is V-1 grade of vertical burning.
(5) MGOE-EP curing: uniformly mixing 0.16g of curing agent diamino diphenyl sulfone with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture by the following steps: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The performance of the biobased epoxy MGOE-EP curing system is: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 350 ℃, and the carbon residue rate at 800 ℃ is 48.2%; the glass transition temperature is 174 ℃; bending strength 138MPa; the flame retardant grade is V-0 grade of vertical burning.
(6) MGOE-EP curing: uniformly mixing 0.26g of curing agent diaminodiphenylmethane with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture, wherein the curing procedure is as follows: 135 DEG CThe temperature is kept for 2 hours, the temperature is kept at 175 ℃ for 2 hours, and the temperature is kept at 200 ℃ for 2 hours. The performance of the biobased epoxy MGOE-EP curing system is: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 342 ℃, and the carbon residue rate at 800 ℃ is 44.8%; the glass transition temperature is 164 ℃; bending strength 134MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
(7) MGOE-EP curing: uniformly mixing 0.32g of curing agent diamino diphenyl sulfone with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture by the following steps: the temperature is kept at 135 ℃ for 2 hours, 175 ℃ for 2 hours and 200 ℃ for 2 hours. The performance of the biobased epoxy MGOE-EP curing system is: n (N) 2 Under atmosphere, the 5% thermal weight loss temperature is 355 ℃, and the carbon residue rate at 800 ℃ is 46.5%; the glass transition temperature is 170 ℃; flexural strength 151MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
Example 2
(1) Synthesis of intermediate MGOE: 200mL of N, N-methyleneacetamides, magnolol (10.0 g,37.5 mmol) and acetic anhydride (53.6 g,525 mmol) are firstly added into a 500mL three-neck flask, and magnetically stirred, and after the mixture is completely dissolved; introducing N 2 Sodium acetate (0.2 g) was added thereto, and after stirring for 30 minutes, the reaction temperature was kept at 130℃and the reaction was continued for 12 hours. After the reaction, the reaction solution is washed with water and dried to obtain the intermediate MGOE with a yield of 95%.
(2) Synthesis of novel biobased epoxy precursor MGOE-EP containing pendant active ester groups: dissolving intermediate MGOE (7.0 g,20 mmol) obtained in the step (1) in 10mL of dichloromethane, stirring for 20-60 minutes, and then dropwise adding 3-m-chloroperoxybenzoic acid (60 mmol dissolved in 130mL of dichloromethane) into magnolol solution under ice bath condition; after the dripping is completed, the temperature is kept at room temperature, and the reaction is carried out for 1 day; after completion of the reaction, the reaction mixture was filtered, and the obtained filtrates were each treated with Na 2 SO 3 Solution reduction of NaHCO 3 And NaCl aqueous solution are washed and dried in sequence to obtain the novel bio-based epoxy precursor MGOE-EP containing the active ester side group, and the yield is 97%.
(3) MGOE-EP self-curing: 1g of MGOE-EP and 0.5wt% of 4-dimethylaminopyridine were mixed homogeneously and defoamed in vacuo at 90℃for 1 hourThen casting 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 properties of the resulting self-curing biobased epoxy resin were: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 364 ℃, and the carbon residue rate at 800 ℃ is 50.0%; the glass transition temperature is 205 ℃; the bending strength is 117MPa; the flame retardant grade is V-1 grade of vertical burning.
(4) MGOE-EP self-curing: 1g of MGOE-EP and 0.5wt% of 2, 4, 6-tris (dimethylaminomethyl) phenol were mixed uniformly and defoamed in vacuo at 90℃for 1 hour, and then poured into a mold, followed by a curing procedure of: 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 resulting self-curing biobased epoxy resin were: n (N) 2 Under atmosphere, the 5% thermal weight loss temperature is 360 ℃, and the carbon residue rate at 800 ℃ is 50.8%; the glass transition temperature is 201 ℃; bending strength 119MPa; the flame retardant grade is V-1 grade of vertical burning.
(5) MGOE-EP self-curing: 1g of MGOE-EP and 0.5wt% imidazole were mixed homogeneously, vacuum defoamed at 90℃for 1 hour, poured into a mold, and cured 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 resulting self-curing biobased epoxy resin were: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 366 ℃, and the carbon residue rate at 800 ℃ is 51.8%; the glass transition temperature is 210 ℃; bending strength 122MPa; the flame retardant grade is V-1 grade of vertical burning.
(6) MGOE-EP curing: uniformly mixing 0.13g of curing agent diaminodiphenylmethane with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture, 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 biobased epoxy MGOE-EP curing system is: n (N) 2 Under the atmosphere, the 5% thermal weight loss temperature is 356 ℃, and the carbon residue rate at 800 ℃ is 49.7%; the glass transition temperature is 177 ℃; bending strength 135MPa; the flame retardant grade is V-1 grade of vertical burning.
(7) MGOE-EP curing: uniformly mixing 0.26g of curing agent diaminodiphenylmethane with 1g of MGOE-EP at 90 DEG CAfter vacuum defoamation for 1 hour, pouring in a mould, and solidifying 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 performance of the biobased epoxy MGOE-EP curing system is: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 342 ℃, and the carbon residue rate at 800 ℃ is 45.6%; the glass transition temperature is 174 ℃; the bending strength is 154MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
(8) MGOE-EP curing: uniformly mixing 0.32g of curing agent diamino diphenyl sulfone with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture 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 performance of the biobased epoxy MGOE-EP curing system is: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 355 ℃, and the carbon residue rate at 800 ℃ is 47.5%; the glass transition temperature is 190 ℃; bending strength 159MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
(9) MGOE-EP curing: uniformly mixing 0.16g of curing agent diamino diphenyl sulfone with 1g of MGOE-EP, vacuum defoaming for 1 hour at 90 ℃, pouring in a mould, and curing the mixture 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 performance of the biobased epoxy MGOE-EP curing system is: n (N) 2 Under the atmosphere, the 5% thermal weight loss temperature is 356 ℃, and the carbon residue rate at 800 ℃ is 49.7%; the glass transition temperature is 186 ℃; bending strength 145MPa; the flame retardant grade is V-0 grade of vertical burning.
