WO2024197823A1 - 一种生物基环氧单体及中温固化环氧树脂体系与制备方法 - Google Patents

一种生物基环氧单体及中温固化环氧树脂体系与制备方法 Download PDF

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WO2024197823A1
WO2024197823A1 PCT/CN2023/085503 CN2023085503W WO2024197823A1 WO 2024197823 A1 WO2024197823 A1 WO 2024197823A1 CN 2023085503 W CN2023085503 W CN 2023085503W WO 2024197823 A1 WO2024197823 A1 WO 2024197823A1
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monomer
bio
epoxy resin
medium
resin system
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French (fr)
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袁莉
张雅洁
顾嫒娟
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Suzhou University
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof

Definitions

  • the invention relates to a novel bio-based epoxy monomer and preparation of a high-performance degradable multifunctional epoxy resin system cured at medium temperature, belonging to the technical field of polymer chemical synthesis and high-performance resin preparation.
  • Epoxy resin is a typical high-performance thermosetting resin, which has shown great application value in cutting-edge industrial fields such as electronic information, aerospace, electrical insulation, and rail transportation.
  • epoxy monomers are derived from bisphenol A, which is non-renewable and comes from petroleum resources.
  • biomass raw materials such as vegetable oil, lignin, isosorbide, starch, eugenol, vanillin, and cardanol have been widely used to synthesize bio-based thermosetting epoxy resins, and have shown broad application prospects in coatings, adhesives, composite materials, and electronic packaging.
  • thermosetting resins due to the large amount of flexible segments contained in the synthetic raw materials, most bio-based epoxy monomer cured products have poor mechanical strength and low glass transition temperature ( Tg ), which limits their practical application. Studies have shown that the introduction of rigid structures in epoxy monomers and the use of high-temperature curing agents can improve the mechanical and thermal properties of epoxy matrices. In addition, like other thermosetting resins, the highly cross-linked network structure formed by bio-based epoxy resins is difficult to recycle and its waste will also cause serious environmental problems. Although some chemical and physical methods (such as mechanical grinding, pyrolysis, etc.) have been used to treat thermosetting resins, these methods usually require high energy consumption and harsh conditions.
  • the purpose of the present invention is to provide a novel bio-based epoxy monomer and a medium-temperature cured high-performance degradable multifunctional epoxy resin system.
  • the epoxy monomer is synthesized using biomass protocatechuic aldehyde, erythritol, and epichlorohydrin as raw materials, and a medium-temperature curing process is used to prepare a multifunctional high-performance epoxy resin system with self-repairing, shape memory, and degradability.
  • a novel bio-based epoxy monomer and a medium-temperature-cured high-performance degradable multifunctional epoxy resin system and preparation thereof wherein the bio-based epoxy monomer is synthesized using protocatechuic aldehyde, erythritol and epichlorohydrin as raw materials, and is a tetraepoxy monomer called DGEVP; the bio-based epoxy monomer is used as a raw material, an anhydride curing agent and a catalyst are added, and a medium-temperature curing procedure ( ⁇ 120°C) is adopted to obtain a high-performance degradable multifunctional epoxy resin system.
  • the bio-based epoxy monomer is synthesized using protocatechuic aldehyde, erythritol and epichlorohydrin as raw materials, and is a tetraepoxy monomer called DGEVP; the bio-based epoxy monomer is used as a raw material, an anhydride curing agent and a catalyst are added, and a medium-temperature curing procedure (
  • the invention discloses a method for preparing the bio-based epoxy monomer.
  • Protocatechuic aldehyde and erythritol are used as raw materials to prepare a tetrahydroxy monomer; and then the tetrahydroxy monomer and epichlorohydrin are used as raw materials to prepare the bio-based epoxy monomer.
  • protocatechuic aldehyde and erythritol are used as raw materials, and a tetrahydroxy monomer is prepared by reaction in the presence of a catalyst and in a solvent; preferably, the reaction is carried out at 70-100° C. for 12-24 hours; preferably, the catalyst is p-toluenesulfonic acid monohydrate (p-TSA.H2O), and the solvent is N,N-dimethylformamide; further preferably, the reaction is carried out in the presence of a dehydrating agent; the molar ratio of protocatechuic aldehyde, erythritol, and p-toluenesulfonic acid monohydrate is 200: (100-120): (4-6).
  • tetrahydroxy monomer and epichlorohydrin are used as raw materials, in the presence of an organic ammonium salt and in an alkaline environment to prepare the bio-based epoxy monomer; preferably, tetrahydroxy monomer (VP) and epichlorohydrin (ECH) are reacted at 40-80° C.
  • the organic ammonium salt is tetrabutylammonium bromide
  • sodium hydroxide solution is added to form an alkaline environment
  • sodium hydroxide solution is added at room temperature, and then reacted for 2-4 hours to prepare the bio-based epoxy monomer
  • the molar ratio of tetrahydroxy monomer, epichlorohydrin and tetrabutylammonium bromide is 1: (40-250): (1-3).
  • the invention discloses a medium-temperature curing epoxy resin system, comprising the above-mentioned bio-based epoxy monomer, anhydride curing agent and catalyst, which is a novel bio-based medium-temperature curing high-performance degradable multifunctional epoxy resin system; after medium-temperature curing, a high-performance degradable multifunctional epoxy resin is obtained.
  • the present invention discloses a method for preparing the above-mentioned medium-temperature curing epoxy resin system, wherein the above-mentioned bio-based epoxy monomer DGEVP and a catalyst are melt-mixed uniformly, and then an anhydride compound is added at 60-80°C, prepolymerized for 20-40 minutes, to obtain a medium-temperature curing epoxy resin system; and then a medium-temperature (curing temperature is lower than 125°C) curing procedure is used for curing to obtain a high-performance biodegradable multifunctional epoxy resin.
  • the molar ratio of the epoxy group of the bio-based epoxy monomer to the anhydride group of the anhydride compound is 1: (0.8-1.0); the catalyst is 0.5-5% of the mass of DGEVP; preferably, the temperature of the melt mixing of DGEVP and the catalyst is 140-210°C.
