Biomass-based epoxy resin and preparation method thereof

Abstract

The present invention discloses a biomass-based epoxy resin and preparation method thereof; under conditions of N,N-dimethylformamide as a catalyst, 2,5-furandicarboxylic acid and thionyl chloride are acylated to obtain 2,5-furan diformyl chloride; then it is dissolved with dichloromethane; under tertiary amine conditions an esterification reaction takes place, and bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylic acid ester is thus obtained; by means of meta-chloroperoxybenzoic acid, its unsaturated double bond is epoxidized to obtain a biomass-based epoxy resin. The process of the present invention is simple; the raw materials come from biomass 2,5-furandicarboxylic acid and eugenol; in comparison with bisphenol-A epoxy resin based on petroleum and coal resources, the raw materials are green and renewable, and are advantageous to reducing the consumption of renewable resources with regard to polymeric material. The obtained cured epoxy resin has excellent thermal properties and modulus, and has broad prospects for application.

Claims

1. A preparation method of a biomass-based epoxy resin, characterized in comprising the following steps: (1) by mole, mixing 100 parts of 2,5-furandicarboxylic acid, 150 to 250 parts of thionyl chloride and N,N-dimethylformamide catalyst and stirring to react at a temperature of 70 to 80 C. for 3 to 5 h, naturally cooling to room temperature, removing thionyl chloride by vacuum distillation, and drying to obtain 2,5-furan dicarboxylic acid chloride; (2) by mole, dissolving 190 to 210 parts of eugenol and 240 to 300 parts of tertiary amine in 3120 to 7800 parts of dichloromethane solvent to obtain eugenol solution; at a temperature of 5 to 0 C., adding a solution by 100 parts of said 2,5-furan dicarboxylic acid chloride dissolved in 3120 to 7800 parts of dichloromethane dropwise in said eugenol solution, after completion of dropwise addition, heating the reaction solution to the temperature of 20 to 30 C., and continuing the reaction for 2 to 4 h; and then removing dichloromethane under vacuum rotary evaporation, washing and drying to obtain bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate; (3) by mole, dissolving 100 parts of said bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate in 4680 to 9360 parts of dichloromethane, then adding 300 to 400 parts of metachloroperbenzoic acid in under stirring at the temperature of 20 to 30 C., continuing to react for 2 to 4 days, and then a filtrate is obtained after filtration; washing and removing the solvent in the filtrate, and then washing again to obtain a white solid, which is the biomass-based epoxy resin.

2. The preparation method of a biomass-based epoxy resin according to claim 1, wherein said tertiary amine is one of triethylamine, N-ethyl diisopropylamine, pyridine, or any combination thereof.

3. A biomass-based epoxy resin obtained by the preparation method according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is synthesis of 2,5-furan dicarboxylic acid chloride in the example 1.

(2) FIG. 2 is synthesis of bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate.

(3) FIG. 3 is the .sup.1H-NMR spectrum of bis(4-allyl-2-methoxyphenyl) furan-2,5-dicarboxylate prepared in Example 1 of this invention.

(4) FIG. 4 is synthesis of fully biobased epoxy resin prepared in Example 1 of this invention.

(5) FIG. 5 is the .sup.1H-NMR spectrum of fully biobased epoxy resin prepared in Example 1 of this invention.

(6) FIG. 6 is the .sup.13C-NMR spectrum of fully biobased epoxy resin prepared in Example 1 of this invention.

(7) FIG. 7 is the high resolution mass spectrum of fully biobased epoxy resin prepared in Example 1 of this invention.

(8) FIG. 8 is dynamic mechanical analyses (DMA) curves of fully biobased epoxy resin prepared in Example 1 and DGEBA prepared in Control Example 2 of this invention.

DETAILED DESCRIPTION OF THE INVENTION

(9) The technical solution of this invention will be further described below with the accompanying figures and examples.

