WO2021121426A1 - Synthèse et utilisation de résine époxyde à base d'acide protocatéchique - Google Patents

Synthèse et utilisation de résine époxyde à base d'acide protocatéchique Download PDF

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Publication number
WO2021121426A1
WO2021121426A1 PCT/CN2020/138136 CN2020138136W WO2021121426A1 WO 2021121426 A1 WO2021121426 A1 WO 2021121426A1 CN 2020138136 W CN2020138136 W CN 2020138136W WO 2021121426 A1 WO2021121426 A1 WO 2021121426A1
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WIPO (PCT)
Prior art keywords
epoxy resin
protocatechin
monomer
protocatechuic acid
epoxy
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PCT/CN2020/138136
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English (en)
Chinese (zh)
Inventor
房强
陈星融
王钦宏
孙晶
顾群
侯加仁
高俊飞
方林玄
Original Assignee
中国科学院上海有机化学研究所
中国科学院天津工业生物技术研究所
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Publication of WO2021121426A1 publication Critical patent/WO2021121426A1/fr

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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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the technical field of high-performance polymer manufacturing, in particular to a method for preparing an epoxy resin with a high glass transition temperature starting from the glucose fermentation product protocatechin.
  • epoxy resin As a thermosetting resin, epoxy resin was first used as a surface coating in 1947 and realized its first commercial application. Due to the wide selection of curing agents, from alkyl amines, alcohols, mercaptans to aromatic amines, phenols, etc., the cured epoxy resin has a wide range of adjustable thermodynamic and mechanical properties. Therefore, it means that epoxy resin has the potential to be used in different application scenarios.
  • epoxy resins are commonly used as base resins, adhesives, surface coatings, and include aerospace fields. The largest proportion of its applications is still surface coatings.
  • composite materials made of epoxy resin mixed with inorganic fillers (graphene, etc.) or glass fibers are also a hot field of its current application.
  • epoxy resin has a wide range of uses, there are still many problems with its use.
  • commercialized bisphenol A epoxy resins release trace amounts of bisphenol A during use.
  • bisphenol A can act like a hormone, which may damage the fragile endocrine system and cause problems in the physical development of adolescents.
  • Canada became the first country in the world to publicly announce the ban on BPA on all food packaging and containers (including milk bottles). Subsequently, Australia, the United States, and China have successively made the same measures.
  • the purpose of the present invention is to provide a new type of epoxy resin with high glass transition temperature based on biomass protocatechin.
  • the first aspect of the present invention provides a protocatechin epoxy resin, which is prepared by curing with a monomer represented by the following formula I:
  • the resin is prepared by curing with an aromatic amine curing agent.
  • the epoxy resin is prepared by curing and molding the protocatechuic acid epoxidized monomer as shown in formula I and 4,4'-diaminodiphenylmethane (DDM) .
  • the second aspect of the present invention provides a method for preparing the epoxy resin as shown in the first aspect of the present invention, including the steps:
  • step (ii) Dissolving by ultrasonic or organic solvent to make the mixture obtained in step (i) form a uniform and transparent solution;
  • the glass transition temperature of the epoxy resin is ⁇ 250°C (tested by DMA method).
  • the curing and molding are performed by a molding process selected from the group consisting of injection molding, solution spin coating, or solution drip coating.
  • the molding method includes the steps of: mixing the epoxy monomer and DDM as described in the first aspect of the present invention and heating to 40-60°C, ultrasonically melting into a uniform and transparent solution, or dissolving in In the organic solvent, the mixture becomes a uniform and transparent solution, and the solvent is removed by heating under nitrogen. The residue is cured at elevated temperature to obtain a cured resin.
  • the solvent is selected from the following group: cyclohexanone, dichloromethane, chloroform, acetone, or a combination thereof.
  • the method further comprises: preparing the monomer of formula I by the following steps:
  • the reaction temperature is 70°C-140°C.
  • the reaction temperature is 10°C-40°C.
  • the protocatechuic acid used in the step (1) is obtained from glucose fermentation.
  • the phase transfer catalyst is selected from the following group: benzyltriethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, cetyltrimethylammonium chloride , Or a combination thereof.
  • the total reaction time of the steps (1) and (2) is 1 to 10 hours, preferably 2 to 5 hours.
  • the strong alkaline aqueous solution is a strong alkaline aqueous solution selected from the group consisting of potassium hydroxide, sodium hydroxide, or a combination thereof.
  • the concentration of the strong alkali aqueous solution is 10-50wt%, preferably 15-25wt%.
  • the third aspect of the present invention provides a protocatechin epoxy resin, characterized in that the protocatechin epoxy resin includes a copolymer unit represented by the following formula II:
  • the copolymer unit is obtained by the preparation method of the second aspect of the present invention.
  • Figure 1 is the CTE curve of DDM curing protocatechin-based epoxy resin and E51 epoxy resin
  • Figure 2 shows the DMA curves of DDM cured protocatechin-based epoxy resin and E51 epoxy resin.
  • the inventor found that when DDM is used as the curing agent to perform curing and copolymerization with protocatechuic acid epoxide, it can achieve excellent results with high glass transition temperature and high energy storage. Modulus, and low thermal expansion coefficient of protocatechin epoxy resin. Based on the above findings, the inventor completed the present invention.
  • Protocatechuic acid also known as 3,4-dihydroxybenzoic acid
  • the currently commercialized protocatechuic acid all come from chemical synthesis processes. Due to the long synthetic route, unsatisfactory yield and purity, this chemical is expensive.
  • protocatechuic acid is almost always used as a pharmaceutical intermediate or fine chemical, and there are few examples of its application in materials.
  • through biological fermentation technology starting from cheap glucose, it is possible to obtain satisfactory protocatechuic acid.
  • the present invention uses the protocatechuic acid obtained by biological fermentation to prepare a novel epoxy resin.
