CN114395216A - Bio-based hyperbranched polymer epoxy resin and preparation method thereof - Google Patents
Bio-based hyperbranched polymer epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bio-based hyperbranched polymer epoxy resin, which is prepared by dynamically crosslinking ferulic acid hyperbranched epoxy resin and citric acid hyperbranched polyester. The invention also discloses a preparation method of the resin. The epoxy resin prepared by the invention is obtained by dynamically crosslinking ferulic acid hyperbranched epoxy resin and citric acid hyperbranched polyester, and a large number of interface covalent bonds are formed in a crosslinked network structure, so that the epoxy resin has a function of repeatable processing; the degradation product ferulic acid and citric acid hyperbranched polyester can be prepared into full-bio-based epoxy resin again, and the green closed-loop recovery of the epoxy resin is realized. The resin prepared by the method has excellent mechanical property, heat resistance, solvent resistance, hydrolysis resistance, creep resistance and corrosion resistance, can replace petroleum-based epoxy resin, and is applied to the fields of electronic packaging, insulating materials, printed circuit boards and the like.
Description
Technical Field
The invention relates to the technical field of high-performance high-molecular resin, in particular to bio-based hyperbranched polymer epoxy resin and a preparation method thereof.
Background
Epoxy resins have the advantages of high strength, good solvent resistance, water and corrosion resistance, good insulating properties, etc., and are therefore widely used. Because the irreversible crosslinked network of the epoxy resin makes the degradation and recovery of the epoxy resin very difficult, the epoxy resin is mostly incinerated or buried, which wastes resources and pollutes the environment. Therefore, the design of high-performance green recyclable epoxy resin is of great significance.
The epoxy resin constructed based on the dynamic covalent bond generates the rearrangement of a cross-linked network structure under the external stimulation, thereby endowing the epoxy resin with the characteristics of self-repairing, repeatable processing and the like, and providing an effective way for the green recovery of the epoxy resin and the composite material thereof. Since 2011 the Leible proposed the Vitrimer concept based on the epoxy resin/anhydride dynamic exchange network, researchers constructed various epoxy resin systems based on beta-hydroxy ester exchange, D-A reaction, disulfide exchange, dynamic imine bond exchange and the like, and realized the self-repairing and remoldable processing of epoxy resin. However, the self-repairing performance and the mechanical strength of the epoxy resin containing the dynamic covalent bond are mutually contradictory, and the introduction of the dynamic covalent bond reduces the crosslinking density, the strength and the modulus of the epoxy resin. At present, it has been reported that epoxy resin containing dynamic covalent bond generally does not have strong thermal property and mechanical property, so it is necessary to design a high-performance reworkable epoxy resin. In addition, a large amount of organic solvent is required in the chemical degradation process of the epoxy resin at present, only part of degradation products can be reused, and secondary environmental pollution is easily caused.
The hyperbranched polymer has the characteristics of a highly branched structure, approximately spherical molecular shape, a large number of active terminal groups for modification on the outer surface, a unique microporous structure in the interior and the like. Compared with linear polymers, the polymer has the advantages of less molecular chain entanglement, difficult crystallization, low viscosity, good solubility and higher chemical reaction activity, and more functional materials can be obtained through terminal group modification. The excellent characteristics enable the hyperbranched polymer to show wide application prospects in polymer blending modification, coatings, drug release, self-assembled films and other aspects. Hyperbranched polymer toughened epoxy resin is a research hotspot in recent years, and the unique structure and performance of hyperbranched polymer enables the hyperbranched polymer to have a modification effect which is obviously different from that of linear polymer when used as a toughening agent of epoxy resin. The problem of difficult recovery of high-performance epoxy resin is hopeful to be solved by utilizing the bio-based hyperbranched epoxy resin to dynamically crosslink the epoxy resin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bio-based hyperbranched polymer epoxy resin constructed based on dynamic covalent bonds.
The invention also provides a preparation method of the bio-based hyperbranched polymer epoxy resin.
