CN111040131A - Synthesis and application of epoxy resin based on catechin - Google Patents
Synthesis and application of epoxy resin based on catechin Download PDFInfo
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- CN111040131A CN111040131A CN201911329150.6A CN201911329150A CN111040131A CN 111040131 A CN111040131 A CN 111040131A CN 201911329150 A CN201911329150 A CN 201911329150A CN 111040131 A CN111040131 A CN 111040131A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/3218—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
Abstract
The invention provides synthesis and application of epoxy resin based on catechin, and particularly provides a catechin epoxidation monomer which has a structure shown in a formula I. The monomer can form the catechin epoxy resin through curing, so that the catechin epoxy resin can be used for preparing aerospace special materials.
Description
Technical Field
The invention relates to the technical field of high-performance polymer manufacturing, in particular to a method for preparing epoxy resin with high glass transition temperature from protocatechuic acid serving as a glucose fermentation product.
Background
Epoxy resin was used as a thermosetting resin, which was first commercialized as a surface coating in 1947. Because the selection range of the curing agent is wide, and the curing agent is selected from alkyl amines, alcohols, thiols, aromatic amines, phenols and the like, the cured epoxy resin has wide controllable thermodynamic and mechanical properties. Therefore, the epoxy resin has the potential for use in different application scenarios. Currently, epoxy resins are commonly used as base resins, adhesives, surface coatings, and in the aerospace field. The largest proportion of the paint is surface paint. In addition, composite materials prepared by epoxy resin doped with inorganic fillers (such as graphene) or glass fibers are also a popular field of the current application. It is reported that today's air and naval airlines use over 1000 pounds of fiber-reinforced epoxy resin per aircraft. Although the application of epoxy resin in the automobile industry is not mass-produced at present, the epoxy resin will be rapidly developed again after mass production in the future.
Although epoxy resins have a wide range of uses, there are still a number of problems with their use. For example, commercial bisphenol A type epoxy resins release trace amounts of bisphenol A during use. Bisphenol a, as a synthetic estrogen, acts like a hormone and may destroy the fragile endocrine system, causing problems in the physical development of adolescents. Canada was the first country in the world to announce banning of bisphenol a on all food packaging and containers (including baby bottles) as early as 2008, followed by australia, the united states, china, etc. in succession by the same act. These problems are also sufficient to illustrate that there are many problems with current commercial epoxies. In addition to safety issues, energy issues are also significant issues that are commonly encountered with other fossil energy-based materials (polyethylene, polypropylene, etc.) in addition to epoxy. With the increasing decrease of petroleum energy, sustainable energy sources, such as solar energy, wind energy, etc., are developed to the utmost in various countries. The field of materials is more focused on renewable resources which can be obtained in large quantities, such as anethole, eugenol, lignin, cellulose and the like, which can be obtained from plants and crops in a large quantity. How to convert them into high-performance materials simply and efficiently to gradually replace the existing fossil energy is the focus of current research.
Disclosure of Invention
The invention aims to provide a novel biomass catechin-based epoxy resin with high glass transition temperature.
In a first aspect of the present invention, a catechin epoxy resin is prepared by curing a monomer represented by the following formula I:
in another preferred embodiment, the resin is prepared by curing with an aromatic amine-based curing agent.
In another preferred embodiment, the epoxy resin is prepared by curing and molding an epoxy monomer of protocatechuic acid shown in formula I and 4, 4' -diaminodiphenylmethane (DDM).
In a second aspect of the present invention, there is provided a method for preparing an epoxy resin as set forth in the first aspect of the present invention, comprising the steps of:
(i) mixing an epoxy monomer according to the first aspect of the present invention with DDM and heating for 40-60 min;
(ii) (ii) forming the mixture obtained in step (i) into a homogeneous transparent solution by ultrasound or organic solvent dissolution;
(iii) removing the solvent from the solution under an inert atmosphere;
(iv) (iv) curing the residue obtained in step (iii) at elevated temperature to obtain the epoxy resin according to the first aspect of the present invention.
In another preferred embodiment, the glass transition temperature of the epoxy resin is more than or equal to 250 ℃ (DMA test).
In another preferred embodiment, the curing and forming are performed by a forming process selected from the group consisting of: and (4) pouring a mold, performing solution spin coating, or performing solution drop coating.