  • the acid anhydride compound is a low melting point petroleum-based anhydride, a bio-based anhydride or a mixture thereof, mainly including glutaric anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride or a mixture thereof.
  • the catalyst is an organic metal complex, such as one or more of zinc acetylacetonate, zirconium acetylacetonate, aluminum acetylacetonate, iron acetylacetonate, and cadmium acetylacetonate.
  • the medium temperature curing procedure is a step-by-step temperature increase method, and the preferred medium temperature curing procedure is 80° C./2h+100° C./2h+120° C./0-4h.
  • the novel bio-based epoxy monomer of the present invention adopts a high-performance degradable multifunctional epoxy resin body cured at medium temperature, which has excellent mechanical properties, bending strength: 105-156MPa, impact strength: 13.5-32kJ/ cm2 , tensile strength: 45-81MPa; good heat resistance, Tg : 113-158°C; and multifunctional properties such as self-repair, shape memory and mild degradability.
  • the present invention has the following beneficial effects:
  • the present invention uses natural raw materials to synthesize tetraepoxy monomers, which have high reaction activity due to the high content of epoxy groups.
  • the process for preparing tetraepoxy monomers in the present invention is also applicable to the reaction of protocatechuic aldehyde and other polyol compounds with epichlorohydrin to prepare epoxy monomers with multiple epoxy functional groups.
  • the present invention uses anhydride as a curing agent and adopts a medium-temperature curing procedure (80°C/2h+100°C/2h+120°C/0-4h) to obtain a high-performance resin system with multifunctional properties such as self-repairing, shape memory and mild acid degradability.
  • the resin system of the present invention has the advantages of low curing temperature and short curing time, which can effectively save energy consumption.
  • the comprehensive mechanical and thermal properties of the cured system are significantly better than the currently reported biomass epoxy system with mild degradation characteristics containing dynamic reversible bonds, and are comparable to the mechanical and thermal properties of traditional commercial bisphenol A epoxy resin systems cured with the same curing agent.
  • FIG1 is a schematic diagram of the synthesis of VP and DGEVP.
  • Figure 2 shows the FTIR spectra of PCA, erythritol, VP and DGEVP (a); the 1 H NMR spectra of VP (b); the 13 C NMR spectra of VP (c); the 1 H NMR spectra of DGEVP (d); the 13 C NMR spectra of DGEVP (e); and the LC-MS spectra of VP (f) and DGEVP (g).
  • FIG3 is a diagram showing the healing process of scratches on the surface of the cured sample of Example 1 at 200° C.
  • a scalpel is used to scratch the surface of the cured sample to form a scratch with a depth of about 22 ⁇ m, and then the sample is placed in an oven.
  • FIG4 is a diagram showing the shape deformation and recovery of the cured sample of Example 1 at 130° C.
  • the cured sample is first bent at 130° C. and shaped at room temperature. The bent sample is then placed in an oven and allowed to recover in a short time.
  • FIG. 5 is a DSC curve of the resin system in Example 1 compared with Example 1, 10° C./min.
  • FIG. 7 is a diagram showing the healing process of scratches on the surface of the cured sample of Example 2 at 200° C.
  • FIG8 is a shape deformation and recovery diagram of the cured sample of Example 2 at 130° C. and a graph of three shape memory cycle curves.
  • FIG. 9 is a diagram showing the healing process of scratches on the surface of the cured sample of Example 3 at 210° C.
  • FIG. 10 is a diagram showing the shape deformation and recovery of the cured sample of Example 3 at 176° C.
  • FIG. 11 is a diagram showing the healing process of scratches on the surface of the cured sample of Example 3 at 200° C.
  • FIG. 12 is a diagram showing the shape deformation and recovery of the cured sample of Example 4 at 160° C.
  • the present invention uses protocatechuic aldehyde, erythritol and epichlorohydrin as the main raw materials to synthesize a tetraepoxy monomer (DGEVP), and uses the epoxy monomer as the raw material, adds anhydride curing agent and catalyst, and adopts a medium temperature curing procedure ( ⁇ 120°C) to obtain a high-performance biodegradable multifunctional epoxy resin system.
  • DGEVP tetraepoxy monomer
  • the present invention uses protocatechuic aldehyde and erythritol as raw materials to prepare a tetrahydroxy monomer; then uses tetrahydroxy monomer and epichlorohydrin as raw materials to prepare the bio-based epoxy monomer.
  • the specific reaction example is as follows:
  • Protocatechuic aldehyde, erythritol, catalyst p-toluenesulfonic acid monohydrate (p-TSA.H2O), solvent N,N-dimethylformamide and dehydrating agent petroleum ether are placed in a reactor equipped with a water separator and a spherical condenser; under nitrogen protection, the mixture is reacted at 70-100°C for 12-24 hours, the product is cooled, then poured into deionized water to precipitate, filtered and washed with water, and finally dried in a vacuum oven to obtain a tetrahydroxy monomer product (VP).
  • the molar ratio of protocatechuic aldehyde, erythritol, p-toluenesulfonic acid monohydrate, N,N-dimethylformamide and petroleum ether is 200: (100-120): (4-6): 300-500: 2000-4000; the molar ratio of tetrahydroxy monomer VP, epichlorohydrin (ECH) and tetrabutylammonium bromide is 1: (40-250): (1-3).
  • Protocatechuic aldehyde (PCA, 0.2 mol), erythritol (0.1 mol), catalyst p-toluenesulfonic acid monohydrate (p-TSA ⁇ H 2 O, 0.0042 mmol), solvent N,N-dimethylformamide (0.39 mol) and dehydrating agent petroleum ether (3.3 mol) were placed in a reactor equipped with a water separator and a spherical condenser.
  • FIG. 1 (a) shows a schematic diagram of the synthesis of VP.
  • Figure 2 shows the infrared spectra (FTIR) of PCA, erythritol, VP and DGEVP; the nuclear magnetic resonance spectrum ( 1H NMR) and carbon nuclear magnetic resonance spectrum ( 13C NMR) of VP; the 1H NMR and 13C NMR of DGEVP; and the liquid chromatography-mass spectra (LC-MS) of VP and DGEVP.