In order to solve the first technical problem, the bio-based hyperbranched polymer epoxy resin provided by the invention is prepared by dynamically crosslinking ferulic acid hyperbranched epoxy resin and citric acid hyperbranched polyester, wherein the ferulic acid hyperbranched epoxy resin is a compound including but not limited to the following structure:
(1)
wherein
(2)
(3)
The citric acid hyperbranched polyester has the following structure:
wherein
In order to solve the second technical problem, the bio-based hyperbranched polymer epoxy resin provided by the invention is prepared by the following preparation method:
(1) uniformly mixing ferulic acid and epoxy chloropropane, stirring and reacting at 80-120 ℃ for 1-4 h, adding 10-40 wt% of sodium hydroxide aqueous solution, continuing to react at 20-40 ℃ for 1-6h, and filtering, washing, separating liquid and distilling under reduced pressure after the reaction is finished to obtain the linear ferulic acid epoxy resin FEP.
(2) Stirring and reacting FEP, a ternary hydroxyl compound and an ionic liquid at the temperature of 60-140 ℃ for 1-12 h to obtain the ferulic acid hyperbranched epoxy resin FEHBP.
(3) And stirring and reacting the citric acid and the acid anhydride at 100-160 ℃ for 1-6 hours to obtain the citric acid hyperbranched polyester CHBP.
(4) The FEP, the FEHBP and the CHBP are mixed and stirred uniformly, poured into a mold and cured for 4-8 hours at the temperature of 80-120 ℃ to obtain the all-bio-based epoxy resin.
Heating and degrading the full-bio-based epoxy resin in 10-40% sodium hydroxide aqueous solution at 60-100 ℃ for 30-60 min, adjusting the pH value of the degradation solution to be neutral (pH 7) by using 0.5-2 mol/L organic acid, and then respectively carrying out reduced pressure distillation on an aqueous layer and an organic layer to obtain closed-loop recovered ferulic acid (r-FA) and closed-loop recovered citric acid hyperbranched polyester (r-CHBP). The organic acid is one or more than two of hydrochloric acid, formic acid, phosphoric acid and oxalic acid. The molar ratio of the total bio-based epoxy resin, the sodium hydroxide and the organic acid is 1 (0.55-0.65) to 0.50-0.60.
Uniformly mixing r-FA and epoxy chloropropane, stirring and reacting at 80-120 ℃ for 1-4 h, adding 10-40 wt% of sodium hydroxide aqueous solution, continuing to react at 20-40 ℃ for 1-6h, and filtering, washing, separating liquid and distilling under reduced pressure after the reaction is finished to obtain the linear ferulic acid epoxy resin FEP. The molar ratio of the r-FA to the epoxy chloropropane to the sodium hydroxide is 1.0 (10.0-20.0) to 2.0-4.0.
Stirring r-FEP, the ternary hydroxyl compound and the ionic liquid at the temperature of 60-140 ℃ for reacting for 1-6h to obtain the ferulic acid hyperbranched epoxy resin FEHBP. The molar ratio of the FEP to the ternary hydroxyl compound to the ionic liquid is 1:0.33 (0.005-0.01), the ternary hydroxyl compound is one or more of trimethylolpropane, trihydroxyethyl isocyanurate and glycerol, and the ionic liquid is one or more of tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt, N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate and tetrabutylammonium hexafluorophosphate.
(6) And mixing and stirring r-FEP, r-FEHBP and r-CHBP uniformly, pouring into a mould, and curing at 80-120 ℃ for 4-8 h to obtain the closed-loop recycled all-bio-based epoxy resin. The molar ratio of the r-FEP, the r-FEHBP and the r-CHBP is 1.0 (1.0-1.5) to 1.0-5.0.
And crushing the full-bio-based epoxy resin, and then carrying out hot pressing at 80-160 ℃ and 2-10 MPa for 30-60 min to obtain the fully-bio-based epoxy resin for repeated processing. The ferulic acid hyperbranched polymer containing dynamic covalent bonds has the advantages of low viscosity, strengthening, toughening, degrading and the like, and the epoxy resin prepared by the ferulic acid hyperbranched polymer can form a dynamic crosslinking network containing a large amount of beta-hydroxy ester, so that the ferulic acid hyperbranched polymer has high strength and high toughness and also has the capacity of being processed repeatedly and the performance of closed-loop recycling and degrading.
