CN113336909A - Remoldable and degradable biomass benzoxazine resin and preparation method thereof - Google Patents
Remoldable and degradable biomass benzoxazine resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a remoldable and degradable biomass benzoxazine resin and a preparation method thereof, biomass decamethylenediamine and isoeugenol are used as raw materials, and a full biomass benzoxazine monomer is synthesized through a Mannich reaction; the benzoxazine resin is copolymerized with Schiff base monomers and solidified to obtain the biomass benzoxazine resin with remodeling and degradation functions. The invention endows the benzoxazine resin with the characteristics of recycling, reshaping and degrading for the first time. Compared with the prior art, the benzoxazine monomer is synthesized green, and the prepared remoldable and degradable biomass resin has higher thermal property and tensile strength, higher remolding efficiency and simple degradation condition. Can be applied to the fields with high requirements on heat resistance, such as aerospace, electronic information and the like.
Description
Technical Field
The invention relates to preparation of a remoldable and degradable biomass benzoxazine resin, belonging to the technical field of functional polymer materials.
Background
Recycling of waste thermosetting resins has been a challenge that has plagued their use in sophisticated fields and sustainable environmental development. However, the permanently crosslinked network structure makes conventional thermosetting resins difficult to recycle or degrade after curing, resulting in the build-up of waste resin. At present, the treatment mode of the waste resin is mainly incineration and landfill, which brings secondary damage to the environment.
In recent years, researchers have prepared a series of recyclable thermosetting resins based on reversible dynamic bonds such as ester bonds, disulfide bonds, schiff base bonds, siloxane bonds, and the like, but challenges remain in designing high-performance, easily reworkable, and degradable thermosetting resins, and the like. Currently, the recovery of most thermosetting resins requires high temperature, high pressure or long time to achieve the remodeling effect, which may cause the degradation of the resin itself, thereby affecting the performance of the resin after remodeling.
In recent years, the research on benzoxazine resins has been greatly advanced. However, the development of remodelable degradable high-performance biomass benzoxazine resins remains a challenge. So far, only one biomass benzoxazine resin based on disulfide dynamic bond is reported, but the heat resistance is low (the glass transition temperature is only 53 ℃), and the requirement of high-end fields on the heat-resistant resin cannot be met. In addition, the reported biomass benzoxazine resin can be summarized, and no report of degradable biomass benzoxazine resin exists. Therefore, in order to meet the demands of the advanced fields on high-performance resins and the greening requirements of the environment sustainable development on the resins, the preparation of high-performance biomass benzoxazine resins with remodelable and degradable properties is a challenging and meaningful topic.
In conclusion, the preparation of the high-performance biomass benzoxazine resin with remoldability and degradability by the green method has great scientific significance and application value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation, recovery and degradation method of a remoldable and degradable biomass benzoxazine resin, which realizes low-cost recovery and utilization of high-performance thermosetting resin and green degradation of waste thermosetting resin.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a remoldable biomass benzoxazine resin comprises the following steps:
(1) heating decamethylenediamine, a formaldehyde compound and isoeugenol for reaction and then recrystallizing to obtain a full-biomass benzoxazine monomer;
(2) melting and mixing the full biomass benzoxazine monomer and the Schiff base monomer, and then solidifying to obtain the remoldable and degradable biomass benzoxazine resin.
In the step (1), the formaldehyde compound is formaldehyde and/or paraformaldehyde; the molar ratio of the decamethylene diamine to the formaldehyde compound to the isoeugenol is 100: 400-440: 200. The heating reaction temperature is 90-110 ℃, and the time is 3-12 h; recrystallizing with ethanol or ethyl acetate.
In the step (2), the molar ratio of the full-biomass benzoxazine monomer to the Schiff base monomer is 1: 0.95-1.1, preferably, the molar ratio of the full-biomass benzoxazine monomer to the Schiff base monomer is 1: 1, the temperature for melting and mixing is 150-160 ℃, and the time is 5-15 min.
In the step (2), the full biomass benzoxazine monomer and the Schiff base monomer are melted, mixed, defoamed and cured; the curing temperature is 160-200 ℃, and the curing time is 3-12 h. Preferably, the curing is performed in a step heating mode, and the heat preservation time at each step temperature is not less than 1h, such as 1-3 h; the temperature difference between adjacent steps is not more than 30 ℃, for example, 10-30 ℃.