Example 1

(10) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(11) 31.20 g 2,5-Furandicarboxylic acid, 35.69 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 3 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(12) As shown in FIG. 1, it gives the synthesis reaction formula of 2,5-furan dicarboxylic acid chloride of this invention;

(13) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(14) 31.20 g Eugenol and 24.29 g triethylamine acting as base are dissolved in 200 mL dichloromethane to make solution A; at the temperature ranging from 5 to 0 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 20 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(15) The reaction equation and .sup.1H-NMR spectra of the fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate obtained in this example are shown in FIG. 2 and FIG. 3, respectively.

(16) FIG. 1 shows the reaction scheme (reaction equation) for synthesizing the intermediate 2,5-furan dicarboxylic acid chloride provided by this example, the reaction is a carboxylic acid acyl chloride reaction. FIG. 2 shows, the reaction scheme (reaction equation) for synthesizing fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate in this example, the reaction is an esterification reaction.

(17) FIG. 3 shows the .sup.1H-NMR spectrum of fully biobased bis(4-allyl-2-methoxy-phenyl)furan-2,5-dicarboxylate obtained in Example 1 of this invention. It can be seen that the peaks at 5.98 ppm and 5.045.20 ppm represent protons of allyl groups, the peak at 3.40 ppm represents the proton of methylene groups adjacent to the double bond of allyl groups, the peak at 3.82 ppm represents the proton of methoxy groups, the peak at 7.43 ppm represents the proton of furan rings, other peaks match with the chemical shifts of protons of the biobased allyl compound.

(18) 3) Preparation of the Biobased Epoxy Resin

(19) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 150 mL dichloromethane, then 30.45 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 20 C. The reaction kept for 2 days, and then a filtrate is obtained after filtration, which is then washed with 63.02 g 10% Na.sub.2SO.sub.3, 53.00 g 10% Na.sub.2CO.sub.3 and deionized water, successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid. The reaction equation, .sup.1H-NMR, .sup.13C-NMR and high resolution mass spectra of the biobased epoxy resin obtained in this example are shown in FIGS. 4, 5, 6, 7 and 8, respectively.

(20) FIG. 4 shows the reaction scheme (reaction equation) for the synthesis of the biobased epoxy resin provided by this example, the reaction is an epoxidation of double bonds

(21) As shown in FIG. 5, it is the .sup.1H-NMR spectrum of the biobased epoxy resin provided by Example 1 in this invention. It can be seen that, the characteristic peaks at 5.98 ppm and 5.08-5.16 ppm corresponding to protons on double bonds of allyl groups are not found, while the characteristic peaks of proton on epoxy group are observed (2.57 ppm, 2.80-2.84 ppm, 3.14-3.20 ppm), other peaks reflect protons on biobased epoxy resin, indicating that the expected compound has been successfully synthesized.

(22) As shown in FIG. 6, it is the .sup.13C-NMR spectrum of the biobased epoxy resin provided by Example 1 in this invention. Characteristic peaks representing carbon atoms on epoxy groups appear at 52.46 ppm and 47.00 ppm.

(23) As shown in FIG. 7, it is the high resolution mass spectrometry of the biobased epoxy resin provided by Example 1 in this invention. Its theoretical molecular weight [M] is 480.1420, the theoretical value of [M+Na.sup.+] is 503.1313, which is well agreed with the experimental value (503.1306).

(24) Based on above figures, it is reasonable to state that the target fully biobased epoxy resin is synthesized in Example 1 of this invention.

(25) Control Example 1, Preparation of Biobased Epoxy Resin:

(26) The biobased epoxy resin provided by Example 1 (9.6 g), methylhexahydrophthalic anhydride (curing agent, 6.7 g) and 2-ethylmethylimidazole (accelerator, 81.7 g) are mixed uniformly, and then precured at a constant temperature of 80 C. for 30 min to get a prepolymer; the prepolymer is poured into a preheated glass mold and degassed under vacuum at 80 C. for 30 min, followed by curing with the procedure of 130 C./2 h+150 C./2 h+170 C./2 h; after natural cooling to room temperature and demolding, the cured biobased epoxy resin is obtained. Its storage modulus-temperature curve is shown in FIG. 8.

