A biomass-derived dynamic polymer and its preparation method

Abstract

The present invention provides a kind of biomass-derived dynamic aggregation thing and preparation method thereof, uses biomass-derived material (eugenol or itaconic acid) as raw material to carry out the preparation of dynamic aggregation thing, wherein containing hydroxyl ester dynamic covalent bond and methacrylate group, by light-initiated free radical polymerization, forms dynamic cross-linked network, prepares dynamic aggregation thing.Preparing dynamic aggregation thing with biomass raw material can effectively avoid the resource shortage and environmental pollution problem brought by using fossil resources and non-renewable resources as raw materials, at the same time, introduces methacrylate group in the system, by light-initiated free radical polymerization, reaction speed is greatly accelerated, can shorten reaction time.

Description

Technical Field

[0001] The present invention relates to the field of smart polymers, and in particular to a biomass-derived dynamic polymer and a preparation method thereof. Background Art

[0002] Due to environmental and non-renewable issues, the recyclability of materials has always been a focus of contemporary scientific research. Traditionally, thermosetting materials with three-dimensional network structures have been widely used in various fields due to their excellent mechanical properties and thermal stability. However, due to their three-dimensional network structure, the materials cannot be dissolved or melted, making them impossible to reprocess or recycle. They can only be used as disposable materials, seriously polluting the environment and wasting resources.

[0003] Dynamic polymers are intelligent materials that can respond to external stimuli, primarily due to the dynamic covalent bonds embedded in their structure. These bonds can undergo a break-reformation process or exchange reaction under certain external stimuli. Introducing dynamic covalent bonds into thermosetting polymers, due to their reversible breakage and exchange properties, enables the polymers to exhibit self-healing and recyclability, making the functionalization, production, processing, and end-of-life treatment of polymer materials more convenient and environmentally friendly.

[0004] Although the introduction of dynamic structures can alleviate the problems of thermosetting polymers' inability to self-repair and difficulty in recycling to a certain extent, the preparation of dynamic polymers using fossil resources and other non-renewable resources as raw materials will inevitably encounter resource shortages and environmental pollution problems. At the same time, traditional curing methods have long curing times (>4 hours) and high curing temperatures (>100°C). It is urgent to develop a new type of intelligent polymer and preparation method to solve the problems existing in the existing technology. Summary of the Invention

[0005] In response to the problems existing in the above-mentioned prior art, the present invention provides a biomass-derived dynamic polymer and a preparation method thereof. The preparation of the dynamic polymer from biomass raw materials can effectively avoid the resource shortage and environmental pollution problems caused by using fossil resources and non-renewable resources as raw materials; at the same time, methacrylate groups are introduced into the system, and the reaction speed is greatly accelerated through light-initiated free radical polymerization.

[0006] The present invention is achieved through the following technical solutions:

[0007] A method for preparing a biomass-derived dynamic polymer comprises the following steps:

[0008] (1) Using boron trifluoride etherate complex as a catalyst, the diol represented by Formula 1 and epichlorohydrin are subjected to a substitution reaction in the presence of sodium hydroxide to prepare a divalent epoxy compound represented by Formula 3;

[0009] Alternatively, using AlI3 as a catalyst, eugenol is subjected to a demethylation reaction in the presence of N,N-dicyclohexylcarbodiimide to obtain a eugenol derivative shown in Formula 8, and then the eugenol derivative shown in Formula 8 is subjected to a substitution reaction with epichlorohydrin in the presence of sodium hydroxide using boron trifluoride etherate as a catalyst to prepare a compound shown in Formula 9;

[0010]

[0011]

[0012] Among them, R1 is , n1=2, 3, 4, 5, 6 or 10;

[0013] (2) using the binary epoxy compound shown in formula 3, itaconic acid and glycidyl methacrylate as monomers to carry out a condensation reaction to obtain a photocurable macromonomer shown in formula 6;

[0014] Alternatively, a photocurable macromonomer represented by Formula 11 is obtained by condensing the compound represented by Formula 9, the dibasic acid represented by Formula 10, and glycidyl methacrylate as monomers;

[0015]

[0016]

[0017] Among them, R2 is , n2=1, 2, 3, 4, 7, 8 or 10;

[0018] (3) Adding a photoinitiator to the photocurable macromonomer shown in Formula 6 or the photocurable macromonomer shown in Formula 11, and photoinitiating free radical polymerization under ultraviolet light to obtain a photocurable dynamic polymer.