  • the present invention provides a protocatechin epoxide monomer, which has a structure shown in the following formula:
  • the shown protocatechin epoxide monomer can be prepared by the following method:
  • Protocatechin is reacted with epichlorohydrin under the catalysis of a phase transfer catalyst, and then the ring is closed under the action of alkaline water, and then separated by simple column chromatography to obtain the target protocatechin epoxy compound. body.
  • the phase transfer catalyst includes benzyl triethyl ammonium chloride, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, and cetyl trimethyl ammonium chloride.
  • the alkaline aqueous solution includes potassium hydroxide and sodium hydroxide, and its mass concentration is 10% to 50%, preferably 20%.
  • the raw material protocatechin used in the protocatechuic acid epoxide monomer of the present invention is produced by bio-based fermentation, thereby broadening the application range of biological resources, and the cured product can be used as a material in the fields of aerospace and electronics , Has great application value.
  • the invention belongs to the field of deep processing and utilization of biomass, and specifically relates to a method for preparing epoxy resin by using protocatechuic acid obtained by glucose fermentation, and the performance and application of the epoxy resin prepared by the method as a high-performance polymer.
  • the protocatechin-based epoxy resin is synthesized in a one-pot method using protocatechin as the raw material and epichlorohydrin as the solvent.
  • the resin is cured with the universal curing agent diaminodiphenylmethane (DDM), and the glass transition temperature of the cured product is greater than 250°C (DMA method test), and under the same conditions, the commercial bisphenol A epoxy resin (E51) is cured
  • the product shows a glass transition temperature below 190°C.
  • the cured product of protocatechin-based epoxy resin also exhibits a high storage modulus and a low linear thermal expansion coefficient.
  • the synthesis method provided by the present invention has mild reaction conditions and high yield, and has great application prospects in the fields of aerospace and electronics.
  • the invention also broadens the application range of biological resources.
  • the protocatechin epoxy compound monomer can be directly used for curing with the curing agent DDM, and is characterized in that the protocatechin epoxy compound monomer and DDM are mixed and heated 40-60 ultrasonically to melt into a uniform and transparent solution , Or dissolved in an organic solvent to make the mixture a uniform and transparent solution, and remove the solvent by heating under nitrogen. The residue is heated and cured to obtain a cured resin.
  • the solvent is selected from the group consisting of ethyl acetate, dichloromethane, chloroform, or a combination thereof.
  • the main advantages of the present invention include:
  • the method provided by the present invention belongs to the deep processing and utilization of biomass, develops new applications of biomass resources, realizes sustainable development, reduces the demand pressure of chemical energy, and promotes the development of green economy.
  • the present invention has simple synthesis steps, mild process conditions and high yield, and can be used for industrialized large-scale production.
  • the experimental method is the same as in Example 1, except that tetraethyl ammonium chloride is used instead of triethyl benzyl ammonium chloride, and 5.2 g of target monomer is obtained by column chromatography.
  • the experimental method is the same as in Example 1, except that tetrabutylammonium chloride is used instead of triethylbenzylammonium chloride, and 5.1 g of the target monomer is obtained by column chromatography.
  • the experimental method is basically the same as in Example 1, except that tetrabutylammonium bromide is used instead of triethylbenzylammonium chloride, and 4.5g of the target monomer is obtained by column chromatography.
  • the experimental method is basically the same as that in Example 1, except that potassium hydroxide aqueous solution is used instead of sodium hydroxide aqueous solution, and 3.9 g of target monomer is obtained by column chromatography.
  • Example 1 Take the target protocatechin epoxy compound monomer obtained in Example 1 and DDM, heat it to 40-60°C ultrasonically to melt into a uniform and transparent solution, or dissolve it in an organic solvent to make the mixture a uniform and transparent solution. Lower the temperature to remove the solvent.
  • the solvent is selected from the group consisting of ethyl acetate, dichloromethane, chloroform or a combination thereof. The residue was heated to 100°C to cure for 1 hour, and at 130°C for 3 hours to cool to obtain a cured resin.
  • the TGA test of the obtained resin showed that its 5% thermal weight loss temperature was 321°C, and the residual carbon rate was 27.7%.
  • E51 is a commercially available bisphenol A epoxy resin, and its structure is shown in Figure (a) below. Its epoxy value is between 0.48-0.54.
  • Example 6 and Example 7 were tested for CTE and DMA, respectively.
  • the test conditions are under nitrogen, from room temperature to 250°C, and the heating rate is 3°C/min.
  • the thermal expansion coefficient, glass transition temperature and storage modulus of the epoxy resin obtained in the present invention and commercial E51 epoxy resin were compared, and the results are shown in Figs. 1 and 2.
  • the thermal expansion coefficient of the cured product of E51 epoxy resin is 72 ppm/°C.
  • the T g is 176°C;
  • the thermal expansion coefficient of the cured product of protocatechin epoxy resin is 66ppm/°C, and the glass transition temperature is greater than 200°C, up to 221°C.
  • the T g of the cured product of E51 epoxy resin is 189°C, while the cured product of protocatechin epoxy resin has no obvious glass transition temperature within 250°C.
  • the storage modulus of the cured product of protocatechin epoxy resin is 1.9 GPa, which is higher than the 1.6 GPa of the cured product of E51 epoxy resin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention concerne la synthèse et l'utilisation d'une résine époxyde à base d'acide protocatéchique. Spécifiquement, un monomère époxydé d'acide protocatéchique a une structure telle que représentée dans la formule suivante (I). Le monomère peut être durci pour former une résine époxyde d'acide protocatéchique, ce qui permet de préparer des matériaux spéciaux aérospatiaux.
PCT/CN2020/138136 2019-12-20 2020-12-21 Synthèse et utilisation de résine époxyde à base d'acide protocatéchique WO2021121426A1 (fr)