  • FTIR infrared spectra
  • 1H NMR nuclear magnetic resonance spectrum
  • 13C NMR carbon nuclear magnetic resonance spectrum
  • DGEVP liquid chromatography-mass spectra
  • the FTIR spectrum of PCA shows characteristic absorption peaks at the hydroxyl group (about 3190-3300 cm -1 ), CH in the benzene ring (3047 cm -1 ), CH in the aldehyde group (-CHO) (2890-2725 cm -1 ), -CHO (1750 cm -1 ), and aromatic rings (1650, 1600 and 1530 cm -1 ).
  • the FTIR spectrum of erythritol shows characteristic absorption peaks of -OH (3100-3500 cm -1 ), CH (2965 and 2908 cm -1 , 1406 cm -1 ), primary and secondary alcohols (1080 and 1050 cm -1 ) and CO (972 cm -1 ).
  • the FTIR spectrum of VP shows new changes, with new strong characteristic peaks at 1005 cm -1 , 1280 cm -1 , 1160 cm -1 and 1107 cm -1 , which are due to the formation of -COC-, -CO-, COC.
  • the characteristic peak of -CHO does not appear in the FTIR spectrum of VP.
  • VP reacts with ECH a characteristic peak appears at 910 cm -1 , which is the characteristic peak of the epoxy group.
  • there is no obvious -OH peak at 3100-3500 cm -1 which means that the bio-based tetrafunctional epoxy monomer DGEVP is successfully synthesized.
  • the LC-MS spectrum shows that the molar mass of VP is 385.0911g/mol, which is consistent with the theoretical value of 385.0900g/mol. This means that VP was successfully synthesized.
  • the 1H NMR spectrum of DGEVP does not show the proton peak in the phenolic hydroxyl group at 8.97ppm.
  • the chemical shift and peak number of DGEVP in 13 C NMR corresponded to the carbon atoms in VP
  • the LC-MS spectrum showed that the molar mass of DGEVP was 609.1948 g/mol, which was consistent with the theoretical value of 609.1948 g/mol. This means that DGEVP was successfully synthesized.
  • a mixture of 100 g DGEVP and 1.25 g zinc acetylacetonate (ZAA) was heated and stirred at 140 °C until it became a transparent liquid, and then 33 g glutaric anhydride (GA) was added at 80 °C and stirred for 20 min to obtain a uniform prepolymer medium-temperature curing epoxy resin system. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven at 80 °C, and then cured according to the temperature program of 80 °C/2h+100 °C/2h to obtain a cured product.
  • ZAA zinc acetylacetonate
  • a mixture of 100 g of bisphenol A epoxy resin (E51) and 1.25 g of zinc acetylacetonate (ZAA) was heated and stirred at 140 ° C to obtain a transparent liquid, and then 30 g of glutaric anhydride (GA) was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven at 80 ° C, and then cured according to the temperature program 80 ° C/2h+100 ° C/2h to obtain a cured product.
  • a mixture of 100 g of bisphenol A epoxy resin (E51) and 1.25 g of zinc acetylacetonate (ZAA) was heated and stirred at 140 ° C to obtain a transparent liquid, and then 30 g of glutaric anhydride (GA) was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subse
  • ZAA zinc acetylacetonate
  • Table 1 shows the mechanical property data, resin system reaction activation energy (Ea), conversion rate of epoxy groups of the cured resin system ( ⁇ ) and glass transition temperature (T g ) of the cured samples of Example 1, Comparative Example 1-1 and Comparative Example 1-2.
  • Ea resin system reaction activation energy
  • ⁇ conversion rate of epoxy groups of the cured resin system
  • T g glass transition temperature
  • the DGEVP cured product not only has mild acid degradation behavior, but also has good crack self-repairing ability at 200°C (Figure 3), and has good shape deformation and recovery ability at a temperature of about T g +20°C ( Figure 4).
  • Traditional bisphenol A epoxy resin cured by anhydride has no acidic degradation behavior, while DGEVP cured product is very easy to degrade under acidic conditions.
  • the prior art uses protocatechuic aldehyde and 4,4-diaminodiphenyl ether (ODA) as raw materials to synthesize semi-bio-based PH-ODA, uses PH-ODA, epichlorohydrin and NaOH as raw materials, adopts a two-step method to synthesize semi-bio-based flame-retardant epoxy prepolymer, and uses curing agent DDM to cure epoxy prepolymer PH-ODA-EP to obtain epoxy cured product PH-ODA-EP/DDM. Compared with DGEBA/DDM, Ea is high.
  • the reaction activity of PH-ODA-EP/DDM curing system is lower than that of DGEBA/DDM curing system, and a curing temperature of 190°C is required. It also contains a part of petroleum-based raw material ODA, and does not achieve full utilization of bio-based raw materials.
  • the epoxy resin/anhydride curing system of the present invention has good self-healing behavior, low curing temperature and low production energy consumption.
  • the curing temperature of the resin system of the present invention is low, while the curing temperature of the existing acetal epoxy/anhydride system is relatively high.
  • Figure 5 shows the DSC curves of the resin systems in Example 1 and Example 1. Obviously, the reaction temperature of DGEVP/GA/ZAA is lower than that of E51/GA/ZAA.
  • a mixture of 100 g DGEVP and 2.5 g zinc acetylacetonate (ZAA) was heated and stirred at 140 ° C until it became a transparent liquid, and then 33 g glutaric anhydride (GA) was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, and then cured according to the temperature program of 80 ° C/2h+100 ° C/2h to obtain a cured product.
  • ZAA zinc acetylacetonate
  • a mixture of 100 g E51 and 2.5 g zinc acetylacetonate (ZAA) was heated and stirred at 140 ° C until it became a transparent liquid, and then 30 g glutaric anhydride (GA) was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, and then cured according to the temperature program of 80 ° C/2h+100 ° C/2h+140 ° C/2h+180 ° C/2h to obtain a cured product.