In another preferred example, the mold filling method includes the steps of: the epoxy monomer according to the first aspect of the present invention and DDM are mixed and heated to 40-60 ℃, ultrasonically melted to a uniform and transparent solution, or dissolved in an organic solvent to make the mixture a uniform and transparent solution, and the solvent is removed by heating under nitrogen. The residue is solidified by heating to obtain the solidified resin. The solvent is selected from the following group: cyclohexanone, dichloromethane, trichloromethane, acetone, or combinations thereof.
In another preferred example, the method further comprises: preparing a monomer of formula I by:
(1) under the catalysis of a phase transfer catalyst, protocatechuic acid is reacted with epichlorohydrin to obtain a first reaction mixture;
(2) adding a strong base aqueous solution into the first reaction mixture for reaction to obtain a catechin epoxidation monomer;
in another preferred example, the steps (1) and (2) use epichlorohydrin as a solvent.
In another preferred embodiment, in the step (1), the reaction temperature is 70-140 ℃.
In another preferred embodiment, in the step (1), the reaction temperature is 10 ℃ to 40 ℃.
In another preferred example, the protocatechuic acid used in the step (1) is obtained by fermentation of glucose.
In another preferred embodiment, the phase transfer catalyst is selected from the group consisting of: benzyltriethylammonium chloride, tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, or a combination thereof.
In another preferred embodiment, the total reaction time of steps (1) and (2) is 1 to 10 hours, preferably 2 to 5 hours.
In another preferred embodiment, the aqueous strong base solution is an aqueous strong base solution selected from the group consisting of: potassium hydroxide, sodium hydroxide, or a combination thereof.
In another preferred embodiment, the concentration of the aqueous strong base solution is 10 to 50 wt%, preferably 15 to 25 wt%.
In a third aspect of the present invention, there is provided a catechin epoxy resin, wherein the catechin epoxy resin includes a copolymerization unit represented by the following formula II:
in another preferred embodiment, the copolymerized units are obtained by the method of the second aspect of the present invention.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a CTE plot of a DDM cured protocatechuic acid based epoxy resin and E51 epoxy resin;
figure 2 is a DMA curve of DDM cured protocatechuate-based epoxy resin and E51 epoxy resin.
Detailed Description
The inventors have conducted long-term screening studies on curing agents and found that, when DDM is used as a curing agent and cured and copolymerized with a catechin epoxide, a catechin epoxy resin having a high glass transition temperature, a high storage modulus, and a low thermal expansion coefficient can be obtained with excellent results. Based on the above findings, the inventors have completed the present invention.
Catechin epoxy compound monomer
Protocatechuic acid, also known as 3, 4-dihydroxybenzoic acid, is a compound containing two hydroxyl groups and one carboxyl group, and is well suited for the preparation of epoxy resins. However, the protocatechuic acid commercialized at present is derived from a chemical synthesis process, and the chemical is expensive due to long synthesis route and poor yield and purity. On the other hand, protocatechuic acid is almost used as a pharmaceutical intermediate or fine chemical, and there are few examples of its application to materials. In recent years, it has become possible to obtain desirable protocatechuic acid from inexpensive glucose by a biological fermentation technique. As protocatechuic acid from glucose has price advantage, the development of new application thereof inevitably brings great economic benefit to the biomass protocatechuic acid. The invention prepares and obtains the novel epoxy resin by using protocatechuic acid obtained by biological fermentation.
The invention provides a catechin epoxide monomer, which has a structure shown as the following formula:
the depicted catechin epoxide monomers may be prepared by the following method:
reacting catechin with epoxy chloropropane under the catalysis of a phase transfer catalyst, then closing a ring under the action of alkaline water, and then separating by simple column chromatography to obtain the target catechin epoxy compound monomer.
Wherein, the phase transfer catalyst comprises benzyltriethylammonium chloride, tetrabutylammonium bromide and hexadecyltrimethylammonium chloride. The aqueous alkali solution comprises potassium hydroxide, sodium hydroxide, in a concentration of 10% to 50% by mass, preferably 20%.
The protocatechuic acid used as the raw material of the catechin epoxide monomer is prepared by biological-based fermentation, so that the application range of biological resources is widened, and the cured product can be used as a material in the fields of aerospace and electronics and electricity, and has great application value.