[0019] Preferably, in step (1), when preparing the divalent epoxy compound represented by formula 3, the molar ratio of the diol represented by formula 1, sodium hydroxide and epichlorohydrin is: 1: (2-2.5): (3-6).

[0020] Preferably, in step (1), when preparing the compound represented by formula 9, the molar ratio of N,N-dicyclohexylcarbodiimide, eugenol and aluminum triiodide is 1:(1-2):(1.5-2.5).

[0021] Preferably, in step (2), when preparing the photocurable macromonomer represented by formula 6, the molar ratio of the divalent epoxy compound represented by formula 3, itaconic acid and glycidyl methacrylate is 1:(1-2):(0.01-0.1).

[0022] Preferably, in step (2), when preparing the photocurable macromonomer represented by formula 11, the molar ratio of the compound represented by formula 9, the dibasic acid represented by formula 10 and glycidyl methacrylate is 1:(1-2):(0.01-0.1).

[0023] Preferably, in step (1), the diol represented by formula 1 is one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,10-decanediol.

[0024] Preferably, in step (2), the dibasic acid represented by formula 10 is one of malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid.

[0025] Preferably, in step (3), the photoinitiator is Irgacure 819.

[0026] The biomass-derived light-cured dynamic polymer is obtained by the preparation method.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] This invention uses biomass-derived materials (eugenol or itaconic acid) as raw materials to prepare dynamic polymers containing hydroxyl-ester dynamic covalent bonds and methacrylate groups. Through photoinitiated free radical polymerization, a dynamic crosslinked network is formed to prepare the dynamic polymer. Using biomass raw materials to prepare dynamic polymers effectively avoids the resource shortages and environmental pollution associated with using fossil and non-renewable resources as raw materials. Furthermore, the introduction of methacrylate groups into the system significantly accelerates the reaction rate through photoinitiated free radical polymerization, shortening the reaction time.

[0029] The dynamic polymer prepared by the present invention has good mechanical properties, self-repairing properties, reprocessability, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the feasibility of the technical solution of the present invention, the test diagrams of some products described in the solution are briefly introduced below, among which:

[0031] Figure 1 : Fourier transform infrared spectrum of ethylene glycol diglycidyl ether in Example 1;

[0032] Figure 2 :Ethylene glycol diglycidyl ether in embodiment 1 1 H-NMR spectrum (deuterated chloroform);

[0033] Figure 3 : Fourier transform infrared spectrum of the photocurable macromonomer in Example 1;

[0034] Figure 4 : The photocurable macromonomer in Example 1 1 H-NMR spectrum (deuterated DMSO).

[0035] Example 1

[0036] (1) Weigh 0.2 mol of ethylene glycol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it. Expel air and moisture from the flask. Add 0.5% (0.06 g) of boron trifluoride ether complex based on the mass of ethylene glycol at 50 °C and begin to dropwise add epichlorohydrin (0.6 mol). Control the dropwise addition rate to keep the temperature constant. Allow the reaction to proceed for 1 h to complete the ring-opening reaction.

[0037] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.4 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove the residual water and reactants to obtain the product ethylene glycol diglycidyl ether.

[0038] (2) Weigh a certain amount of itaconic acid, ethylene glycol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1:0.01) in a flask and react at 150 °C for 3 h to obtain a photocurable macromonomer.

[0039] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 20 minutes, a biomass photocurable dynamic polymer based on itaconic acid was obtained.