  • ZAA zinc acetylacetonate
  • GA glutaric anhydride
  • Table 2 shows the mechanical properties data of the cured samples of Example 2 and Comparative Example 2, E a of the resin system, the conversion rate ⁇ of the epoxy group and T g . It can be seen from Table 2 that the mechanical properties and thermal properties of the resin system prepared by the biomass epoxy resin synthesized by the present invention at medium temperature are superior to those of the traditional commercial bisphenol A epoxy resin cured at medium and high temperatures.
  • the activation energy E a of the resin system reaction is low, and even after medium temperature curing, the resin system has a high epoxy group conversion rate. DGEVP cured products are easily degraded under acidic conditions ( Figure 6 (a)).
  • a mixture of 100 g DGEVP and 5.0 g zirconium acetylacetonate (AAZ) was heated and stirred at 200 ° C until it became a transparent liquid, and then 55 g methylhexahydrophthalic anhydride (MeHHPA) was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, and then the cured product was obtained according to the temperature program of 80 ° C/2h+100 ° C/2h+120 ° C/4h.
  • AAZ zirconium acetylacetonate
  • a mixture of 100 g E51 and 5.0 g zirconium acetylacetonate (AAZ) was heated and stirred at 200 ° C until it became a transparent liquid, and then 45 g methylhexahydrophthalic anhydride (MeHHPA) was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer.
  • MeHHPA methylhexahydrophthalic anhydride
  • the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, and then the cured product was obtained according to the temperature program of 80 ° C/2h+100 ° C/2h+140 ° C/2h+180 ° C/2h.
  • Table 3 shows the mechanical property data of the cured samples of Example 3 and Comparative Example 3, the Ea of the resin system, the conversion rate ⁇ of the epoxy group of the cured resin system, and the glass transition temperature Tg .
  • the mechanical properties and thermal properties of the resin system prepared by the biomass epoxy resin synthesized in the present invention at medium temperature are superior to those of the traditional commercial bisphenol A epoxy resin cured at medium and high temperatures.
  • the resin system reaction activation energy Ea is low. Even after medium temperature curing treatment, the resin system has a high epoxy group conversion rate, and its cured product is very easy to degrade under acidic conditions.
  • the DGEVP cured product has good crack self-repairing ability at 200°C ( Figure 9).
  • the DGEVP cured product has good shape deformation and recovery ability above the Tg temperature ( Figure 10).
  • a mixture of 60 g DGEVP and 0.5 g zinc acetylacetonate (ZAA) was heated and stirred at 140 ° C until it became a transparent liquid, and then 22 g citraconic anhydride was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, and then the cured product was obtained according to the temperature program of 80 ° C/2h+100 ° C/2h+120 ° C/2h.
