WO2022062370A1 - Résine époxydique résistante aux températures élevées biosourcée à diélectricité et à conductivité thermique améliorées, son procédé de préparation et son application - Google Patents

Résine époxydique résistante aux températures élevées biosourcée à diélectricité et à conductivité thermique améliorées, son procédé de préparation et son application Download PDF

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WO2022062370A1
WO2022062370A1 PCT/CN2021/087179 CN2021087179W WO2022062370A1 WO 2022062370 A1 WO2022062370 A1 WO 2022062370A1 CN 2021087179 W CN2021087179 W CN 2021087179W WO 2022062370 A1 WO2022062370 A1 WO 2022062370A1
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epoxy resin
preparation
thermal conductivity
high temperature
curing agent
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PCT/CN2021/087179
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English (en)
Chinese (zh)
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郭凯
孟晶晶
陈鹏飞
杨锐
戴林丽
朱宁
张锴
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南京工业大学
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Priority to GB2306059.3A priority Critical patent/GB2616136A/en
Publication of WO2022062370A1 publication Critical patent/WO2022062370A1/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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the field of polymer synthesis, and in particular relates to a dielectric and thermal conductivity-enhanced bio-based high temperature resistant epoxy resin and a preparation method and application thereof.
  • Epoxy resin polymers are usually formed by cross-linking polymerization of epoxy resin monomer materials and curing agents.
  • most of the currently commercialized epoxy resins are produced from petroleum raw materials, and more than 90% of the total epoxy resin production is bisphenol A epoxy resin.
  • one of its raw materials, epichlorohydrin can be produced from biomass raw material glycerol
  • the other main raw material, bisphenol A can currently only be produced from petroleum raw materials.
  • Oil is a non-renewable resource, which has been consumed in large quantities.
  • a series of problems such as shortage of oil resources, soaring oil prices and environmental pollution have forced people to focus their research on the field of sustainable development.
  • bisphenol A epoxy resin has high viscosity at room temperature and poor fluidity, which requires higher construction technology, and the cured epoxy resin has poor flame retardancy and electrical conductivity, and its application in high-tech fields is limited.
  • the 2019 patent CN110408003A discloses a preparation method of magnolol epoxy resin, and the corresponding difunctional and tetrafunctional epoxy resins are prepared from natural magnolia derivatives as raw materials.
  • Magnolia bark derivatives can be used in the preparation of Chinese herbal medicines and cosmetics, and have been proven to be safe and low-toxic compounds.
  • Using this as raw material to prepare epoxy resin can reduce the health hazard of epoxy resin to human body.
  • the preparation process of the bio-based epoxy resin is simple and efficient, which is beneficial to large-scale production. What is more noteworthy is that the bio-based epoxy resin has excellent heat resistance, mechanical properties and flame retardant properties after curing.
  • Patent CN107057289A in 2017 discloses a high thermal conductivity and high temperature resistant epoxy resin and a preparation method thereof.
  • the potting epoxy resin is used as a potting material and is applied to new energy power batteries and motors, wind power generation stators and motors with high conductivity and high temperature resistance. of potting.
  • bio-based epoxy resin materials with high thermal conductivity, high temperature resistance and electrical conductivity at the same time There are few literature reports on bio-based epoxy resin materials with high thermal conductivity, high temperature resistance and electrical conductivity at the same time. Therefore, through the in-depth development of bio-based compounds, the preparation of high-temperature-resistant bio-based epoxy resin materials with enhanced dielectric and thermal conductivity has good research and application value, and is also one of the frontier directions of bio-based material functional transformation and application research.
  • the technical problem to be solved by the present invention is to provide a dielectric and thermal conductivity-enhanced bio-based high temperature resistant epoxy resin for the deficiencies of the prior art.
  • the technical problem to be solved by the present invention is to provide the above-mentioned dielectric and thermal conductivity-enhanced bio-based high temperature resistant epoxy resin and a preparation method thereof.
  • the final technical problem to be solved by the present invention is to provide the application of the above-mentioned dielectric and thermal conductivity-enhanced bio-based high temperature resistant epoxy resin in dielectric capacitor materials.
  • the present invention discloses a bio-based high temperature resistant epoxy resin with enhanced dielectric and thermal conductivity.
  • the dielectric constant is basically kept constant at 8.2-10 in the frequency range of 0-3 MHz.
  • the variation of the dielectric loss of the epoxy resin with frequency is not higher than 0.075.
  • the thermal conductivity of the epoxy resin is not less than 0.43W/m ⁇ K, and the heat capacity ratio is not less than 2.3J/g ⁇ K