[0040] Example 2

[0041] (1) Weigh 0.2 mol of 1,3-propylene glycol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it. Expel air and moisture from the flask. Add 0.6% (0.09 g) of boron trifluoride ether complex based on the mass of 1,3-propylene glycol at 50 °C and begin to dropwise add epichlorohydrin (0.6 mol). Control the dropwise addition rate to keep the temperature constant. Allow the reaction to proceed for 1 h to complete the ring-opening reaction.

[0042] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.42 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 1,3-propylene glycol diglycidyl ether.

[0043] (2) A certain amount of itaconic acid, 1,3-propylene glycol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.2:0.02) were weighed into a flask and reacted at 150 °C for 3 h to obtain a photocurable macromonomer.

[0044] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 25 minutes, a biomass photocurable dynamic polymer based on itaconic acid was obtained.

[0045] Example 3

[0046] (1) Weigh 0.2 mol of 1,4-butanediol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it. Remove the air and moisture from the three-necked flask. Add 0.7% (0.13 g) of boron trifluoride etherate complex based on the mass of 1,4-butanediol at 50 °C and begin to dropwise add epichlorohydrin (0.8 mol). Control the dropwise addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction. Lower the temperature to 40 °C. After the temperature stabilizes, add a 40% (mass fraction) NaOH (0.44 mol) aqueous solution. After reacting for 40 minutes, remove the sodium chloride generated by the reaction by hot filtration. Place the filtrate in a separatory funnel and let it stand for phase separation. Distill the crude product under reduced pressure to remove the residual water and reactants, and obtain the product 1,4-butanediol diglycidyl ether.

[0047] (2) A certain amount of itaconic acid, 1,4-butanediol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.4:0.04) were weighed into a flask and reacted at 150 °C for 3 h to obtain a photocurable macromonomer.

[0048] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under the light of an ultraviolet lamp (405 nm, 18 W). After 25 minutes, a biomass photocurable dynamic polymer based on itaconic acid was obtained.

[0049] Example 4

[0050] (1) Weigh 0.2 mol of 1,5-pentanediol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it. Remove the air and moisture from the three-necked flask. At 50 °C, add 0.8% (0.17 g) of boron trifluoride ether complex based on the mass of 1,5-pentanediol and begin to dropwise add epichlorohydrin (1 mol). Control the dropwise addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction. Lower the temperature to 40 °C. After the temperature is constant, add a 40% (mass fraction) NaOH (0.46 mol) aqueous solution. After reacting for 40 minutes, remove the sodium chloride generated by the reaction by suction filtration while hot. Place the filtrate in a separatory funnel and let it stand for phase separation. Distill the crude product under reduced pressure to remove the residual water and reactants, and obtain the product 1,5-pentanediol diglycidyl ether.

[0051] (2) A certain amount of itaconic acid, 1,5-pentanediol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.6:0.06) were weighed into a flask and reacted at 150 °C for 3 h to obtain a photocurable macromonomer.

[0052] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under the light of an ultraviolet lamp (405 nm, 18 W). After 30 minutes, a biomass photocurable dynamic polymer based on itaconic acid was obtained.

[0053] Example 5

[0054] (1) Weigh 0.2 mol of 1,6-hexanediol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it. Expel air and moisture from the flask. Add 0.9% (0.21 g) of boron trifluoride ether complex based on the mass of 1,6-hexanediol at 50 °C and begin to dropwise add epichlorohydrin (1.2 mol). Control the dropwise addition rate to keep the temperature constant. Allow the reaction to proceed for 1 h to complete the ring-opening reaction.

[0055] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.48 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 1,6-hexanediol diglycidyl ether.

[0056] (2) A certain amount of itaconic acid, 1,6-hexanediol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.8:0.08) were weighed into a flask and reacted at 150 °C for 3 h to obtain a photocurable macromonomer.

[0057] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under the light of an ultraviolet lamp (405 nm, 18 W). After 30 minutes, a biomass photocurable dynamic polymer based on itaconic acid was obtained.