  • ZAA zinc acetylacetonate
  • a mixture of 60 g E51 and 0.5 g zinc acetylacetonate (ZAA) was heated and stirred at 140 ° C until it became a transparent liquid, and then 18 g citraconic anhydride was added at 80 ° C and stirred for 20 min to obtain a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, and then cured according to the temperature program of 80 ° C/2 h + 100 ° C/2 h + 140 ° C/2 h + 180 ° C/2 h to obtain a cured product.
  • ZAA zinc acetylacetonate
  • Table 4 shows the mechanical property data, resin system reaction activation energy Ea, conversion rate ⁇ of epoxy groups of the cured resin system and glass transition temperature Tg of the cured samples of Example 4 and Comparative Example 4.
  • the resin system reaction activation energy Ea is low. Even after medium temperature curing treatment, the resin system has a high epoxy group conversion rate, and its cured product is very easy to degrade under acidic conditions.
  • the DGEVP cured product has good crack self-repairing ability at 200°C ( Figure 11).
  • the DGEVP cured product has good shape deformation and recovery ability above Tg temperature ( Figure 12).

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Abstract

本发明公开了一种生物基环氧单体及中温固化环氧树脂体系与制备方法，具体以原儿茶醛、赤藓糖醇为原料制备四羟基单体；然后以四羟基单体、环氧氯丙烷为原料制备所述生物基环氧单体；将生物基环氧单体与催化剂熔融混合均匀，然后于60～80℃下加入酸酐化合物，预聚得到中温固化环氧树脂体系；再经过中温固化得到高性能可降解多功能环氧树脂。相对于现有生物质环氧单体甚至是传统商品化的双酚A环氧树脂，本发明树脂体系具有固化温度低及固化时间短的优势，能有效节约能耗，且固化体系的综合力学性和热性能明显优于现有报道的含动态可逆键的具有温和降解特性的生物质环氧体系，较同固化剂固化的商品化双酚A型环氧树脂体系力学及热性能更优。

Description

一种生物基环氧单体及中温固化环氧树脂体系与制备方法 技术领域
本发明涉及一种新型生物基环氧单体及其中温固化的高性能可降解多功能环氧树脂体系制备，属于高分子化学合成及高性能树脂制备技术领域。
 背景技术
环氧树脂是作为典型的高性能热固性树脂，在电子信息、航空航天、电气绝缘、轨道交通等尖端工业领域显示出巨大的应用价值。目前，90%以上的环氧单体都是由双酚A衍生而来的，而双酚A是不可再生的，来源于石油资源。鉴于有限的石油资源、气候变化以及二氧化碳排放等环境问题，生物质原料如植物油、木质素、异山梨醇、淀粉、丁香酚、香草醛、腰果酚等已广泛用于合成生物基热固性环氧树脂，并在涂料、胶粘剂、复合材料、电子封装等领域显示广泛的应用前景。但是，由于合成原料含有大量的柔性链段，大多数生物基环氧单体固化物的力学强度较差、玻璃化转变温度（T g）较低，从而限制了它们的实际应用。研究表明，在环氧单体中引入刚性结构和使用高温固化剂可以提高环氧基体的力学性能和热性能。此外，同其他热固性树脂一样，生物基环氧树脂形成的高度交联网状结构是难以回收处理，其废弃物同样会引发严重的环境问题，尽管一些化学和物理方法（如机械研磨、热解等）已被用于处理热固性树脂，但这些方法通常需要高能耗和苛刻的条件。因此，有效延缓材料的使用寿命及制备易降解环氧树脂体系可以避免材料的过度消耗并降低废弃材料能耗处理。实践证明，在聚合物体系中创建动态可逆键可以实现裂纹修复，并延长材料使用寿命，遗憾的是，目前基于含动态可逆键的具有温和降解行为的环氧树脂体系普遍存在T g较低，力学强度较差等问题，即使个别环氧树脂体系具有优异的力学及热性能，但是通常会使用高温固化剂，固化温度偏高，能耗较大。可见，积极发展低中温固化的高性能的含动态可逆键的具有温和降解行为生物基环氧树脂体系对于促进生物基环氧树脂的应用具有重要的经济价值与社会意义。
技术问题
本发明的目的是提供一种新型生物基环氧单体及其中温固化的高性能可降解多功能环氧树脂体系制备。以生物质原儿茶醛、赤藓糖醇、环氧氯丙烷为原料合成了环氧单体，实现了中温固化工艺制备具有自修复、形状记忆、可降解的多功能高性能环氧树脂体系。
 技术解决方案
为实现上述发明目的，本发明采用如下技术方案：
一种新型生物基环氧单体及其中温固化的高性能可降解多功能环氧树脂体系与制备，其中，生物基环氧单体以原儿茶醛、赤藓糖醇及环氧氯丙烷为原料合成，为一种四环氧基单体，称为DGEVP；所述生物基环氧单体为原料，加入酸酐固化剂及催化剂，采用中温固化程序（≤120°C）获得高性能可降解多功能环氧树脂体系。
本发明公开了所述生物基环氧单体的制备方法，以原儿茶醛、赤藓糖醇为原料制备四羟基单体；然后以四羟基单体、环氧氯丙烷为原料制备所述生物基环氧单体。
本发明中，以原儿茶醛、赤藓糖醇为原料，在催化剂存在下、溶剂中，反应制备四羟基单体；优选的，反应为70～100℃反应12～24小时；优选的，催化剂为对甲苯磺酸一水合物（p-TSA.H2O），溶剂为N,N-二甲基甲酰胺；进一步优选的，反应在除水剂存在下进行；原儿茶醛、赤藓糖醇、对甲苯磺酸一水合物的摩尔比为200∶（100～120）∶（4～6）。