(10) MGOE-EP curing: 0.3g of curing agent phthalic anhydride, 1g of MGOE-EP and 0.5wt% of 4-dimethylaminopyridine are uniformly mixed, and after vacuum defoamation for 1 hour at 90 ℃, the mixture is poured into a mold, 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 biobased epoxy MGOE-EP curing system is: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 335 ℃, and the carbon residue rate at 800 ℃ is 44.5%; the glass transition temperature is 160 ℃; bending strength 141MPa; the flame retardant rating is the highest V-1 rating for vertical combustion.
(11)MGOE-EP curing: 0.2g of curing agent tetrahydrophthalic anhydride, 1g of MGOE-EP and 0.5wt% of 4-dimethylaminopyridine are uniformly mixed, and after vacuum defoamation for 1 hour at 90 ℃, the mixture is poured into a mold, 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 biobased epoxy MGOE-EP curing system is: n (N) 2 In the atmosphere, the 5% thermal weight loss temperature is 333 ℃, and the carbon residue rate at 800 ℃ is 43.5%; the glass transition temperature is 152 ℃; bending strength 121MPa; the flame retardant rating is the highest V-0 rating for vertical combustion.
Claims (3)
1. The preparation method of the bio-based epoxy resin containing the active ester side group is characterized in that a bio-based epoxy precursor MGOE-EP of the bio-based epoxy resin containing the active ester side group has the following structure:
the preparation method comprises the following steps:
(1) Dissolving magnolol, acetic anhydride and sodium acetate in N, N-methylene acetamide, and reacting for 7-14 hours under the nitrogen atmosphere at the temperature of 80-150 ℃; washing the reaction liquid with water after the reaction is finished, and drying to obtain an intermediate MGOE; wherein, the mol ratio of magnolol to acetic anhydride is 1:2-1:10; the mass of the sodium acetate is 1-10% of the mass of the magnolol;
(2) Performing an epoxidation reaction on the intermediate MGOE obtained in the step (1) by adopting an epoxidation reagent; the reaction temperature is kept at 20-140 ℃ and the reaction time is 8-24 hours; purifying and drying the reaction liquid after the reaction is finished to obtain an active ester side group-containing self-curable bio-based epoxy precursor MGOE-EP;
wherein the epoxidation reagent is an organic peroxyacid, hydrogen peroxide or acetone and ketone peroxide system, and the molar ratio of the acetone to the ketone peroxide is 1:1, a step of;
(3) Uniformly mixing the biobased epoxy precursor MGOE-EP obtained in the step (2) with an accelerator and a petroleum-based curing agent respectively, performing vacuum defoaming, pouring in a mold, and performing curing molding to obtain a self-curing biobased epoxy resin product and a biobased epoxy resin curing product respectively;
in the step (3), the promoter is 4-dimethylaminopyridine, 2.4.6-tris (dimethylaminomethyl) phenol, pyridine, imidazole, dimethylcyclohexylamine, boron trifluoride amine complex or triethylamine; uniformly mixing an accelerator and a biobased epoxy precursor MGOE-EP according to the mass ratio of 0.1-3% at 100-140 ℃, pouring the mixture into a mold after vacuum defoaming, 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;
the petroleum-based curing agent is polyamine or anhydride, the petroleum-based curing agent is added into the bio-based epoxy precursor MGOE-EP at 25-120 ℃, after uniform mixing and vacuum defoaming, the resin is poured into a mold, and is kept at 100-165 ℃ for 3-7 hours, then is kept at 165-190 ℃ for 1-3 hours, then is kept at 190-230 ℃ for 1-5 hours, and finally is cured at 230-250 ℃ for 1-5 hours.
2. The method of claim 1, wherein the organic peroxyacid is 3-m-chloroperoxybenzoic acid, peroxyacetic acid, peroxybenzoic acid, or trifluoroperoxyacetic acid.
3. The method according to claim 1, wherein the polyamine is ethylenediamine, isophoronediamine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone or m-phenylenediamine; the anhydride is phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic dianhydride or trimellitic anhydride.
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| KR101386068B1 (en) * | 2011-01-26 | 2014-04-21 | 주식회사 바이오랜드 | Novel 4-Ｏ-Methylhonokiol Derivatives and Composition for Treating Inflammatory Disease Comprising the Same as Active Ingredient |
| CN110408003B (en) * | 2019-07-02 | 2022-03-29 | 大连理工大学 | Preparation method of bio-based epoxy resin based on natural magnolia bark derivatives |
| CN110511360B (en) * | 2019-08-30 | 2021-12-10 | 广东同宇新材料有限公司 | Active ester resin and preparation method and application thereof |
| CN112457472B (en) * | 2020-11-25 | 2022-10-04 | 广东工业大学 | Low-viscosity bio-based magnolol epoxy resin and preparation method thereof |
| CN112876509B (en) * | 2021-04-13 | 2021-10-22 | 南京工业大学 | Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin |
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