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CN201911329150.6 2019-12-20
CN201911329150.6A CN111040131A (zh) 2019-12-20 2019-12-20 一种基于儿茶酸的环氧树脂的合成和应用

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CN114560996A (zh) * 2022-03-29 2022-05-31 中海石油(中国)有限公司 一种利用单宁酸固化制备的可降解生物环氧树脂及其高温堵漏应用

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CN111040131A (zh) * 2019-12-20 2020-04-21 中国科学院上海有机化学研究所 一种基于儿茶酸的环氧树脂的合成和应用
CN114075100A (zh) * 2020-08-10 2022-02-22 中国科学院上海有机化学研究所 一种基于白藜芦醇的树脂单体及基于其的高耐热树脂
CN113024380B (zh) * 2021-03-04 2023-01-17 中国科学院天津工业生物技术研究所 一种基于原儿茶酸的丙烯酸树脂的合成和应用
CN116444462B (zh) * 2022-02-25 2024-05-03 南京工业大学 一种新型异香兰素环氧树脂单体及其制备方法
CN115894403B (zh) * 2022-12-20 2024-03-12 中国科学院天津工业生物技术研究所 一种基于原儿茶酸的树脂助剂的合成和应用

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CN114560996A (zh) * 2022-03-29 2022-05-31 中海石油(中国)有限公司 一种利用单宁酸固化制备的可降解生物环氧树脂及其高温堵漏应用
CN114560996B (zh) * 2022-03-29 2023-07-21 中海石油(中国)有限公司 一种利用单宁酸固化制备的可降解生物环氧树脂及其高温堵漏应用

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