In the invention, vanillin and diaminodiphenyl ether are used as raw materials to prepare Schiff base monomers; preferably, the vanillin and the diaminodiphenyl ether are subjected to reflux reaction in ethanol, then the obtained product is filtered, and then a filter cake is washed to obtain the Schiff base monomer. Further preferably, the molar ratio of the vanillin to the diaminodiphenyl ether is (2-2.2) to 1, preferably 2: 1, and the reflux reaction time is 2-4 hours.
The remodelable and degradable biomass benzoxazine resin disclosed by the invention can be reshaped by hot pressing after being crushed, so that the remodelable and degradable biomass benzoxazine resin can be recycled. In particular, the remodelable and degradable biomass benzoxazine resin can be degraded in an acid solution, which is the first example of degradable benzoxazine resin reported so far.
In the invention, the preparation of the full biomass benzoxazine monomer by heating and reacting decamethylenediamine, a formaldehyde compound and isoeugenol is as follows:
the preparation of the Schiff base monomer by taking vanillin and diaminodiphenyl ether as raw materials is schematically shown as follows:
the preparation method comprises the following steps of melting, mixing and solidifying the full biomass benzoxazine monomer and the Schiff base monomer to obtain the remoldable biomass benzoxazine resin:
the invention discloses an application of the remoldable and degradable biomass benzoxazine resin in preparation of remoldable and degradable materials; preferably, the degradation is carried out in a mixed solution of acetic acid and water.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes the full biomass raw materials of decanediamine and isoeugenol as raw materials to synthesize the full biomass benzoxazine monomer, and the adopted raw materials are all green full biomass raw materials. The remoldable and degradable biomass benzoxazine resin prepared by the invention has outstanding heat resistanceT g 129 ℃ and also has high storage modulus (3.47 GPa), tensile modulus (1.87 GPa) and tensile strength (65.8 MPa), thereby providing a reliable basis for the application of the resin in the advanced field, and the high heat resistance of the resin is benefited by the phenols at multiple crosslinking sites in the resin, a large number of hydrogen bond structures in a crosslinking network and rigid Schiff base monomersDue to the combined action of rigid benzoxazine structure and flexible decamethylene diamine structure in the cross-linked network.
In particular, the remodelable and degradable biomass benzoxazine resin prepared by the method has the characteristics of remodelable recycling and degradation for the first time. The application method overcomes the defects that the traditional benzoxazine polymer can not be recycled after being molded and the waste thermosetting resin can not be degraded.
In a word, the preparation method of the remoldable and degradable biomass benzoxazine resin provided by the invention is environment-friendly, has a simple preparation process, is easy for industrial large-scale production, saves the processing cost, and meets the requirement of sustainable development of the environment.
Drawings
FIG. 1 is an infrared (FTIR) spectrum of a benzoxazine/Schiff base blend in example 1 of the present invention;
FIG. 2 is a differential calorimetry (DSC) curve of the benzoxazine/Schiff base blend of example 1 of the present invention, nitrogen, 10 deg.C/min;
FIG. 3 is an FTIR spectrum of a benzoxazine resin in example 1 of the present invention;
FIG. 4 is a tan delta-temperature curve (stretching mode, heating rate 3 deg.C/min) of the benzoxazine resin in example 1 of the present invention;
FIG. 5 is a thermogravimetric analysis (TGA) curve (temperature rise rate 10 deg.C/min, nitrogen) of benzoxazine resin in example 1 of the present invention;
FIG. 6 is a storage modulus-temperature curve (tensile mode, heating rate 3 ℃/min) of the benzoxazine resin in example 1 of the present invention;
FIG. 7 is a stress-strain curve of a benzoxazine resin in example 1 of the present invention;
FIG. 8 is an electron photograph of the reshaping process of benzoxazine resin in example 1 of the present invention;
FIG. 9 is a TGA curve (ramp rate 10 deg.C/min, nitrogen) of a post-reshaped benzoxazine resin prepared according to example 1 of the present invention;
FIG. 10 is a stress-strain curve of a reshaped benzoxazine resin prepared according to example 1 of the present invention;
FIG. 11 is an electron photograph showing the degradation process of the benzoxazine resin in example 1 of the present invention.