(27) Control Example 2, Preparation of DGEBA Resin:

(28) DGEBA (its trademark is E44, epoxide equivalent is 210-240 g/eq, 10.0 g), methylhexahydrophthalic anhydride (7.4 g) and 2-ethylmethylimidazole (accelerator, 87.0 g) are mixed uniformly, and then precured at a constant temperature of 80 C. for 30 min; the prepolymer is poured into a preheated glass mold and degassed under vacuum at 80 C. for 30 min to get a prepolymer, followed by curing with the procedure of 130 C./2 h+150 C./2 h+170 C./2 h; after natural cooling to room temperature and demolding, the cured DGEBA resin is obtained. Its storage modulus-temperature curve is shown in FIG. 8.

(29) As shown in FIG. 8, it is DMA curves of the biobased epoxy resin prepared in Control Example 1 and the DGEBA resin prepared in Control Example 2 of this invention. It can be seen that, the storage modulus of epoxy resin prepared in Control Example 1 at 50 C. is 2229 MPa, 19.9% higher than that of DGEBA resin prepared in Control Example 2 (1860 MPa). T.sub.g of the epoxy resin provided in Control Example 1 is 153.4 C., while that of DGEBA resin prepared in Comparative Example 2 is 144.1 C. The figure demonstrates that the biobased epoxy resin provided in this invention has a high modulus and T.sub.g after curing. This is due to the fact that there is furan group in the chemical structure of the biobased epoxy resin-based provided by this invention, which can improve the rigidity and heat resistance of epoxy resins.

Example 2

(30) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(31) 31.20 g 2,5-Furandicarboxylic acid, 35.69 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 3 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(32) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(33) 32.84 g Eugenol and 27.33 g triethylamine acting as base are dissolved in 300 mL dichloromethane to make solution A; at the temperature range of 2.51 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 300 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 20 C. for 3 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(34) 3) Preparation of the Biobased Epoxy Resin

(35) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 225 mL dichloromethane, then 35.5 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 25 C. The reaction kept for 3 days, and then a filtrate is obtained after filtration, which is then washed with 84.03 g 10% Na.sub.2SO.sub.3, 70.66 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 3

(36) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(37) 31.20 g 2,5-Furandicarboxylic acid, 35.69 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 3 h at 70 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(38) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(39) 34.48 g Eugenol and 30.36 g triethylamine acting as base are dissolved in 500 mL dichloromethane to make solution A; at the temperature range of 11 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 500 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 20 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

Example 4

(40) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(41) 31.20 g 2,5-Furandicarboxylic acid, 35.69 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 3 h at 70 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(42) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(43) 31.20 g Eugenol and 31.03 g triethylamine acting as base are dissolved in 300 mL dichloromethane to make solution A; at the temperature range of 41 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 20 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(44) 3) Preparation of the Biobased Epoxy Resin

(45) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 150 mL dichloromethane, then 30.45 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 20 C. The reaction kept for 2 days, and then a filtrate is obtained after filtration, which is then washed with 63.02 g 10% Na.sub.2SO.sub.3, 53.00 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 5

(46) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(47) 31.20 g 2,5-Furandicarboxylic acid, 35.69 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 3 h at 70 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(48) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(49) 34.48 g Eugenol and 23.73 g triethylamine acting as base are dissolved in 500 mL dichloromethane to make solution A; at the temperature range of 11 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 500 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 20 C. for 4 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(50) 3) Preparation of the Biobased Epoxy Resin

(51) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 225 mL dichloromethane, then 35.5 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 25 C. The reaction kept for 3 days, and then a filtrate is obtained after filtration, which is then washed with 84.03 g 10% Na.sub.2SO.sub.3, 70.66 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 6

(52) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(53) 31.20 g 2,5-Furandicarboxylic acid, 47.59 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 4 h at 75 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(54) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(55) 31.20 g Eugenol and 24.29 g triethylamine acting as base are dissolved in 200 mL dichloromethane to make solution A; at the temperature ranging from 5 to 0 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 25 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(56) 3) Preparation of the Biobased Epoxy Resin