  • the thermal conductivity of the epoxy resin is not lower than 0.743W/m ⁇ K, and the heat capacity ratio is not lower than 5.364J/g ⁇ K.
  • the initial decomposition temperature of the epoxy resin is 405-420°C, and the temperature corresponding to the maximum decomposition rate is 445-455°C; preferably, the initial decomposition temperature of the epoxy resin is 410°C , the temperature corresponding to the maximum decomposition rate is 451 °C.
  • the epoxy resin can be extinguished after burning for 60s, more preferably 25s.
  • the present invention discloses a preparation method of the above epoxy resin, and the epoxy resin monomer used in the preparation process includes a compound represented by the formula DBDBBB;
  • the epoxy resin monomer may be the compound represented by the formula DBDBBB itself, or a mixture of the compound represented by the formula DBDBBB and other monomers, such as a mixture of the compound represented by the formula DBDBBB and DGEBA.
  • the compound shown in formula DBDBBB is prepared by reacting with honokiol (compound shown in formula C) and epichlorohydrin;
  • the reaction is to mix epichlorohydrin, tetrabutylammonium bromide and 50% w/w sodium hydroxide aqueous solution at room temperature for 30 minutes, and then dropwise add the honokiol dissolved in tetrahydrofuran dropwise , After the reaction at 50°C is complete, extract with dichloromethane, and dry the organic phase obtained from the extraction with anhydrous sodium sulfate, then rotate and concentrate, and separate by silica gel column (petroleum ether and ethyl acetate 30/1-6/1) to obtain.
  • silica gel column petroleum ether and ethyl acetate 30/1-6/1
  • the weight ratio of epichlorohydrin, tetrabutylammonium bromide and sodium hydroxide aqueous solution is (38-42):1:(26-32).
  • the mass ratio of magnolol to epichlorohydrin is 1:(4-5); and the dosage ratio of magnolol to tetrahydrofuran is 0.2-0.3 g/mL.
  • the preparation method of epoxy resin, epoxy DBDBBB and amine curing agent prepare corresponding bio-based epoxy resin polymer material through solvent-free curing reaction; specifically, it includes the following steps:
  • step (2) under a nitrogen atmosphere, at a certain temperature, add a curing agent to the deoxidized epoxy resin monomer obtained in step (1), melt at high temperature, stir evenly, and pour into a mold;
  • step (2) The mold in step (2) is solidified at high temperature under nitrogen atmosphere, cooled under nitrogen atmosphere, and demolded to obtain.
  • the curing agent is a diamine curing agent.
  • the bisamine curing agent is 4,4'-diaminodiphenylsulfone (44DDS) shown in formula A and 3,3'-diaminodiphenylsulfone (44DDS) shown in formula B. 33DDS) any one or two combinations (1mol curing agent contains 4mol NH-);
  • step (2) the added amount of the curing agent is controlled so that the molar ratio of the ethylene oxide group in the epoxy resin monomer to the NH- in the curing agent is 1:0.85-1:1.2.
  • the high temperature melting temperature is 120-195°C, preferably 150-170°C.
  • step (3) in the high temperature curing, the temperature is 170-215°C, preferably 200-215°C.
  • step (3) the high temperature curing, the curing time is 3-10h, preferably 4-6h.
  • the present invention discloses the application of the above-mentioned dielectric and thermal conductivity-enhanced bio-based high temperature resistant epoxy resin in a dielectric capacitor material.
  • the bio-based epoxy resin material prepared by the DBDBBB/DDS system in the present invention not only has excellent thermal stability and flame retardancy, but also has excellent dielectric properties and thermal conductivity.
  • DBDBBB The dielectric parameters (9.74, 0.026) of /44DDS are similar to those of fluorine-containing polyvinylidene fluoride dielectric material (PVDF) (10, 0.04), showing good replaceability.
  • PVDF polyvinylidene fluoride dielectric material
  • the present invention has the following advantages:
  • bio-based raw materials of the present invention and honokiol are prepared by simple conversion to obtain green and environmentally friendly non-petroleum-based epoxy resin materials, the raw materials are widely sourced, the products obtained therefrom have strong replaceability to petroleum-based products, and have high biosafety, Fully realize the efficient use of biological resources and meet the development requirements of green chemistry.
  • the polymer system composed of raw materials in the present invention has certain flame retardancy, does not use halogen-based or phosphorus-based flame retardants or inorganic flame retardants, and has high biological safety.
  • the dielectric constant ( ⁇ ') of the obtained epoxy resin material is >5, the dielectric constant of traditional resin materials is between 2 and 4, and the dielectric constant of this system is increased to between 8.2 and 10. Significant improvement over conventional polymer materials.
  • thermal conductivity In terms of thermal conductivity, the low thermal conductivity ( ⁇ 0.3W/m ⁇ K) of traditional polymer resins limits its application in the electronics industry to a large extent; and the thermal conductivity and specific heat capacity of common epoxy resin materials 0.2-2.2W/m ⁇ K, 0.8-1.5J/g ⁇ K, respectively, while the epoxy resin material reported in this patent has both good thermal conductivity and heat capacity ratio (0.743W/m ⁇ K, 5.364J/ g ⁇ K), which can meet the application of corresponding functional electronic products.