Preferably, the molar ratio of the ferulic acid to the epichlorohydrin to the sodium hydroxide is 1.0 (10.0-20.0) to 2.0-4.0.
Preferably, the mol ratio of the FEP, the ternary hydroxyl compound and the ionic liquid is 1:0.33 (0.005-0.01), the ternary hydroxyl compound is one or more of trimethylolpropane, trihydroxyethyl isocyanurate and glycerol,
preferably, the ionic liquid is one or more of tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt, N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate and tetrabutylammonium hexafluorophosphate.
Preferably, the acid anhydride is one or more of itaconic anhydride and phthalic anhydride, and the molar ratio of the citric acid to the acid anhydride is (2.0-80.0): 1.0
The mol ratio of FEP, FEHBP and CHBP is 1 (0.003-0.009): 0.04-0.05).
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
1. the ferulic acid hyperbranched epoxy resin and the citric acid hyperbranched polyester prepared by the invention can form a large number of interface covalent bonds in a crosslinking network structure when the epoxy resin is dynamically crosslinked, so that the epoxy resin can be repeatedly processed.
2. The ferulic acid hyperbranched polymer and the citric acid hyperbranched polyester dynamically crosslinked epoxy resin prepared by the invention can be controllably degraded into ferulic acid and citric acid hyperbranched polyester under the action of a sodium hydroxide aqueous solution, and the degraded products of ferulic acid and citric acid hyperbranched polyester can be used for preparing the all-bio-based epoxy resin again, so that the green closed-loop recovery of the epoxy resin is realized.
3. The ferulic acid hyperbranched polymer and the citric acid hyperbranched polyester prepared by the invention can obviously improve the mechanical property, the heat resistance, the solvent resistance, the hydrolysis resistance, the creep resistance and the corrosion resistance of the bio-based epoxy resin, can replace the traditional petroleum-based epoxy resin, and have simple preparation process and low raw material cost, thereby being suitable for industrial production.
4. The ferulic acid hyperbranched polymer has the advantages of remarkably reducing viscosity and curing shrinkage rate of full-biological epoxy resin, and is expected to be applied to the fields of electronic and electrical appliances such as electronic packaging, insulating materials, printed circuit boards and the like.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments, but the scope of the present invention is not limited to these embodiments, and any equivalent changes or modifications made according to the principle of the technical solution of the present invention should be included in the scope of the present invention.
Example 1
194.0g of Ferulic Acid (FA) and 1295.0g of Epichlorohydrin (ECH) are uniformly mixed, stirred and reacted for 4 hours at 80 ℃, and then 300.0g of 40 wt% sodium hydroxide aqueous solution is added to continue the reaction for 2 hours at 30 ℃. After the reaction is finished, filtering, washing, separating liquid, drying an organic layer by using anhydrous sodium sulfate, and then distilling under reduced pressure to remove epichlorohydrin to obtain the linear ferulic acid epoxy resin (FEP), wherein the yield is about 86.6%, and the epoxy value is 0.53mol/100 g.
300.0g of FEP and 43.7g of trimethylolpropane are stirred and reacted for 6 hours at 110 ℃ to obtain the ferulic acid hyperbranched epoxy resin FEHBP, the number average molecular weight of which is 4887g/mol and the epoxy value of which is 0.29mol/100g by GPC test.
153.6g of citric acid and 11.2g of itaconic anhydride are stirred and reacted for 6h at 100 ℃ to obtain the citric acid-based hyperbranched epoxy resin CHBP, the number average molecular weight of which is 1504g/mol and the acid value of which is 671mgKOH/g according to GPC test.
Uniformly mixing 300.0g of FEP, 30.0g of FEHBP and 205.3g of CHBP, pouring into a silicon rubber mold, and curing at 100 ℃ for 4 hours to obtain the all-bio-based epoxy resin.
100.0g of all-bio-based epoxy resin is heated and degraded in 200ml of 30.0 wt.% sodium hydroxide aqueous solution at 80 ℃ for 40min, the pH value of the degradation solution is adjusted to be neutral (pH is 7) by using about 500ml of 3mol/L hydrochloric acid, then the filtration is carried out, the obtained solid is dried at 80 ℃ for 12h to obtain closed-loop recovered ferulic acid (r-FA), and the filtrate is subjected to reduced pressure distillation and is extracted by ethanol to obtain closed-loop recovered citric acid hyperbranched polyester (r-CHBP).