本发明中，以四羟基单体、环氧氯丙烷为原料，在有机铵盐存在下，碱性环境下，制备所述生物基环氧单体；优选的，四羟基单体（VP）与环氧氯丙烷（ECH）在有机铵盐存在下，于40～80℃反应1～12小时，然后在碱性环境下反应2～4小时，制备所述生物基环氧单体；优选的，有机铵盐为四丁基溴化铵；加入氢氧化钠溶液形成碱性环境；进一步优选的，室温下加入氢氧化钠溶液，然后反应2～4小时，制备所述生物基环氧单体；四羟基单体、环氧氯丙烷、四丁基溴化铵的摩尔比为1∶（40～250）∶（1～3）。
本发明公开了一种中温固化环氧树脂体系，包括上述生物基环氧单体、酸酐固化剂及催化剂，为一种新型生物基中温固化的高性能可降解多功能环氧树脂体系；经过中温固化，得到高性能可降解多功能环氧树脂。
本发明公开了上述中温固化环氧树脂体系的制备方法，将上述生物基环氧单体DGEVP与催化剂熔融混合均匀，然后于60～80℃下加入酸酐化合物，预聚20～40min，得到中温固化环氧树脂体系；然后采用中温（固化温度低于125℃）固化程序固化，得到高性能可降解多功能环氧树脂。其中，生物基环氧单体的环氧基团、酸酐化合物的酸酐基团的摩尔比为1∶（0.8～1.0）；催化剂为DGEVP质量的0.5～5%；优选的，DGEVP与催化剂熔融混合的温度为140～210℃。
本发明中，酸酐化合物为低熔点石油基酸酐、生物基酸酐或者其混合物，主要包括戊二酸酐、顺丁烯二酸酐、甲基四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐、十二烯基琥珀酸酐、顺丁烯二酸酐、柠康酸酐、丁二酸酐或其混合物。
本发明中，催化剂为有机金属络合物，如乙酰丙酮锌、乙酰丙酮锆、乙酰丙酮铝、乙酰丙酮铁、乙酰丙酮镉中的一种或几种。
本发明中，中温固化程序为阶梯升温方式，优选中温固化程序为80℃/2h+ 100℃/2h+120℃/0～4h。
本发明新型生物基环氧单体采用中温固化的高性能可降解多功能环氧树脂体具有优异的力学性能，弯曲强度：105～156MPa、冲击强度：13.5～32kJ/cm 2、拉伸强度：45～81MPa；良好的耐热性，T g：113～158℃；并兼具多功能型如自修复、形状记忆及温和的降解性。
有益效果
较之现有技术，本发明具有如下有益效果：
(1)本发明采用天然原料合成四环氧单体，由于环氧基的含量偏高，反应活性高。本发明中制备四环氧单体工艺同样适用于原儿茶醛和其他多元醇化合物及环氧氯丙烷反应制备多环氧官能团的环氧单体。
(2)本发明以酸酐为固化剂，采用中温固化程序（80℃/2h+ 100℃/2h+120℃/0-4h）可得到具多功能型如自修复、形状记忆及温和的酸降解性的高性能树脂体系，相对于现有生物质环氧单体甚至是传统商品化的双酚A环氧树脂，本发明树脂体系具有固化温度低及固化时间短的优势，能有效节约能耗，且固化体系的综合力学性和热性能明显优于现有报道的含动态可逆键的具有温和降解特性的生物质环氧体系，可与同固化剂固化的传统的商品化双酚A型环氧树脂体系力学及热性能相媲美。
 附图说明
图1为VP和DGEVP的合成示意图。
图2为PCA、赤藓糖醇、VP和DGEVP的FTIR图（a）；VP的 1H NMR图（b）；VP的 13C NMR图（c）；DGEVP的 1H NMR图（d）；DGEVP的 13C NMR图（e）；VP（f）和DGEVP（g）的LC-MS图。
图3为实施例1固化物样品表面划痕在200°C愈合过程图，用手术刀在固化物表面划动，形成深度约为22μm的划痕，然后放入烘箱。
图4为实施例1固化物样品在130°C形状变形及恢复图，首先在130℃下将固化物弯曲，室温定型，然后将弯曲样品放入烘箱，短时间内恢复。
图5为实施例1对比实施例1中树脂体系的DSC曲线，10℃/min。
图6为在50°C下，实施例2固化产物在1M盐酸溶液（丙酮/水= 9:1，v:v）中的降解图（a）；在50°C下，实施例2固化产物在0.1 M HCl溶液（丙酮/水=9:1，v:v）中的主要降解产物的实时1H NMR图（b）。
图7为实施例2固化物样品表面划痕在200°C愈合过程图。
图8为实施例2固化物样品在130°C形状变形及恢复图及三次形状记忆循环曲线图。
图9为实施例3固化物样品表面划痕在210°C愈合过程图。
图10为实施例3固化物样品在176°C形状变形及恢复图。
图11为实施例3固化物样品表面划痕在200°C愈合过程图。
图12为实施例4固化物样品在160°C形状变形及恢复图。
 本发明的实施方式
本发明以原儿茶醛、赤藓糖醇及环氧氯丙烷为主要原料合成的四环氧基单体（DGEVP），并以此环氧单体为原料，加入酸酐固化剂及催化剂，采用中温固化程序（≤120°C）获得高性能可降解多功能环氧树脂体系。本发明以原儿茶醛、赤藓糖醇为原料制备四羟基单体；然后以四羟基单体、环氧氯丙烷为原料制备所述生物基环氧单体。具体反应示例如下：
（1）将原儿茶醛，赤藓糖醇，催化剂对甲苯磺酸一水合物（p-TSA.H2O）， 溶剂N,N-二甲基甲酰胺和除水剂石油醚置于配有分水器和球形冷凝管的反应器；在氮气保护下，将混合物在70～100℃反应12～24小时，将产物冷却，然后倒入去离子水中析出沉淀，经抽滤并用水洗涤，最后在真空烘箱中干燥，得到四羟基单体产物（VP）。
（2）将得到的四羟基单体VP与环氧氯丙烷（ECH），四丁基溴化铵加入反应器中，在40～80℃反应1～12小时，然后在室温下滴加氢氧化钠溶液，滴加完成后继续反应2～4小时，再经抽滤得到粗产物，加入二氯甲烷和水，收集有机层，得到的有机层用无水硫酸镁干燥，再通过旋转蒸发仪除去溶剂及可能的ECH，最后干燥，得到目标环氧单体（DGEVP）。
上述技术方案中，原儿茶醛、赤藓糖醇、对甲苯磺酸一水合物、N,N-二甲基甲酰胺及石油醚的摩尔比为200∶（100～120）∶（4～6）∶300～500∶2000～4000；四羟基单体VP、环氧氯丙烷（ECH）、四丁基溴化铵的摩尔比为1∶（40～250）∶（1～3）。
为使本领域技术人员更好的理解本发明的技术方案，下面将通过具体实施方式来及附图对本发明的技术方案进行进一步清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。此外，除非另有说明，本发明使用的所有科学和技术术语具有与本发明所属技术领域人员通常理解的相同含义。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。本发明的原料以及具体制备操作与性能测试为常规技术。
合成例 四环氧单体的制备
（1）将原儿茶醛（PCA，0.2mol），赤藓糖醇（0.1mol），催化剂对甲苯磺酸一水合物（p-TSA·H 2O，0.0042mmol），溶剂N,N-二甲基甲酰胺（0.39mol）和除水剂石油醚(3.3mol)置于配有分水器和球形冷凝管的反应器。在氮气保护下，将混合物在90℃反应24小时，将产物冷却，然后倒入去离子水中析出沉淀，经抽滤并用去离子水洗涤五次，最后在真空烘箱中干燥6h，得到四羟基单体产物（VP）。图1（a）表示VP的合成示意图。