  • the decomposition temperature of the material obtained by the present invention is the highest (410°C) in the current bio-based epoxy resin, and the temperature corresponding to the maximum decomposition rate also reaches the corresponding maximum value (451°C), showing excellent thermal stability.
  • the present invention is the first time to synthesize a high temperature resistant polymer material based on bio-based and honokiol, which can meet the replacement of some related petroleum-based chemicals and further realize the functionalization of bio-based materials. Research lays the foundation.
  • Figure 1 is a 1 H-NMR of DBDBBB.
  • Figure 2 is an infrared spectrum of DBDBBB/44DDS and DBDBBB/33DDS epoxy resins (Examples 4, 5).
  • Figure 3 is the TG spectra of DBDBBB/44DDS and DBDBBB/33DDS epoxy resins (Examples 4, 5).
  • Figure 4 shows the dielectric properties of epoxy resins (Examples 4, 5).
  • Figure 5 shows the thermal conductivity of epoxy resins at room temperature (Examples 4, 5).
  • Figure 6 is a flame retardant test of DBDBB/44DDS and DBDBB/33DDS epoxy resins (Examples 4, 5).
  • Thermogravimetric test parameters Test instrument Discovery TGA-550, temperature range 40-900°C, nitrogen flow rate 20mL/min, heating rate 20°C/min.
  • Dielectric test parameters test instrument Novocontrol Concept 80, 25°C, test frequency 0Hz-3MHz.
  • Thermal conductivity test test instrument NETZSCH LFA427, 25°C, argon flow rate 80mL/min.
  • the epoxy resin monomer DBDBBB (3.78 g) prepared in Example 1 was weighed in the sample bottle, and nitrogen was introduced to remove the oxygen component. Under a nitrogen atmosphere, 4,4'-diaminodiphenylsulfone (compound A, 1.24g), further remove the air, fully mix and stir, and heat up to 165 ° C to melt and mix the two evenly.
  • the material was poured into a 170°C stainless steel grinding plate, then heated in an atmosphere of 210°C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain a transparent epoxy resin polymer.
  • the epoxy resin monomer DBDBBB (3.78 g) prepared in Example 1 was weighed in the sample bottle, and nitrogen was introduced to remove the oxygen component. Under a nitrogen atmosphere, 3,3'-diaminodiphenylsulfone (compound B, 1.24g), further remove the air, fully mix and stir, and heat up to 180 ° C to melt and mix the two evenly.
  • the material was poured into a stainless steel abrasive plate at 170 °C, and the material was poured into a stainless steel abrasive plate, then heated in an atmosphere of 210 °C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain light yellow and transparent epoxy resin polymerization thing.
  • the epoxy resin monomer DBDBBB (7.56 g) prepared in Example 1 was weighed in the sample bottle, and nitrogen was introduced to remove the oxygen component. Under nitrogen atmosphere, 4,4'-diaminodiphenylsulfone (compound A, 2.48g), further remove the air, fully mix and stir, and heat up to 150 ° C to melt and mix the two evenly.
  • the material was poured into a stainless steel grinding plate at 170°C, heated in an atmosphere of 210°C, cured for 2 hours, and then cooled naturally in a nitrogen atmosphere to obtain a transparent epoxy resin polymer.
  • the dielectric constant of the obtained epoxy resin polymer is 9.74, and the change in dielectric loss with frequency is 0.026.
  • the epoxy resin monomer DBDBBB (7.56 g) prepared in Example 1 was weighed in the sample bottle, and nitrogen was introduced to remove the oxygen component. Under a nitrogen atmosphere, 3,3'-diaminodiphenylsulfone (compound B, 2.48g), further remove the air, fully mix and stir, and heat up to 170 ° C to melt and mix the two evenly.
  • the material was poured into a stainless steel abrasive plate at 170 °C, and the material was poured into a stainless steel abrasive plate, then heated in an atmosphere of 210 °C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain light yellow and transparent epoxy resin polymerization thing.
  • Example 4 the epoxy resin monomer was replaced from DBDBBB to DGEBA, poured after melting at 180 °C, and then cured at 215 °C for 2 hours.
  • the epoxy resin material obtained by the combustion test found that the combustion continued for 155s and then extinguished. It can be seen that the flame retardant performance of the corresponding DBDBBB material system is better. Dielectric test found that in the range of 0-3MHz, the dielectric loss of DGEBA/44DDS polymer varies with frequency (0.1-0.45), which is significantly higher than that of DBDBBB/DDS system ( ⁇ 0.075).
  • DGEBA/ The DDS system has large energy consumption and large heat generation, and is not suitable for use as a dielectric material; in addition, the thermal conductivity and specific heat capacity of DGEBA/44DDS are small, 0.333W/m ⁇ K and 1.96J/g, respectively. ⁇ K”, which is significantly smaller than the bio-based DBDBBB/DDS system.
  • the thermal conductivity and specific heat capacity of common epoxy resin materials are 0.2-2.2W/m ⁇ K, 0.8-1.5J/g ⁇ K, respectively. Therefore, based on the development of bio-based DBDBBB The polymer system not only has flame retardancy, but also has significantly enhanced dielectric and thermal conductivity.
  • the present invention provides an idea and method for a bio-based high temperature resistant epoxy resin with enhanced dielectric and thermal conductivity and a preparation method thereof.
  • the above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can also be made, and these improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