(57) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 300 mL dichloromethane, then 40.6 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 30 C. The reaction kept for 4 days, and then a filtrate is obtained after filtration, which is then washed with 126.04 g 10% Na.sub.2SO.sub.3, 105.99 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 7

(58) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(59) 31.20 g 2,5-Furandicarboxylic acid, 47.59 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 4 h at 75 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(60) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(61) 32.84 g Eugenol and 27.33 g triethylamine acting as base are dissolved in 300 mL dichloromethane to make solution A; at the temperature range of 2.51 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 300 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 25 C. for 3 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(62) 3) Preparation of the Biobased Epoxy Resin

(63) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 150 mL dichloromethane, then 30.45 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 20 C. The reaction kept for 2 days, and then a filtrate is obtained after filtration, which is then washed with 63.02 g 10% Na.sub.2SO.sub.3, 53.00 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 8

(64) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(65) 31.20 g 2,5-Furandicarboxylic acid, 47.59 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 4 h at 75 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(66) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(67) 34.48 g Eugenol and 30.36 g triethylamine acting as base are dissolved in 500 mL dichloromethane to make solution A; at the temperature range of 11 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 500 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 25 C. for 4 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(68) 3) Preparation of the Biobased Epoxy Resin

(69) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 225 mL dichloromethane, then 35.5 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 20 C. The reaction kept for 2 days, and then a filtrate is obtained after filtration, which is then washed with 84.03 g 10% Na.sub.2SO.sub.3, 70.66 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 9

(70) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(71) 31.20 g 2,5-Furandicarboxylic acid, 31.03 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 4 h at 75 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(72) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(73) 31.20 g Eugenol and 31.03 g triethylamine acting as base are dissolved in 200 mL dichloromethane to make solution A; at the temperature range of 41 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 25 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(74) 3) Preparation of the Biobased Epoxy Resin

(75) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 300 mL dichloromethane, then 40.6 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 30 C. The reaction kept for 4 days, and then a filtrate is obtained after filtration, which is then washed with 126.04 g 10% Na.sub.2SO.sub.3, 105.99 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 10

(76) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(77) 31.20 g 2,5-Furandicarboxylic acid, 47.59 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 4 h at 75 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(78) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(79) 34.48 g Eugenol and 23.73 g triethylamine acting as base are dissolved in 500 mL dichloromethane to make solution A; at the temperature range of 11 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 500 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 25 C. for 4 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(80) 3) Preparation of the Biobased Epoxy Resin

(81) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 150 mL dichloromethane, then 30.45 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 20 C. The reaction kept for 2 days, and then a filtrate is obtained after filtration, which is then washed with 63.02 g 10% Na.sub.2SO.sub.3, 53.00 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 11

(82) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(83) 31.20 g 2,5-Furandicarboxylic acid, 59.48 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 5 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(84) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(85) 31.20 g Eugenol and 24.29 g triethylamine acting as base are dissolved in 200 mL dichloromethane to make solution A; at the temperature ranging from 5 to 0 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 30 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(86) 3) Preparation of the Biobased Epoxy Resin

(87) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 225 mL dichloromethane, then 35.5 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 25 C. The reaction kept for 3 days, and then a filtrate is obtained after filtration, which is then washed with 84.03 g 10% Na.sub.2SO.sub.3, 70.66 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 12

(88) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(89) 31.20 g 2,5-Furandicarboxylic acid, 59.48 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 5 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(90) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(91) 32.84 g Eugenol and 27.33 g triethylamine acting as base are dissolved in 300 mL dichloromethane to make solution A; at the temperature range of 2.51 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 300 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 30 C. for 3 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(92) 3) Preparation of the Biobased Epoxy Resin

(93) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 300 mL dichloromethane, then 40.6 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 30 C. The reaction kept for 4 days, and then a filtrate is obtained after filtration, which is then washed with 126.04 g 10% Na.sub.2SO.sub.3, 105.99 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 13