[0058] Example 6

[0059] (1) Weigh 0.2 mol of 1,10-decanediol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it. Expel air and moisture from the flask. Add 1% (0.35 g) of boron trifluoride ether complex based on the mass of 1,10-decanediol at 50 °C and begin to dropwise add epichlorohydrin (1.2 mol). Control the dropwise addition rate to keep the temperature constant. Allow the reaction to proceed for 1 h to complete the ring-opening reaction.

[0060] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.5 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 1,10-decanediol diglycidyl ether.

[0061] (2) A certain amount of itaconic acid, 1,10-decanediol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:2:0.1) were weighed into a flask and reacted at 150 °C for 3 h to obtain a photocurable macromonomer.

[0062] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under the light of an ultraviolet lamp (405 nm, 18 W). After 35 minutes, a biomass photocurable dynamic polymer based on itaconic acid was obtained.

[0063] Example 7

[0064] (1) Aluminum triiodide (1.5 mmol), acetonitrile (15 ml), N,N-dicyclohexylcarbodiimide (1 mmol) and eugenol (1 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, and stirred for 18 hours. The mixture was cooled to room temperature and acidified with 2 mol / L dilute hydrochloric acid (50 ml). The mixture was extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness using a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0065] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 0.5% (0.04 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.15 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0066] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.1 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0067] (2) A certain amount of malonic acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1:0.01) were weighed into a flask and reacted at 150°C for 3 h to obtain a photocurable macromonomer.

[0068] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 25 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0069] Example 8

[0070] (1) Aluminum triiodide (5 mmol), acetonitrile (20 ml), N,N-dicyclohexylcarbodiimide (3 mmol) and eugenol (3.5 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, reacted for 18 hours, and then stirred. After cooling to room temperature, the mixture was acidified with 2 mol / L dilute hydrochloric acid (50 ml), extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness using a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0071] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 0.6% (0.05 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.18 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0072] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.11 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0073] (2) A certain amount of succinic acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.2:0.02) were weighed into a flask and reacted at 150°C for 3 hours to obtain a photocurable macromonomer.

[0074] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 25 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0075] Example 9

[0076] (1) Aluminum triiodide (5.5 mmol), acetonitrile (20 ml), N,N-dicyclohexylcarbodiimide (3 mmol) and eugenol (4 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, reacted for 18 hours, then stopped stirring. After cooling to room temperature, the mixture was acidified with 2 mol / L dilute hydrochloric acid (50 ml), extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness using a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0077] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 0.6% (0.05 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.2 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0078] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.11 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0079] (2) Weigh a certain amount of glutaric acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.4:0.04) in a flask and react at 150°C for 3 hours to obtain a photocurable macromonomer.

[0080] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 30 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0081] Example 10

[0082] (1) Aluminum triiodide (6 mmol), acetonitrile (25 ml), N,N-dicyclohexylcarbodiimide (3 mmol) and eugenol (4.5 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, and stirred for 18 hours. The mixture was cooled to room temperature and acidified with 2 mol / L dilute hydrochloric acid (50 ml). The mixture was extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness using a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0083] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 0.7% (0.06 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.22 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0084] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.12 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0085] (2) A certain amount of adipic acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.6:0.06) were weighed into a flask and reacted at 150°C for 3 h to obtain a photocurable macromonomer.

[0086] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 30 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0087] Example 11

[0088] (1) Aluminum triiodide (5.5 mmol), acetonitrile (30 ml), N,N-dicyclohexylcarbodiimide (3 mmol) and eugenol (5 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, reacted for 18 hours, and then stirred. After cooling to room temperature, the mixture was acidified with 2 mol / L dilute hydrochloric acid (50 ml), extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness using a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0089] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 0.8% (0.05 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.25 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0090] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.12 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0091] (2) A certain amount of azelaic acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.6:0.07) were weighed into a flask and reacted at 150°C for 3 hours to obtain a photocurable macromonomer.