（2）将得到的四羟基单体VP（10g, 0.0026mol）与环氧氯丙烷（ECH）（51g, 0.551mol），四丁基溴化铵（1g，0.0031mol）依次加入反应器中，在80℃反应3小时后，然后在室温下滴加氢氧化钠水溶液（40wt%，11g），5分钟滴完，继续反应3小时，经抽滤得到粗产物，加入二氯甲烷和水，收集有机层，得到的有机层用无水硫酸镁干燥，再通过旋转蒸发仪除去溶剂，最后在90℃真空干燥5h，即为目标环氧单体（DGEVP）。图1（b）表示DGEVP的合成示意图。
图2是PCA、赤藓糖醇、VP和DGEVP的红外光谱（FTIR）图；VP的核磁共振谱（ 1H NMR）和碳核磁共振谱（ 13C NMR）图；DGEVP的 1H NMR和 13C NMR图；VP和DGEVP的液相色谱-质谱（LC-MS）图。VE是由PCA和赤藓糖醇缩合得到的，DGEVP是由VE上的羟基与ECH反应得到。如图1(a)所示，PCA的FTIR光谱显示了在羟基（约3190-3300 cm -1），苯环中C-H （3047 cm -1），醛基（-CHO）中C-H（2890-2725 cm -1），-CHO（1750 cm -1），和 芳香环（1650、1600和1530 cm -1）的特征吸收峰。赤藓糖醇的FTIR谱显示 -OH（3100-3500 cm -1），C-H（2965和 2908 cm -1，1406 cm -1），伯醇和仲醇（1080和1050 cm -1）C-O（972 cm -1）的特征吸收峰。与PCA和赤藓糖醇的光谱相比，VP的FTIR谱图出现了新的变化，在1005 cm -1、1280 cm -1、1160 cm -1和1107cm -1处有新强特征峰，这是由于形成的-C-O-C-、-C-O-、C-O-C产生的，此外，在VP的FTIR谱中没有出现-CHO的特征峰。当VP与ECH反应后，在910 cm -1处出现特征峰，为环氧基团的特征峰，同时在3100-3500 cm -1无出现明显的-OH峰，这意味着生物基四功能环氧单体DGEVP成功合成。
为进一步确定VP和DGEVP的化学结构，采用 1H NMR and 13C NMR表征了产物的结构，在VP的 1H NMR核磁谱图中，在δ=8.97 ppm 是苯环链接的OH中氢质子，在 δ=6.83, 6.76, 6.58 ppm 对应的是苯环中的氢质子；在 δ=5.58 ppm 对应-O-CH-O- 中的氢质子；在δ=4.18 ppm 和3.90-3.67 ppm 处对应-CH-O 和-C-CH 2-中的氢质子，VP的 13C NMR中的化学位移和峰数与VP中的碳原子也一一对应。此外，LC-MS谱显示VP的摩尔质量为 385.0911g/mol, 与理论值385.0900g/mol一致。这意味着VP成功合成。在DGEVP的1H NMR谱图中, 在δ=3.42-3.31ppm，2.89ppm和2.76ppm处为环氧基中的氢质子，在δ=3.76-3.64ppm 处为-O-CH-CH 2-中的氢质子，在δ=3.88-3.79ppm为-CH 2-O-CH 2-C-中的氢质子，在δ=5.58 ppm为醛基结构中的氢质子，在δ=7.10，7.00 和 6.94 ppm 为苯环中的氢质子。与VP的 1H NMR谱图相比，DGEVP的 1H NMR 谱图没有在8.97 ppm显示酚羟基中的质子峰。此外，DGEVP的 13C NMR中的化学位移和峰数与VP中的碳原子也一一对应，而LC-MS谱显示DGEVP的摩尔质量为 609.1948 g/mol, 与理论值609.1948g/mol 一致。这意味着DGEVP成功合成。
实施例1 中温固化环氧树脂体系及高性能可降解多功能环氧树脂
将100gDGEVP与1.25g乙酰丙酮锌（ZAA）的混合物在140℃下加热并搅拌至透明液体，然后在80°C加入33g戊二酸酐（GA），搅拌20min后得到均匀的预聚物中温固化环氧树脂体系。随后，将预聚物倒入预热模具中，在80°C真空烘箱中脱除气泡，再按照温度程序80°C/2h+100°C/2h固化得到固化产物。
对比实施例1
将100g双酚A环氧树脂（E51）与1.25g乙酰丙酮锌（ZAA）的混合物在140°C下加热并搅拌透明液体，然后在80°C加入30g戊二酸酐（GA），搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在80°C真空烘箱中脱除气泡，再按照温度程序80°C/2h+100°C/2h固化得到固化产物。
对比实施例1-1
将100g双酚A环氧树脂（E51）与1.25g乙酰丙酮锌（ZAA）的混合物在140°C下加热并搅拌至透明液体，然后在80°C加入30g戊二酸酐（GA），搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在80°C真空烘箱中脱除气泡，再按照温度程序80℃/2h+100℃/2h+140℃/2h +180℃/2h固化得到固化产物。
表1是实施例1、对比实施例1-1和对比实施例1-2固化物样品的力学性能数据、树脂体系反应活化能（Ea）、固化树脂体系环氧基的转化率（α）及玻璃化转变温度（T g）。从表1可以看出，本发明合成的生物质环氧树脂在中温下制备的树脂体系的力学性能与热性能均比中温及高温固化的传统的商品化的双酚A环氧树脂性能优异，树脂体系反应活化能 E a 较低，即使经中温固化处理，树脂体系也具有高的环氧基转化率，而且本发明较现有双酚A环氧树脂（DGEBA）具有明显高的T g，克服了现有生物质环氧树脂T g较双酚A环氧树脂差的问题。尤其是，DGEVP固化物在不但具有温和的酸降解行为，其在200°C具有良好的裂纹自修复能力（图3），在温度约T g+20°C具有良好的形状变形及恢复能力（图4）。酸酐固化的传统双酚A环氧树脂无酸性降解行为，DGEVP的固化物极易在酸性条件下降解。
a,b,c:弯曲强度、冲击强度及拉伸强度测试参照树脂浇铸体性能测试标准GB/T 2567-2008测试。
d:利用 Kissinger 极值法计算表观活化能。
e：基于样品的红外光谱，采用内标法计算环氧基团的转化率。
f: 采用DMA获得T g。
g:将50mg样品浸泡在10ml盐酸溶液观察降解时间。
现有技术以原儿茶醛和4,4-二氨基二苯醚（ODA）为原料，合成了半生物基PH-ODA，以PH-ODA、环氧氯丙烷和NaOH 为原料，采用二步法合成半生物基阻燃环氧预聚物，采用固化剂DDM固化环氧预聚物PH-ODA-EP，得环氧固化物PH-ODA-EP/DDM，与DGEBA/DDM相比，Ea高，PH-ODA-EP/DDM 固化体系的反应活性低于DGEBA/DDM 固化体系，需要190℃的固化温度，且含有一部分石油基原料ODA，并未实现完全利用生物基原料。相比于现有报道含螺旋缩醛、单环缩醛及双环缩醛结构双环氧基单体的固化物体系相比，本发明环氧树脂/酸酐固化体系具有良好的自修复行为，且固化温度低，生产能耗小。