Catechin epoxy resin
The invention belongs to the field of deep processing and utilization of biomass, and particularly relates to a method for preparing epoxy resin by using protocatechuic acid obtained by fermenting glucose, and performance and application of the epoxy resin prepared by the method as a high-performance polymer. Specifically, protocatechuic acid-based epoxy resin is synthesized by a one-pot method by using protocatechuic acid as a raw material and epoxy chloropropane as a solvent. The resin was cured with the general curing agent diaminodiphenylmethane (DDM) and the cured product had a glass transition temperature greater than 250 ℃ (as measured by DMA method), whereas the cured product of the commercial bisphenol a type epoxy resin (E51) exhibited a glass transition temperature below 190 ℃ under the same conditions. In addition, the protocatechuic acid-based epoxy resin cured product also exhibits a high storage modulus and a low linear thermal expansion coefficient. The synthesis method provided by the invention has the advantages of mild reaction conditions, high yield and wide application prospect in the fields of aerospace, electronics and electricity. The invention also widens the application range of biological resources.
The catechol epoxy compound monomer can be directly used for curing with curing agent DDM, and is characterized in that the catechol epoxy compound monomer and the DDM are mixed and heated for 40-60 ultrasonic melting to form uniform and transparent solution, or are dissolved in organic solvent to change the mixture into the uniform and transparent solution, and the solvent is removed by heating under nitrogen. The residue is solidified by heating to obtain the solidified resin. The solvent is selected from the following group: ethyl acetate, dichloromethane, trichloromethane, or combinations thereof.
Compared with the prior art, the invention has the main advantages that:
(1) the method provided by the invention belongs to the field of biomass deep processing and utilization, develops new application of biomass resources, realizes sustainable development, reduces the demand pressure of chemical energy, and promotes green economic development.
(2) The method has the advantages of simple synthesis steps, mild process conditions and high yield, and can be used for industrial large-scale production.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
EXAMPLE 1 Synthesis of protocatechuic acid epoxy monomers
Under the protection of nitrogen gas, magnetons, 100mmol of protocatechuic acid and 94mL of epichlorohydrin are added into a 250mL dry three-necked flask. 5mmol triethylbenzylammonium chloride were subsequently added. Heating to 100 ℃ for reaction for 2 hours, cooling to room temperature, adding 120mL of 20 wt% sodium hydroxide aqueous solution, reacting for 2 hours at room temperature, adding water for washing, extracting with ethyl acetate for multiple times, drying with anhydrous sodium sulfate, concentrating, and carrying out column chromatography to obtain 6.4g of the target colorless oily epoxy compound monomer.
1H NMR(400MHz,DMSO-d6)δ7.62(dd,J＝8.4,2.0Hz,1H),7.52(d,J＝2.1Hz,1H),7.14(d,J＝8.6Hz,1H),4.61(dd,J＝12.4,2.7Hz,1H),4.50–4.39(m,2H),4.06(dd,J＝12.4,6.4Hz,1H),3.92(dddd,J＝21.9,11.4,6.6,1.8Hz,2H),3.39(dqd,J＝7.9,4.0,2.2Hz,3H),2.90–2.81(m,3H),2.74(ddt,J＝7.3,5.0,2.7Hz,3H).13C NMR(101MHz,CDCl3)δ165.71,152.74,148.00,124.53,122.87,115.26,112.91,70.14(d,J＝6.8Hz),69.74(d,J＝6.8Hz),65.36,49.98(d,J＝7.4Hz),49.49,44.63(d,J＝7.5Hz).
EXAMPLE 2 Synthesis of protocatechuic acid epoxy monomers
The experimental procedure is the same as in example 1, except that tetraethylammonium chloride is used in place of triethylbenzylammonium chloride and column chromatography is used to obtain 5.2g of the target monomer.
EXAMPLE 3 Synthesis of protocatechuic acid epoxy monomers
The experimental procedure is the same as in example 1, except that tetrabutylammonium chloride is used in place of triethylbenzylammonium chloride and column chromatography is used to obtain 5.1g of the target monomer.
EXAMPLE 4 Synthesis of protocatechuic acid epoxy monomers
The experimental procedure is substantially the same as in example 1, except that tetrabutylammonium bromide is used instead of triethylbenzylammonium chloride, and column chromatography is carried out to obtain 4.5g of the target monomer.