[0092] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 35 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0093] Example 12

[0094] (1) Aluminum triiodide (6.5 mmol), acetonitrile (35 ml), N,N-dicyclohexylcarbodiimide (3 mmol) and eugenol (5.5 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, reacted for 18 hours, and then stirred. After cooling to room temperature, the mixture was acidified with 2 mol / L dilute hydrochloric acid (50 ml), extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness on a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0095] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 0.9% (0.07 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.28 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0096] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.13 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0097] (2) A certain amount of sebacic acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:1.8:0.08) were weighed into a flask and reacted at 150°C for 3 hours to obtain a photocurable macromonomer.

[0098] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 35 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0099] Example 13

[0100] (1) Aluminum triiodide (7 mmol), acetonitrile (40 ml), N,N-dicyclohexylcarbodiimide (3 mmol) and eugenol (6 mmol) were added to a 100 ml eggplant-shaped flask, heated to 80 °C, and stirred for 18 hours. The mixture was cooled to room temperature and acidified with 2 mol / L dilute hydrochloric acid (50 ml). The mixture was extracted with ethyl acetate, washed with a saturated aqueous solution of sodium thiosulfate (10 ml) and then with saturated brine (10 ml), dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness using a rotary evaporator. The residue was purified by flash column chromatography (eluent: ethyl acetate / petroleum ether = 1:4) to obtain 4-allylcatechol.

[0101] Weigh 0.05 mol of 4-allylcatechol and add it to a three-necked flask. Place the three-necked flask in a magnetic stirrer and heat it to remove air and moisture from the flask. Add 1% (0.08 g) of boron trifluoride ether complex based on the mass of 4-allylcatechol at 50°C, and start adding epichlorohydrin (0.3 mol) dropwise. Control the addition rate to keep the temperature constant. React for 1 hour to complete the ring-opening reaction.

[0102] The temperature was lowered to 40°C, and after the temperature was constant, a 40% mass fraction of NaOH (0.13 mol) aqueous solution was added dropwise. After the reaction lasted for 40 minutes, the sodium chloride generated by the reaction was removed by hot filtration. The filtrate was placed in a separatory funnel and allowed to stand for phase separation. The upper crude product was distilled under reduced pressure to remove residual water and reactants to obtain the product 4-allylcatechol diglycidyl ether.

[0103] (2) A certain amount of dodecanedioic acid, 4-allylcatechol diglycidyl ether and glycidyl methacrylate (molar ratio of 1:2:0.1) were weighed into a flask and reacted at 150°C for 3 h to obtain a photocurable macromonomer.

[0104] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to the prepared photocurable macromonomer, and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W). After 40 minutes, a biomass photocurable dynamic polymer based on eugenol was obtained.

[0105] Figure 1 is the Fourier transform infrared spectrum of ethylene glycol diglycidyl ether in Example 1; Figure 1 The epoxy groups (843 cm -1 ), ether bond (1101cm -1 ) and other typical peaks on ethylene glycol diglycidyl ether, as well as 1452 cm -1 -CH2 deformation vibration peak; 2999cm -1, 2874 are the stretching vibration peaks of -CH2, indicating that ethylene glycol diglycidyl ether has been successfully prepared.

[0106] Figure 2 For the ethylene glycol diglycidyl ether in Example 1 1 H-NMR spectrum (deuterated chloroform); Figure 2 The peaks at δ=2.76~2.84, δ=2.59~2.66 and δ=3.11~3.21 are hydrogen E, F and D on the epoxy group, respectively, and the integrated areas of the three peaks are basically equal; the peaks at δ=3.73~3.84 and δ=3.36~3.46 are hydrogen at A and C on COC, respectively, and the peak at δ=3.58~3.72 is hydrogen B substituted by methylene on COC, which is consistent with the theoretical value, confirming that the prepared substance is ethylene glycol diglycidyl ether.