(94) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(95) 31.20 g 2,5-Furandicarboxylic acid, 59.48 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 5 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(96) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(97) 34.48 g Eugenol and 30.36 g triethylamine acting as base are dissolved in 500 mL dichloromethane to make solution A; at the temperature range of 11 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 500 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 30 C. for 4 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(98) 3) Preparation of the Biobased Epoxy Resin

(99) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 150 mL dichloromethane, then 30.45 g metachloroperbenzoic acid (75 wt %) is slowly added under stirring at 20 C. The reaction kept for 2 days, and then a filtrate is obtained after filtration, which is then washed with 63.02 g 10% Na.sub.2SO.sub.3, 53.00 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 14

(100) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(101) 31.20 g 2,5-Furandicarboxylic acid, 59.48 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 5 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(102) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(103) 31.20 g Eugenol and 31.03 g triethylamine acting as base are dissolved in 200 mL dichloromethane to make solution A; at the temperature range of 41 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 30 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(104) 3) Preparation of the Biobased Epoxy Resin

(105) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 225 mL dichloromethane, then 35.5 g metachloroperbenzoic acid (85 wt %) is slowly added under stirring at 25 C. The reaction kept for 3 days, and then a filtrate is obtained after filtration, which is then washed with 84.03 g 10% Na.sub.2SO.sub.3, 70.66 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 15

(106) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(107) 31.20 g 2,5-Furandicarboxylic acid, 59.48 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 5 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(108) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(109) 34.48 g Eugenol and 23.73 g triethylamine acting as base are dissolved in 500 mL dichloromethane to make solution A; at the temperature range of 11 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 500 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 30 C. for 4 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is obtained.

(110) 3) Preparation of the Biobased Epoxy Resin

(111) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 300 mL dichloromethane, then 40.6 g metachloroperbenzoic acid (75 wt %) is slowly added under stirring at 30 C. The reaction kept for 3 days, and then a filtrate is obtained after filtration, which is then washed with 126.04 g 10% Na.sub.2SO.sub.3, 105.99 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.

Example 16

(112) 1) Synthesis of 2,5-Furan Dicarboxylic Acid Chloride

(113) 31.20 g 2,5-Furandicarboxylic acid, 59.48 g thionyl chloride and N,N-dimethylformamide (DMF, catalyst, 0.05 mL) are mixed; the reaction is carried out for 4 h at 80 C. with stirring, and then the mixture is naturally cooled to room temperature. After removing the thionyl chloride under reduced pressure and drying, 2,5-furan dicarboxylic acid chloride is obtained.

(114) 2) Synthesis of Fully Biobased bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate

(115) 31.20 g Eugenol and 8.10 g trimethylamine, 10.34 g N-ethyldiisopropylamine, 7.91 g pyridine, which acted as base are dissolved in 200 mL dichloromethane to make solution A; at the temperature ranging from 5 to 0 C., 2,5-furan dicarboxylic acid chloride (19.30 g) is dissolved in 200 mL dichloromethane solution to get 2,5-furan dicarboxylic acid chloride solution, which is then slowly dropped into solution A; After dropwise addition is completed, the reaction solution is slowly heated and maintained at 30 C. for 2 h; after the reaction is over, removing the solvent under reduced pressure, followed by washing with deionized water and drying, successively, a fully biobased bis(4-allyl-2-methoxyphenyl)-furan-2,5-dicarboxylate is obtained.

(116) 3) Preparation of the Biobased Epoxy Resin

(117) 22.42 g Bis(4-allyl-2-methoxyphenyl)furan-2,5-dicarboxylate is dissolved in 300 mL dichloromethane, then 40.6 g metachloroperbenzoic acid (75 wt %) is slowly added under stirring at 25 C. The reaction kept for 3 days, and then a filtrate is obtained after filtration, which is then washed with 126.04 g 10% Na.sub.2SO.sub.3, 105.99 g 10% Na.sub.2CO.sub.3 and deionized water successively; the organic layer is obtained by separating and dried over anhydrous sodium sulfate; dichloromethane is removed to obtain a yellow solid which is washed by diethyl ether to get a white solid.