EXAMPLE 5 Synthesis of protocatechuic acid epoxy monomers
The experimental procedure is substantially the same as in example 1, except that aqueous potassium hydroxide solution is used in place of aqueous sodium hydroxide solution, and column chromatography is performed to obtain 3.9g of the objective monomer.
EXAMPLE 6 curing of protocatechuic acid epoxy resins
The epoxy compound monomer of the target catechin obtained in example 1 and DDM were mixed and heated to 40-60 ℃ and ultrasonically melted to a uniform and transparent solution, or dissolved in an organic solvent to change the mixture to a uniform and transparent solution, and the solvent was removed by heating under nitrogen. The solvent is selected from the following group: ethyl acetate, dichloromethane, trichloromethane or combinations thereof. And (3) heating the residue to 100 ℃ for solidification for 1h, solidifying at 130 ℃ for 3h, and cooling to obtain the solidified resin.
TGA tests were carried out on the resulting resin and showed a five percent thermogravimetric temperature of 321 ℃ and a carbon residue of 27.7%.
Comparative example 1E51 curing of epoxy resin
E51 is a commercially available bisphenol A epoxy resin, and its structure is shown in the following figure (a). The epoxy value is between 0.48 and 0.54.
The E51 epoxy resin was mixed with the DDM in accordance with the mixing procedure in example 6. The residue is heated to 170 ℃ to be solidified for 3h and cooled to obtain solidified resin.
Test examples thermo-mechanical Properties study of cured resin
The resin bars prepared in example 6 and example 7 were subjected to CTE and DMA tests, respectively. The test conditions are from room temperature to 250 ℃ under nitrogen, and the heating rate is 3 ℃/min. The epoxy resin obtained in the present invention was compared with a commercial E51 epoxy resin in terms of thermal expansion coefficient, glass transition temperature and storage modulus, and the results are shown in FIGS. 1 and 2.
As can be seen from FIG. 1, the thermal expansion coefficient of the cured product of the E51 epoxy resin was 72 ppm/deg.C. T isgIs 176 ℃; the protocatechuic acid epoxy resin cured product has a thermal expansion coefficient of 66 ppm/DEG C, a glass transition temperature of more than 200 ℃ and up to 221 ℃.
As can be seen from FIG. 2, E51 epoxy resin cured product Tg189 ℃ C, whereas no significant glass transition temperature was found in the cured product of protocatechuic epoxy resin at 250 ℃. In addition, the protocatechuic acid epoxy resin cured product has a storage modulus of 1.9GPa, which is higher than that of 1.6GPa of the E51 epoxy resin cured product.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. The catechin epoxy resin is characterized by being prepared by curing a monomer shown as the following formula I:
2. the catechin epoxy resin according to claim 1, wherein said epoxy resin is prepared by curing and molding a protocatechuic acid epoxidizing monomer represented by formula I with 4, 4' -diaminodiphenylmethane (DDM).
3. The method for preparing an epoxy resin according to claim 1, comprising the steps of:
(i) mixing the epoxy monomer of claim 1 and DDM and heating for 40-60 min;
(ii) (ii) forming the mixture obtained in step (i) into a homogeneous transparent solution by ultrasound or organic solvent dissolution;
(iii) removing the solvent from the solution under an inert atmosphere;
(iv) (iv) curing the residue obtained in step (iii) at elevated temperature to obtain the epoxy resin of claim 1.
4. The method of claim 3, further comprising: preparing a monomer of formula I by:
(1) under the catalysis of a phase transfer catalyst, protocatechuic acid is reacted with epichlorohydrin to obtain a first reaction mixture;
(2) adding a strong base aqueous solution into the first reaction mixture for reaction to obtain a catechin epoxidation monomer;
5. the process of claim 1, wherein steps (1) and (2) use epichlorohydrin as the solvent.
6. The method of claim 1, wherein in step (1), the reaction temperature is in the range of 70 ℃ to 140 ℃.
7. The method of claim 1, wherein in step (1), the reaction temperature is in the range of 10 ℃ to 40 ℃.
8. The method of claim 1, wherein the phase transfer catalyst is selected from the group consisting of: benzyltriethylammonium chloride, tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, or a combination thereof.