[0107] Figure 3 is the Fourier transform infrared spectrum of the photocurable macromonomer in Example 1; compared with Figure 1 , epoxy group (843cm -1 ) peak disappears, corresponding to the opening of the epoxy group, and the peak position of COC shifts to 1158cm -1 Mobile; In addition, 1631 cm -1 、1704cm -1 、3668 cm -1 A new peak appears at , which corresponds to the carbon-carbon double bond, carbonyl group on ester and hydroxyl group produced in the macromonomer after monomer polymerization, indicating that the photocurable macromonomer has been successfully prepared.

[0108] Figure 4 is the photocurable macromonomer in Example 1 1 H-NMR spectrum (deuterated DMSO); Figure 4 The peaks at δ=5.65~5.74, δ=5.82~5.87, δ=6.07~6.13 and δ=6.25~6.29 are hydrogen A on the outermost C=C; the peaks at δ=5.73~5.82 and δ=6.13~6.24 are hydrogen F on C=C of itaconic acid; the peak at δ=4.95~5.12 is hydrogen C on the hydroxyl group; the peak at δ=4.79~4.94 is hydrogen G on the C adjacent to the hydroxyl group outside the polymer repeating unit; the peak at δ=3.90~4.16 is hydrogen H on the C adjacent to the hydroxyl group within the polymer repeating unit; the peak at δ=3.59~3.88 is hydrogen B and D on the C adjacent to the ester group; and the peak at δ=3.43~3.58 is hydrogen E on the C between C=C and the ester group, which are consistent with the theoretical values, confirming that the prepared substance is the photocurable macromonomer in the experimental plan. DETAILED DESCRIPTION

[0109] In order to further understand the present invention, the present invention is described below in conjunction with embodiments. These descriptions are only for further explaining the features and advantages of the present invention and are not intended to limit the claims of the present invention.

[0110] In a preferred embodiment of the present invention, the dynamic polymer is prepared using biomass-derived diol and itaconic acid with a relatively flexible structure as raw materials, comprising the following steps:

[0111] (1) A divalent epoxide (Formula 3) was prepared by a substitution reaction between a biomass diol (Formula 1) and epichlorohydrin (Formula 2). The ring-opening reaction was carried out using a boron trifluoride etherate complex (0.5% to 1% by mass of the diol) as a catalyst, and the ring-closing reaction was completed using a 40% by mass sodium hydroxide solution. The molar ratio of the biomass diol (Formula 1), sodium hydroxide, and epichlorohydrin (Formula 2) was 1:(2-2.5):(3-6).

[0112]

[0113] Among them, R1 is , n1=2, 3, 4, 5, 6 or 10.

[0114] (2) A photocurable macromonomer (Formula 6) having a flexible chain segment is obtained by condensing a binary epoxy compound (Formula 3), itaconic acid (Formula 4), and glycidyl methacrylate (Formula 5) as monomers. The molar ratio of the binary epoxy compound (Formula 3), itaconic acid (Formula 4), and glycidyl methacrylate (Formula 5) is 1:(1-2):(0.01-0.1).

[0115]

[0116] Wherein, X is the degree of polymerization.

[0117] (3) About 1 wt% of the photoinitiator Irgacure 819 was added to a certain amount of photocurable macromonomer (Formula 6), and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W) to obtain a photocurable dynamic polymer based on itaconic acid (Formula 7).

[0118]

[0119] Among them, R x It is the compound shown in formula 6.