194.0g r-FA, 1295.0g ECH and 1.94g TBAB are mixed uniformly, stirred and reacted at 80 ℃ for 4 hours, and then 300.0g of 40 wt% aqueous solution of sodium hydroxide is added to continue the reaction for 2 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then reduced pressure distillation is carried out to remove epichlorohydrin, and then the closed-loop recycled linear ferulic acid epoxy resin (r-FEP) is obtained, the yield is 85.9%, and the epoxy value is 0.53mol/100 g.
300.0g r-FEP and 43.7g Trimethylolpropane (TMP) are stirred and reacted for 6h at 110 ℃ to obtain ring-closed recycled ferulic acid hyperbranched epoxy resin r-FEHBP, and the number average molecular weight of the ring-closed recycled ferulic acid hyperbranched epoxy resin r-FEHBP is 4858g/mol, and the epoxy value of the ring-closed recycled ferulic acid hyperbranched epoxy resin is 0.28mol/100 g.
Heating and stirring 300.0g r-FEP, 30.0g r-FEHBP and 205.3g r-CHBP at 120 ℃, uniformly mixing, pouring into a mold, and curing at 100 ℃ for 4h to obtain the closed-loop recycled full bio-based epoxy resin.
Crushing the full-biology-based epoxy resin, and then carrying out hot pressing at 120 ℃ and 5MPa for 30min to obtain the repeatedly processed full-biology-based epoxy resin.
Example 2
194.0g of Ferulic Acid (FA) and 1104.0g of Epichlorohydrin (ECH) are uniformly mixed, stirred at 100 ℃ for reaction for 3 hours, cooled to room temperature, added with 320.0g of 30 wt% sodium hydroxide aqueous solution and continuously reacted for 3 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then is subjected to reduced pressure distillation to remove epichlorohydrin, so that the linear ferulic acid epoxy resin (FEP) is obtained, the yield is about 84.6%, and the epoxy value is 0.52mol/100 g.
300.0g of FEP and 81.2g of trihydroxyethyl isocyanurate are stirred and reacted for 4 hours at the temperature of 120 ℃ to obtain the ferulic acid hyperbranched epoxy resin FEHBP, the number average molecular weight of which is 5458g/mol and the epoxy value of which is 0.20mol/100g by GPC test.
499.2g of citric acid and 11.2g of itaconic anhydride are heated and mixed evenly for 6h at 120 ℃ to obtain the citric acid-based hyperbranched epoxy resin CHBP, the number average molecular weight of which is 4672g/mol and the acid value of which is 648mgKOH/g according to GPC test.
300.0g of FEP, 30.0g of FEHBP and 207.2g of CHBP are mixed uniformly and poured into a mould, and the mixture is cured for 3 hours at 120 ℃ to obtain the all-bio-based epoxy resin.
100.0g of all-bio-based epoxy resin is heated and degraded in 200ml of 30.0 wt.% sodium hydroxide aqueous solution at 80 ℃ for 40min, the pH value of the degradation solution is adjusted to be neutral (pH is 7) by using about 500ml of 3mol/L hydrochloric acid, then the filtration is carried out, the obtained solid is dried at 80 ℃ for 12h to obtain closed-loop recovered ferulic acid (r-FA), and the filtrate is subjected to reduced pressure distillation and is extracted by ethanol to obtain closed-loop recovered citric acid hyperbranched polyester (r-CHBP).
197.0g r-FA, 1104.0g ECH and 1.552g TBAB were mixed well, stirred at 100 ℃ for reaction for 3 hours, then 320.0g30 wt% aqueous solution of sodium hydroxide was added to continue the reaction for 3 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then reduced pressure distillation is carried out to remove epichlorohydrin, and then the closed-loop recycled linear ferulic acid epoxy resin (r-FEP) is obtained, the yield is 84.9%, and the epoxy value is 0.51mol/100 g.