9. The method of claim 1, wherein the aqueous strong base solution is an aqueous strong base solution selected from the group consisting of: potassium hydroxide, sodium hydroxide, or a combination thereof.
10. The catechin epoxy resin is characterized by comprising a copolymerization unit shown as the following formula II:
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| CN201911329150.6A CN111040131A (en) | 2019-12-20 | 2019-12-20 | Synthesis and application of epoxy resin based on catechin |
| PCT/CN2020/138136 WO2021121426A1 (en) | 2019-12-20 | 2020-12-21 | Synthesis and use of protocatechuic acid-based epoxy resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021121426A1 (en) * | 2019-12-20 | 2021-06-24 | 中国科学院上海有机化学研究所 | Synthesis and use of protocatechuic acid-based epoxy resin |
| CN113024380A (en) * | 2021-03-04 | 2021-06-25 | 中国科学院天津工业生物技术研究所 | Synthesis and application of protocatechuic acid-based acrylic resin |
| CN115894403A (en) * | 2022-12-20 | 2023-04-04 | 中国科学院天津工业生物技术研究所 | Synthesis and application of protocatechuic acid-based resin auxiliary agent |
| CN116444462A (en) * | 2022-02-25 | 2023-07-18 | 南京工业大学 | Novel isovanillin epoxy resin monomer and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560996B (en) * | 2022-03-29 | 2023-07-21 | 中海石油(中国)有限公司 | Degradable biological epoxy resin prepared by tannic acid curing and high Wen Dulou application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040082720A1 (en) * | 2000-07-18 | 2004-04-29 | Fmc Corporation | Adducts of amine-terminated polyolefins and epoxides |
| CN107365410A (en) * | 2016-05-12 | 2017-11-21 | 常州杰美新高分子科技有限公司 | A kind of resources conservation, the plant base catalysis material of efficient green |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58210078A (en) * | 1982-05-31 | 1983-12-07 | Kanegafuchi Chem Ind Co Ltd | Novel epoxy resin and its preparation |
| CN102276788B (en) * | 2011-05-09 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Epoxy resin based on gallic acids as well as preparation method and application thereof |
| CN106543413A (en) * | 2016-12-07 | 2017-03-29 | 陕西高新实业有限公司 | The preparation method of novel non-toxic gallic acid epoxy resin stabilizer |
| CN111040131A (en) * | 2019-12-20 | 2020-04-21 | 中国科学院上海有机化学研究所 | Synthesis and application of epoxy resin based on catechin |
-
2019
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-
2020
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040082720A1 (en) * | 2000-07-18 | 2004-04-29 | Fmc Corporation | Adducts of amine-terminated polyolefins and epoxides |
| CN107365410A (en) * | 2016-05-12 | 2017-11-21 | 常州杰美新高分子科技有限公司 | A kind of resources conservation, the plant base catalysis material of efficient green |
Non-Patent Citations (1)
| Title |
|---|
| CHAHINEZ AOUF ET AL.: "Study of the O-glycidylation of natural phenolic compounds.The relationship between the phenolic structure and the reaction mechanism", 《TETRAHEDRON》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021121426A1 (en) * | 2019-12-20 | 2021-06-24 | 中国科学院上海有机化学研究所 | Synthesis and use of protocatechuic acid-based epoxy resin |
| CN113024380A (en) * | 2021-03-04 | 2021-06-25 | 中国科学院天津工业生物技术研究所 | Synthesis and application of protocatechuic acid-based acrylic resin |
| CN116444462A (en) * | 2022-02-25 | 2023-07-18 | 南京工业大学 | Novel isovanillin epoxy resin monomer and preparation method thereof |
| CN116444462B (en) * | 2022-02-25 | 2024-05-03 | 南京工业大学 | Novel isovanillin epoxy resin monomer and preparation method thereof |
| CN115894403A (en) * | 2022-12-20 | 2023-04-04 | 中国科学院天津工业生物技术研究所 | Synthesis and application of protocatechuic acid-based resin auxiliary agent |
| CN115894403B (en) * | 2022-12-20 | 2024-03-12 | 中国科学院天津工业生物技术研究所 | Synthesis and application of protocatechuic acid-based resin auxiliary agent |
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| WO2021121426A1 (en) | 2021-06-24 |
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