Detailed Description
The preparation process of the remoldable and degradable biomass benzoxazine resin disclosed by the invention specifically comprises the following steps:
(1) heating decamethylenediamine, a formaldehyde compound and isoeugenol for reaction and then recrystallizing to obtain a full-biomass benzoxazine monomer;
(2) melting and mixing the full biomass benzoxazine monomer and the Schiff base monomer, and then solidifying to obtain the remoldable and degradable biomass benzoxazine resin.
The remodelable and degradable biomass benzoxazine resin has excellent comprehensive performance, can achieve a better remodeling effect, has excellent solvent resistance in a common solvent, can be hydrolyzed under an acidic condition, and can be simultaneously recycled and degraded on the basis. The technical scheme of the invention is further described with reference to the accompanying drawings and embodiments; all starting materials are commercially available or routinely prepared according to the prior art and the test methods involved are all those routine in the art.
Example 1
(1) Preparation of benzoxazine monomers
3.28g of isoeugenol, 1.20g of paraformaldehyde (CAS #: 30525-89-4) and 1.72g of decamethylenediamine were added to a 50mL round-bottomed flask at room temperature, followed by conventional stirring at 100 ℃ for 5 hours, followed by natural cooling to room temperature to obtain a crude product; the crude product was recrystallized from ethanol (20 mL) to give a white solid (4.15 g, 76% yield) as all-biomass benzoxazine monomer (IE-dea),1H NMR (400 MHz, Chloroform-d) δ 6.75 (s, 2H, Ar-H), 6.55 (s, 2H, Ar-H), 6.30 (d, J = 15.5, 2H, CH), 6.11-6.03 (m, 2H, CH), 4.96 (s, 4H,CH2), 3.98 (s, 4H,CH2), 3.90 (s,6H,CH3), 2.82-2.71 (m, 4H,CH2), 1.91-1.84 (m, 6H, CH3), 1.60-1.52 (p, J = 7.1 Hz, 4H, CH2), 1.35-1.24 (m, 12H, CH2). 13C NMR (101 MHz, CDCl3) δ 147.6, 142.7, 130.6, 130.0, 123.7, 120.5, 117.1, 106.6, 82.9, 55.7, 51.4, 50.0, 29.5, 29.5, 28.2, 27.2, 18.4. HRMS (ESI+) m/z calcd for C34H49N2O4K+ [M + K + H]+588.3324 and found 588.4171. As can be seen, the O-CH on the oxazine ring2-N and Ar-CH2The characteristic peaks for-N appear at 4.96ppm and 3.90ppm, respectively.1H NMR demonstrated the accuracy of the chemical structure of the full biomass benzoxazine monomer.
(2) Preparation of Schiff base monomer
Vanillin (3.04 g, 20 mmol), diaminodiphenyl ether (2.0 g, 10 mmol) and 10mL ethanol were added to a 50mL round bottom flask, followed by heating to reflux and conventional stirring for 3 h; then naturally cooling to room temperature, and carrying out suction filtration to obtain a crude product. The crude product was washed with ethanol (20 mL) to give a pale yellow solid (3.84 g, 82% yield) as Schiff base monomer (V-oda),1H NMR (400 MHz, Chloroform-d) δ 8.37 (s, 2H, CH=N), 7.78-7.54 (m, 2H, Ar-H), 7.37-7.17 (m, 6H, Ar-H), 7.13-6.90 (m, 6H, Ar-H), 3.96 (s, 6H, CH3) The successful synthesis of the monomer was demonstrated. It can be seen that the CH = N peak appears at 8.37ppm, indicating successful synthesis of the schiff base monomer.