300.0g r-FEP and 81.2g of trihydroxyethyl isocyanurate are stirred and reacted for 4 hours at the temperature of 120 ℃ to obtain the ring-closed recycled ferulic acid hyperbranched epoxy resin r-FEHBP, and the number average molecular weight is 5387g/mol and the epoxy value is 0.15mol/100 g.
Uniformly mixing 300.0g r-FEP, 30.0g r-FEHBP and 207.2g r-CHBP, pouring into a mold, and curing at 120 ℃ for 3h to obtain the closed-loop recycled full bio-based epoxy resin.
Crushing the full-biology-based epoxy resin, and then carrying out hot pressing at 140 ℃ and 5MPa for 20min to obtain the repeatedly processed full-biology-based epoxy resin.
Example 3
194.0g of Ferulic Acid (FA) and 1472.0g of Epichlorohydrin (ECH) are uniformly mixed, stirred at 80 ℃ for reaction for 4 hours, cooled to room temperature, and added with 600.0g of 20 wt% sodium hydroxide aqueous solution for continuous reaction for 4 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then is subjected to reduced pressure distillation to remove epichlorohydrin, and then the linear ferulic acid epoxy resin (FEP) is obtained, the yield is 82.1%, and the epoxy value is 0.54mol/100 g.
300.0g of FEP and 30.0g of glycerol are stirred and reacted for 4 hours at 120 ℃ to obtain the citric acid based hyperbranched epoxy resin CHBP, the number average molecular weight of which is 5799g/mol and the epoxy value is 0.19mol/100g by GPC test.
384g of citric acid and 112g of itaconic anhydride are heated and mixed evenly for 6h at 120 ℃ to obtain the citric acid-based hyperbranched epoxy resin CHBP, the number average molecular weight of which is 458g/mol and the acid value of which is 735mgKOH/g according to GPC test.
300.0g of FEP, 30.0g of FEHBP and 202.3g of CHBP are mixed uniformly and poured into a mould, and the mixture is cured for 2 hours at 140 ℃ to obtain the all-bio-based epoxy resin.
Heating 100.0g of all-bio-based epoxy resin in 200ml of 30.0 wt.% sodium hydroxide aqueous solution at 90 ℃ for degradation for 20min, adjusting the pH value of the degradation solution to be neutral (pH 7) by using 500ml of 1mol/L phosphoric acid, filtering, drying the solid at 80 ℃ for 12h to obtain closed-loop recovered ferulic acid (r-FA), distilling the filtrate under reduced pressure, and extracting with ethanol to obtain closed-loop recovered citric acid hyperbranched polyester (r-CHBP).
194.0g r-FA, 1472.0g ECH and 2.328g TBAB are mixed uniformly, stirred and reacted for 4 hours at 80 ℃, and then 600.0g of 20 wt% sodium hydroxide aqueous solution is added for continuous reaction for 4 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then reduced pressure distillation is carried out to remove epichlorohydrin, and then the closed-loop recycled linear ferulic acid epoxy resin (r-FEP) is obtained, the yield is about 82.3%, and the epoxy value is 0.53mol/100 g.
300.0g r-FEP and 30.0g of glycerol are stirred and reacted for 4 hours at 120 ℃ to obtain the ring-closed recycled ferulic acid hyperbranched epoxy resin r-FEHBP, and the number average molecular weight is 5759g/mol and the epoxy value is 0.19mol/100 g.
Heating and stirring 300.0g r-FEP, 30.0g r-FEHBP and 202.3g r-CHBP at 120 ℃, uniformly mixing, pouring into a mold, and curing at 140 ℃ for 4h to obtain the closed-loop recycled full bio-based epoxy resin.
Crushing the full-biology-based epoxy resin, and then carrying out hot pressing at 100 ℃ and 10MPa for 30min to obtain the repeatedly processed full-biology-based epoxy resin.
Example 4
Mixing 194.0g of Ferulic Acid (FA) and 1295.0g of Epichlorohydrin (ECH) uniformly, stirring at 120 ℃ for reaction for 2h, cooling to room temperature, adding 300.0g of 40 wt% sodium hydroxide aqueous solution, and continuing the reaction for 2 h. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then is subjected to reduced pressure distillation to remove epichlorohydrin, so that the linear ferulic acid epoxy resin (FEP) is obtained, the yield is about 81.6%, and the epoxy value is 0.51mol/100 g.