[0120] In another preferred embodiment of the present invention, the dynamic polymer is prepared using biomass-derived dibasic acid and relatively rigid eugenol as raw materials, comprising the following steps:

[0121] (1) Using rigid eugenol (Formula 7) as a raw material, an AlI3-catalyzed demethylation reaction is performed in the presence of N,N-dicyclohexylcarbodiimide to obtain an ortho-dihydroxy eugenol derivative (Formula 8). The molar ratio of N,N-dicyclohexylcarbodiimide, eugenol, and aluminum triiodide is 1:(1-2):(1.5-2.5). Then, a substitution reaction is performed with epichlorohydrin using boron trifluoride etherate as a catalyst to obtain a compound of Formula 9. (The specific process is the same as step 1 of the previous scheme)

[0122]

[0123] (2) A photocurable macromonomer having a rigid segment and a copolymerization reaction is performed using the compound of formula 9, the dibasic acid of formula 10, and the glycidyl methacrylate of formula 5 as monomers, wherein the molar ratio of the compound of formula 9, the dibasic acid of formula 10, and the glycidyl methacrylate of formula 5 is 1:(1-2):(0.01-0.1).

[0124] Among them, R2 is , n2=1, 2, 3, 4, 7, 8 or 10; Y is the degree of polymerization.

[0125] (3) A photoinitiator Irgacure 819 with a mass concentration of about 1 wt% was added to a certain amount of photocurable macromonomer (Formula 11), and free radical polymerization was initiated under ultraviolet light (405 nm, 18 W) to obtain a photocurable dynamic polymer based on eugenol (Formula 12).

[0126]

[0127] Among them, R y It is the compound represented by formula 11.

Claims

1. A method for preparing a biomass-derived dynamic polymer, characterized in that: The steps include: (1) Using boron trifluoride etherate complex as a catalyst, the diol represented by Formula 1 and epichlorohydrin are subjected to a substitution reaction in the presence of sodium hydroxide to prepare a divalent epoxy compound represented by Formula 3; Alternatively, using AlI3 as a catalyst, eugenol is subjected to a demethylation reaction in the presence of N,N-dicyclohexylcarbodiimide to obtain a eugenol derivative shown in Formula 8, and then the eugenol derivative shown in Formula 8 is subjected to a substitution reaction with epichlorohydrin in the presence of sodium hydroxide using boron trifluoride etherate as a catalyst to prepare a compound shown in Formula 9; Among them, R1 is , n1=2, 3, 4, 5, 6 or 10; (2) using the binary epoxy compound shown in formula 3, itaconic acid and glycidyl methacrylate as monomers to carry out a condensation reaction to obtain a photocurable macromonomer shown in formula 6; Alternatively, a photocurable macromonomer represented by Formula 11 is obtained by condensing the compound represented by Formula 9, the dibasic acid represented by Formula 10, and glycidyl methacrylate as monomers; Among them, R2 is , n2=1, 2, 3, 4, 7, 8 or 10; (3) Adding a photoinitiator to the photocurable macromonomer shown in Formula 6 or the photocurable macromonomer shown in Formula 11, and photoinitiating free radical polymerization under ultraviolet light to obtain a photocurable dynamic polymer.

2. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (1), when preparing the divalent epoxy compound represented by formula 3, the molar ratio of the diol represented by formula 1, sodium hydroxide and epichlorohydrin is: 1: (2-2.5): (3-6).

3. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (1), when preparing the compound represented by formula 9, the molar ratio of N,N-dicyclohexylcarbodiimide, eugenol and aluminum triiodide is 1:(1-2):(1.5-2.5).

4. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (2), when preparing the photocurable macromonomer represented by formula 6, the molar ratio of the divalent epoxy compound represented by formula 3, itaconic acid and glycidyl methacrylate is 1:(1-2):(0.01-0.1).

5. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (2), when preparing the photocurable macromonomer represented by formula 11, the molar ratio of the compound represented by formula 9, the dibasic acid represented by formula 10 and glycidyl methacrylate is 1:(1-2):(0.01-0.1).

6. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (1), the diol represented by formula 1 is one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,10-decanediol.

7. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (2), the dibasic acid represented by formula 10 is one of malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid.

8. The method for preparing a biomass-derived dynamic polymer according to claim 1, characterized in that: In step (3), the photoinitiator is Irgacure 819.

9. A biomass-derived dynamic polymer obtained by the preparation method according to any one of claims 1 to 8.

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