Melting and stirring the blend of the full biomass benzoxazine monomer and the Schiff base monomer at a molar ratio of 1: 1 at 150 ℃ for 15min, testing infrared (figure 1) and DSC (figure 2), referring to figure 1, wherein CH = N characteristic peak (1585 cm) of Schiff base structure appears-1) And asymmetric oscillation peak of C-O-C on oxazine ring (1066 cm)-1) Oxazine skeleton vibration and C-H out-of-plane vibration peak (936 cm)-1) Characteristic peak of propenyl group (1585 cm)-1) The successful preparation of the benzoxazine blend is proved; referring to fig. 2, the peak top temperature of the exothermic peak of the DSC curve for the benzoxazine/schiff base blend occurred at 199 ℃. Under the same test conditions, the peak top temperature of the DSC curve exothermic peak of the full biomass benzoxazine monomer (IE-dea) appears at 243 ℃; the inventors have published literature (Heat-resistant and robust biobased cured with a green synthesis protocol. tm. chem., 2021,12,432), the peak top temperatures of the exothermic peaks of DSC curves of two benzoxazine monomers IE-apa and V-apa respectively appear at 249 ℃ and 236 ℃; the peak top temperature of the DSC curve exothermic peak of another Schiff base biomass benzoxazine monomer VFA-apple (see Preparation of high performance bio-based benzoxazine resin through a green solvent-free texture for shape memory application. Polymer 202 (2020) 122673) appeared at 220 ℃; the maximum curing temperature of the benzoxazines of the prior art is higher than 220 ℃, which causes degradation of the resin and disrupts hydrogen bonding interactions, thereby negatively affecting the properties of the benzoxazine resin. Therefore, when the benzoxazine resin is industrially produced, the reduction of the maximum curing temperature is important, and the invention solves the problem and discloses a benzoxazine resin system with the maximum curing temperature not higher than 200 ℃ for the first time.
(3) Preparation of remoldable biomass benzoxazine resin
Melting and stirring a blend (10.0 g in total) of full-biomass benzoxazine monomers and Schiff base monomers in a molar ratio of 1: 1 at 150 ℃ for 15min, pouring molten resin into a mold, defoaming in an oven (10 min at 150 ℃), putting the mold into a forced air drying oven, and curing according to the processes of 160 ℃/2h +180 ℃/2h +200 ℃/2h in sequence; after the solidification is finished, the solidified material is naturally cooled along with an oven, and the remoldable biomass benzoxazine resin (poly (IE-dea/V-oda)) with the FTIR spectrum and T-shape is obtainedgInitial thermal decomposition temperature (T)di5 wt%), storage modulus and tensile strength are shown in FIGS. 3, 4, 5, 6 and 7, respectively.
Referring to FIG. 3, there is an FTIR spectrum of poly (IE-dea/V-oda) which is a cured product of benzoxazine. No characteristic peak of vibration of oxazine ring skeleton and out-of-plane vibration of C-H was observed (936 cm)-1) C-O-C (1206 cm)-1) The formation of a crosslinked network of the resin was demonstrated.
Referring to FIG. 4, there is shown a tan delta temperature curve of a remodelable and degradable biomass benzoxazine resin poly (IE-dea/V-oda). It can be seen that the remodelable, degradable biomass benzoxazine resin T prepared in example 1gAt a temperature of 129 c,the remoldable and degradable biomass benzoxazine resin prepared by the invention is proved to have outstanding heat resistance.
Referring to FIG. 5, there is a Thermogravimetric (TGA) plot of a remodelable and degradable biomass benzoxazine resin poly (IE-dea/V-oda). It can be seen that the T of the remodelable, degradable biomass benzoxazine resin prepared in example 1diThe temperature was 315 ℃.
Referring to fig. 6, there is a plot of storage modulus versus temperature for a remodelable and degradable biomass benzoxazine resin poly (IE-dea/V-oda). It can be seen that the storage modulus of the remodelable, degradable biomass benzoxazine resin prepared in example 1 at 40 ℃ is 3.47 GPa.
See FIG. 7, which is a stress-strain curve of a remodelable and degradable biomass benzoxazine resin poly (IE-dea/V-oda). It can be seen that the tensile modulus of the remodelable and degradable biomass benzoxazine resin prepared in example 1 at normal temperature is 1.87GPa, and the tensile strength is 65.8MPa, which proves that the remodelable and degradable biomass benzoxazine resin prepared by the method has outstanding mechanical properties.