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

Abstract

Une résine époxydique résistante aux températures élevées biosourcée à diélectricité et à conductivité thermique améliorées, son procédé de préparation et son application sont divulgués dans la présente invention. La constante diélectrique de la résine époxydique est comprise entre 8,2 et 10. Le présent procédé présente un processus de fonctionnement simple et une durée de durcissement plus courte ; le matériau polymère de résine époxydique biosourcée obtenu présente des performances excellentes, et la constante diélectrique est augmentée pour atteindre de 8,2 à 10 ; de plus, la résine époxydique présente une bonne conductivité thermique et un bon rapport de capacité calorifique (0,743 W/m·K, 5,364 J/g·K), et peut être appliquée à des produits électroniques fonctionnalisés correspondants.
PCT/CN2021/087179 2020-09-27 2021-04-14 Résine époxydique résistante aux températures élevées biosourcée à diélectricité et à conductivité thermique améliorées, son procédé de préparation et son application WO2022062370A1 (fr)

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CN202011030506.9A CN112142953A (zh) 2020-09-27 2020-09-27 一种介电导热增强型生物基耐高温环氧树脂及其制备方法与应用
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WO2024092864A1 (fr) * 2022-11-02 2024-05-10 南京工业大学 Monomère de résine époxy biosourcé double à base de magnolol/glycosyl furane, son procédé de préparation et son utilisation

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CN113896694B (zh) * 2021-11-16 2022-12-06 韦尔通(厦门)科技股份有限公司 一种多官能团杂化环氧化合物和光热双固化树脂组合物及其制备方法和应用
CN114315814B (zh) * 2021-12-29 2022-10-21 南京工业大学 一种和厚朴酚/糖基呋喃双生物基环氧树脂单体及其制备方法和应用
CN114395110B (zh) * 2022-01-30 2023-04-07 南京工业大学 一种全生物基氰基环氧树脂及其绿色制备方法

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