本发明树脂体系固化温度低，现有含缩醛环氧/酸酐体系的固化温度存在偏高的缺陷，图5 给出了实施例1对比实施例1中树脂体系的DSC曲线，明显地，DGEVP/GA/ZAA比E51/GA/ZAA的反应温度低。
实施例2
将100gDGEVP与2.5g乙酰丙酮锌（ZAA）的混合物在140°C下加热并搅拌至透明液体，然后在80°C加入33g戊二酸酐（GA），搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在真空烘箱中脱除气泡，再按照温度程序80°C/2h+100°C/2h固化得到固化产物。
对比实施例2
将100gE51与2.5g乙酰丙酮锌（ZAA）的混合物在140°C下加热并搅拌至透明液体，然后在80°C加入30g戊二酸酐（GA），再搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在真空烘箱中脱除气泡，再按照温度程序80℃/2h+100℃/2h+140℃/2h +180℃/2h固化得到固化产物。
表2是实施例2及对比实施例2固化物样品的力学性能数据、树脂体系的E a、环氧基的转化率α及T g。从表2可以看出，本发明合成的生物质环氧树脂在中温下制备的树脂体系的力学性能与热性能均比中温及高温固化的传统的商品化的双酚A环氧树脂性能优异，树脂体系反应活化能E a较低，即使经中温固化处理，树脂体系也具有高的环氧基转化率。DGEVP固化物极易在酸性条件下降解（图6（a）），使用实时核磁共振监测了固化物样品在50°C下的0.1M HCl溶液（丙酮/水= 9:1，v:v）中的降解产物，参见图6（b）。此外，DGEVP固化物在200°C具有良好的裂纹自修复能力（图7）。DGEVP固化物在T g温度以上具有良好的形状变形及恢复能力（图8）。
实施例3
将100gDGEVP与5.0g乙酰丙酮锆（AAZ）的混合物在200°C下加热并搅拌至透明液体，然后在80°C下加入55g甲基六氢邻苯二甲酸酐（MeHHPA）下，搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在真空烘箱中脱除气泡，再按照温度程序80°C/2h+100°C/2h+120°C/4h得到固化产物。
对比实施例3
将100gE51与5.0g乙酰丙酮锆（AAZ）的混合物在200°C下加热并搅拌至透明液体，然后在80°C加入45g甲基六氢邻苯二甲酸酐（MeHHPA）下搅20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在真空烘箱中脱除气泡，再按照温度程序80℃/2h+100℃/2h+140℃/2h +180℃/2h得到固化产物。
表3是实施例3及对比实施例3固化物样品的力学性能数据、树脂体系的Ea、固化树脂体系环氧基的转化率α及玻璃化转变温度T g。从表3可以看出，本发明合成的生物质环氧树脂在中温下制备的树脂体系的力学性能与热性能均比中温及高温固化的传统的商品化的双酚A环氧树脂性能优异，树脂体系反应活化能Ea较低，即使经中温固化处理，树脂体系也具有高的环氧基转化率，其固化物极易在酸性条件下降解。此外，DGEVP固化物在200°C具有良好的裂纹自修复能力（图9）。DGEVP固化物在T g温度以上具有良好的形状变形及恢复能力（图10）。
实施例4
将60gDGEVP与0.5g乙酰丙酮锌（ZAA）的混合物在140°C下加热并搅拌至透明液体，然后在80°C下加入22g柠康酸酐，搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在真空烘箱中脱除气泡，再按照温度程序80°C/2h+100°C/2h+120°C/2h得到固化产物。
对比实施例4
将60gE51与0.5g乙酰丙酮锌（ZAA）的混合物在140°C下加热并搅拌至透明液体，然后在80°C加入18g柠康酸酐，再搅拌20min后得到均匀的预聚物。随后，将预聚物倒入预热模具中，在真空烘箱中脱除气泡，再按照温度程序80℃/2h+100℃/2h+140℃/2h +180℃/2h固化得到固化产物。
表4是实施例4及对比实施例4固化物样品的力学性能数据、树脂体系反应活化能Ea、固化树脂体系环氧基的转化率α及玻璃化转变温度Tg。从表4以看出，本发明合成的生物质环氧树脂在中温下制备的树脂体系的力学性能与热性能均比中温及高温固化的传统的商品化的双酚A环氧树脂性能优异，树脂体系反应活化能Ea较低，即使经中温固化处理，树脂体系也具有高的环氧基转化率，其固化物极易在酸性条件下降解。此外，DGEVP固化物在200°C具有良好的裂纹自修复能力（图11）。DGEVP固化物在T g温度以上具有良好的形状变形及恢复能力（图12）。

Claims (11)

  1. 一种生物基环氧单体，其特征在于，所述生物基环氧单体的化学结构式如下：
    。
  2. 权利要求1所述生物基环氧单体的制备方法，其特征在于，以原儿茶醛、赤藓糖醇及环氧氯丙烷为原料合成所述生物基环氧单体。
  3. 根据权利要求2所述生物基环氧单体的制备方法，其特征在于，以原儿茶醛、赤藓糖醇为原料制备四羟基单体；然后以四羟基单体、环氧氯丙烷为原料制备所述生物基环氧单体。
  4. 根据权利要求3所述生物基环氧单体的制备方法，其特征在于，以原儿茶醛、赤藓糖醇为原料，在催化剂存在下、溶剂中，反应制备四羟基单体；以四羟基单体、环氧氯丙烷为原料，在有机铵盐存在下，碱性环境下，制备所述生物基环氧单体。
  5. 根据权利要求4所述生物基环氧单体的制备方法，其特征在于，催化剂为对甲苯磺酸一水合物；原儿茶醛、赤藓糖醇、对甲苯磺酸一水合物的摩尔比为200∶（100～120）∶（4～6）；有机铵盐为四丁基溴化铵；加入氢氧化钠溶液形成碱性环境；四羟基单体、环氧氯丙烷、四丁基溴化铵的摩尔比为1∶（40～250）∶（1～3）。
  6. 一种中温固化环氧树脂体系，其特征在于，包括权利要求1所述生物基环氧单体、酸酐固化剂及催化剂。
  7. 权利要求6所述中温固化环氧树脂体系的制备方法，其特征在于，将权利要求1所述生物基环氧单体与催化剂熔融混合均匀，然后于60～80℃下加入酸酐化合物，预聚得到中温固化环氧树脂体系。
  8. 根据权利要求7所述中温固化环氧树脂体系的制备方法，其特征在于，酸酐化合物为低熔点石油基酸酐、生物基酸酐或者其混合物；催化剂为有机金属络合物。
  9. 一种高性能可降解多功能环氧树脂，由权利要求6所述中温固化环氧树脂体系经过中温固化得到。
  10. 权利要求1所述生物基环氧单体、权利要求6所述中温固化环氧树脂体系或者权利要求9所述高性能可降解多功能环氧树脂在制备高性能可降解多功能环氧材料中的应用。
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