300g of FEP and 81.2g of trihydroxyethyl isocyanurate are stirred and reacted for 4h at the temperature of 140 ℃ to obtain the ferulic acid hyperbranched epoxy resin FEHBP, the number average molecular weight is 6158g/mol and the epoxy value is 0.13mol/100g by GPC test.
153.6g of citric acid and 10.0g of succinic anhydride are heated and mixed evenly for 6h at 120 ℃ to obtain the citric acid-based hyperbranched epoxy resin CHBP, the number average molecular weight of which is 1492g/mol and the acid value of which is 677mgKOH/g by GPC test.
300.0g of FEP, 30.0g of FEHBP and 197.8g of CHBP are mixed uniformly and poured into a mould, and the mixture is cured for 1 hour at 160 ℃ to obtain the all-bio-based epoxy resin.
Heating 100.0g of all-bio-based epoxy resin in 200ml of 30.0% sodium hydroxide aqueous solution at 90 ℃ for degradation for 20min, adjusting the pH value of the degradation solution to be neutral (pH is 7) by using 500ml of 3mol/L formic acid, filtering, drying the solid at 80 ℃ for 12h to obtain closed-loop recovered ferulic acid (r-FA), distilling the filtrate under reduced pressure, and extracting by using ethanol to obtain closed-loop recovered citric acid hyperbranched polyester (r-CHBP).
194.0g r-FA, 1295.0g ECH and 1.97g TEBA are mixed evenly, stirred and reacted for 2 hours at 120 ℃, and then 300.0g of 40wt percent sodium hydroxide aqueous solution is added for continuous reaction for 2 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then reduced pressure distillation is carried out to remove epichlorohydrin, and then the closed-loop recycled linear ferulic acid epoxy resin (r-FEP) is obtained, the yield is 80.9%, and the epoxy value is 0.51mol/100 g.
300.0g r-FEP and 81.2g of trihydroxyethyl isocyanurate are stirred and reacted for 3 hours at the temperature of 140 ℃ to obtain ring-closed recycled ferulic acid hyperbranched epoxy resin r-FEHBP, and the number average molecular weight is 5912g/mol and the epoxy value is 0.13mol/100g by GPC test.
300.0g r-FEP and 30.0g r-FEHBP197.8g r-CHBP are evenly mixed and poured into a mould to be solidified for 1h at 160 ℃ to obtain the closed-loop recycled full bio-based epoxy resin.
Crushing the full-biology-based epoxy resin, and then carrying out hot pressing at 120 ℃ and 5MPa for 30min to obtain the repeatedly processed full-biology-based epoxy resin.
Example 5
Mixing 194.0g of Ferulic Acid (FA) and 1295.0g of Epichlorohydrin (ECH) uniformly, stirring at 120 ℃ for reaction for 2h, cooling to room temperature, adding 300.0g of 40 wt% sodium hydroxide aqueous solution, and continuing the reaction for 2 h. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then is subjected to reduced pressure distillation to remove epichlorohydrin, so that the linear ferulic acid epoxy resin (FEP) is obtained, the yield is about 82.6%, and the epoxy value is 0.54mol/100 g.
Stirring 300.0g r-FEP and 81.2g of trihydroxyethyl isocyanurate for reaction for 3h at 140 ℃ to obtain ferulic acid hyperbranched epoxy resin FEHBP, wherein the number average molecular weight is 4987g/mol and the epoxy value is 0.29mol/100g by GPC test.
499.2g of citric acid and 10.0g of succinic anhydride are heated and mixed evenly for 6h at 120 ℃ to obtain the citric acid-based hyperbranched epoxy resin CHBP, the number average molecular weight of which is 1478g/mol and the acid value of which is 648mgKOH/g according to GPC test.
300.0g of FEP, 30.0g of FEHBP and 172.7g of CHBP are mixed uniformly and poured into a mould, and the mixture is cured for 4 hours at 100 ℃ to obtain the all-bio-based epoxy resin.
100.0g of all-bio-based epoxy resin is heated and degraded in 200ml of 30.0% sodium hydroxide aqueous solution at 80 ℃ for 60min, the pH value of the degradation solution is adjusted to be neutral (pH is 7) by 500g of 3mol/L hydrochloric acid, then the degradation solution is filtered, the solid is dried at 80 ℃ for 12h to obtain closed-loop recovered ferulic acid (r-FA), and the filtrate is subjected to reduced pressure distillation and then is extracted by ethanol to obtain closed-loop recovered citric acid hyperbranched polyester (r-CHBP).
197.0g r-FA, 1295.0g ECH and 1.97g dodecyl trimethyl ammonium chloride are mixed uniformly, stirred and reacted for 2 hours at 120 ℃, and then 300.0g of 40 wt% sodium hydroxide aqueous solution is added to continue the reaction for 2 hours. After the reaction is finished, filtering and washing are carried out, the organic layer is dried by anhydrous sodium sulfate and then reduced pressure distillation is carried out to remove epichlorohydrin, and then the closed-loop recycled linear ferulic acid epoxy resin (r-FEP) is obtained, the yield is 82.9%, and the epoxy value is 0.54mol/100 g.
306.0g r-FEP and 36.9g of trihydroxyethyl isocyanurate are stirred and reacted for 3 hours at the temperature of 140 ℃ to obtain closed-loop recovered ferulic acid hyperbranched epoxy resin r-FEHBP, and the number average molecular weight is 4967g/mol, and the epoxy value is 0.15mol/100 g.
Uniformly mixing 300.0g r-FEP, 30.0g r-FEHBP and 172.7g r-CHBP, pouring into a mold, and curing at 100 ℃ for 4 hours to obtain the closed-loop recycled full bio-based epoxy resin.
Crushing the full-bio-based epoxy resin, and then carrying out hot pressing at 120 ℃ and 5MPa for 30min to obtain the full-bio-based epoxy resin with different repeated processing times.
Example 6
300.0g of bisphenol A epoxy resin, 117.5g of citric acid and 4.17g of 1, 8-diazabicyclo [5.4.0] undec-7-ene were mixed uniformly and poured into a mold, and cured at 100 ℃ for 4 hours.
The epoxy resin obtained by curing is heated in 200ml of 30.0% sodium hydroxide aqueous solution at 80 ℃ for 60min, and the degradation rate is 12.6%.
And crushing the epoxy resin obtained by curing, and then carrying out hot pressing for 30min at 120 ℃ and 5MPa to obtain the epoxy resin with different repeated processing times.
The tensile properties of the epoxy resins obtained in examples 1 to 6 of this embodiment section after curing were measured according to ASTM 3039 after being left at 25 ℃ for 24 hours, the unnotched impact strength was measured according to ASTM D256, the fracture toughness of the materials was measured according to ASTM D5045, the glass transition temperature was measured according to ASTM _ D2863, the relaxation time was measured in the tensile mode of DMA Q800, the sample maintained 1.5% tensile strain at 140 ℃ and the relaxation time of the sample at 140 ℃ when the stress was relaxed to 1/e was designated as the relaxation time of the sample.
The performance indexes of the epoxy resins obtained in the respective examples are shown in tables 1, 2 and 3.
TABLE 1 Properties of all-bio based epoxy resins obtained in examples 1 to 6
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile strength, MPa | 128 | 138 | 75 | 127 | 129 | 41 |
| Impact strength, kJ/m2 | 24.5 | 32.4 | 12.7 | 27.9 | 46.8 | 7.3 |
| Glass transition temperature,. degree.C | 94 | 113 | 81 | 105 | 124 | 48 |
| Creep temperature resistance | 103 | 124 | 83 | 117 | 136 | 47 |
| Relaxation time of 140 ℃ s | 47 | 45 | 101 | 31 | 19 | 2623 |
TABLE 2 Properties of the closed loop recycled all-bio-based epoxy resins obtained in examples 1 to 5
TABLE 3 Properties of the reprocessed epoxy resins obtained in examples 1-6
As can be seen from the above tables 1, 2 and 3, the obtained full-bio-based epoxy resin has excellent mechanical properties, glass transition temperature and creep resistance temperature, and is expected to replace the traditional petroleum-based epoxy resin to be applied to the fields of adhesives, carbon fiber composites, high-temperature-resistant wind power insulating materials and the like.
Claims (10)
1. A bio-based hyperbranched polymer epoxy resin is characterized in that: the bio-based hyperbranched polymer epoxy resin is prepared from ferulic acid hyperbranched epoxy resin and citric acid hyperbranched polyester through dynamic crosslinking, wherein the ferulic acid hyperbranched epoxy resin comprises but is not limited to the following structure:
wherein R is1＝-CH2-CH3，
The citric acid hyperbranched polyester has the following structure:
wherein
2. A preparation method of bio-based hyperbranched polymer epoxy resin is characterized by comprising the following steps:
(1) uniformly mixing ferulic acid and epoxy chloropropane, stirring and reacting at 80-120 ℃ for 1-4 h, adding 10-40 wt% of sodium hydroxide aqueous solution, continuing to react at 20-40 ℃ for 1-6h, and after the reaction is finished, washing with water, separating liquid, and distilling under reduced pressure to obtain linear ferulic acid epoxy resin FEP;
(2) stirring FEP, a ternary hydroxyl compound and an ionic liquid at the temperature of 60-140 ℃ for reacting for 1-12 h to obtain ferulic acid hyperbranched epoxy resin FEHBP;
(3) stirring citric acid and acid anhydride at 100-160 ℃ for reaction for 1-6 hours to obtain citric acid hyperbranched polyester CHBP;
(4) the FEP, the FEHBP and the CHBP are mixed and stirred uniformly, poured into a mold and cured for 4-8 hours at the temperature of 80-120 ℃ to obtain the all-bio-based epoxy resin.
3. The method for preparing the bio-based hyperbranched polymer epoxy resin as claimed in claim 2, wherein the molar ratio of the ferulic acid to the epichlorohydrin to the sodium hydroxide is 1.0 (10.0-20.0) to 2.0-4.0.
4. The preparation method of the bio-based hyperbranched polymer epoxy resin as claimed in claim 2 or 3, wherein the molar ratio of the FEP, the ternary hydroxyl compound and the ionic liquid is 1:0.33 (0.005-0.01), and the ternary hydroxyl compound is one or more than two of trimethylolpropane, triethyiisocyanurates and glycerol.
5. The method for preparing bio-based hyperbranched polymer epoxy resin according to claim 2 or 3, wherein the ionic liquid is one or more of tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt, N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate, and tetrabutylammonium hexafluorophosphate.
6. The preparation method of the bio-based hyperbranched polymer epoxy resin as claimed in claim 2 or 3, wherein the acid anhydride is one or more of itaconic anhydride and phthalic anhydride, and the molar ratio of the citric acid to the acid anhydride is (2.0-80.0): 1.0.
7. The method for preparing bio-based hyperbranched polymer epoxy resin as claimed in claim 2 or 3, wherein the molar ratio of FEP, FEHBP and CHBP is 1 (0.003-0.009): 0.04-0.05).
8. A method for preparing a bio-based hyperbranched polymer epoxy resin from the degradation product of the bio-based hyperbranched polymer epoxy resin prepared by the method of any one of claims 2 to 7, wherein the ferulic acid hyperbranched epoxy resin and the citric acid hyperbranched polyester are obtained by degrading a full-bio-based epoxy resin, and the degradation method comprises the following steps:
(1) heating and degrading in 10-40% sodium hydroxide water solution at 60-100 deg.c for 30-60 min;
(2) then 0.5 mol/L-2 mol/L organic acid is used for adjusting the pH value of the degradation liquid to be neutral;
(3) then, the water layer and the organic layer are respectively distilled under reduced pressure to obtain ferulic acid and citric acid hyperbranched polyester.
9. The method according to claim 8, wherein the organic acid is one or more of hydrochloric acid, formic acid, phosphoric acid, and oxalic acid.
10. The method of claim 8 or 9, wherein the molar ratio of the total bio-based epoxy resin, the sodium hydroxide and the organic acid is 1 (0.55-0.65) to (0.50-0.60).
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