Application examples
The method for recycling and remolding the biomasses benzoxazine resin poly (IE-dea/V-oda)
Pulverizing remodelable and degradable biomass benzoxazine resin by conventional method, and pulverizing the resin at 139 deg.C (T)gAnd hot pressing for 5min at the temperature of 10 ℃) and under the pressure of 5MPa to obtain the recycled biomass benzoxazine resin, wherein the surface of the obtained regular sheet has no macroscopic cracks, and the crushed particles are connected again, so that the benzoxazine resin prepared by the method has the plasticity ability.
See fig. 8, which is an electronic photograph of the remodeling process of the remodelable and degradable biomass benzoxazine resin. It can be seen that the resin obtained by hot pressing at 139 ℃ and 5MPa for 5min has smooth and crack-free surface, and the resin is proved to have excellent remolding property.
See FIG. 9, which is remodeling of remodelable and degradable biomass benzoxazine resinThe latter Thermogravimetric (TGA) curve. It can be seen that the T of the remodelable, degradable biomass benzoxazine resin prepared in example 1 after two remodeling processesdi312 ℃ and 310 ℃ respectively. The resin was demonstrated to maintain excellent thermal stability after remolding.
See fig. 10, which is a stress-strain curve of remodelable and degraded biomass benzoxazine resin after remodeling. The tensile strength of the remoldable and degradable biomass benzoxazine resin prepared in example 1 after two remolding processes is 66.9 MPa and 64.0MPa respectively. The resin is proved to maintain excellent mechanical property after being remolded.
The degradation method of the remodelable and degradable biomass benzoxazine resin poly (IE-dea/V-oda)
Adding the remoldable and degradable biomass benzoxazine resin into a mixed solvent of acetic acid and water at normal temperature (V)Acetic acid/VWater (W)= 2/1), under 100W ultrasonic condition, resin degradation is complete within 20 min. This result demonstrates the degradation properties of the benzoxazine resin prepared according to the present invention.
In contrast, at normal temperature, the remoldable and degradable biomass benzoxazine resin is added into acetic acid or water, and under the ultrasonic condition, the resin cannot be degraded by the water, and the resin can be degraded by the acetic acid only in a small amount.
For comparison, at normal temperature, the remoldable and degradable biomass benzoxazine resin was put into a mixed solvent of hydrochloric acid, water and tetrahydrofuran (pH =1, HCl, V)Tetrahydrofuran (THF)/VWater (W)= 2/1) or a mixed solvent of hydrochloric acid, water and dioxane (pH =1, HCl, V)Dioxane (dioxane)/VWater (W)= 2/1) standing for 4h, the resin could not degrade; the resin was put into a mixed solvent of sulfuric acid, water and tetrahydrofuran (pH =1, H)2SO4，VTetrahydrofuran (THF)/VWater (W)= 2/1) or a mixed solvent of sulfuric acid, water and dioxane (pH =1, H)2SO4，VDioxane (dioxane)/VWater (W)= 2/1) left for 4h, the resin still could not degrade.
The above parameters of the amount of degradation are the same.
See fig. 11, which is an electron photograph of the degradability of the remodelable and degradable biomass benzoxazine resin. In a mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 2/1), the resin can be completely degraded by ultrasonic treatment for 20min at normal temperature, excellent degradation performance of the resin is shown, and particularly, the remoldable and degradable biomass benzoxazine resin has excellent acid and organic solvent resistance and meets the requirement of green degradation of the resin.
Comparative example 1
The preparation method of the benzoxazine monomer 2 comprises the following steps: adding 3.04g of vanillin, 1.20g of paraformaldehyde (CAS #: 30525-89-4) and 1.72g of decamethylenediamine into a 50mL round-bottom flask at room temperature, stirring for 2h at 110 ℃, and then naturally cooling to room temperature to obtain a crude product; the crude product was recrystallized from ethanol (20 mL) to give a yellow solid (3.77 g, 72% yield) noted as benzoxazine monomer 2,1H NMR (400 MHz, Chloroform-d) δ 9.80 (s, 2H, CHO), 7.28 (d, 2H, Ar-H), 7.14 (d, 2H, Ar-H),5.05 (s, 4H, CH2), 4.06 (s, 4H, CH2), 3.94 (s, 6H, CH3), 2.74-2.72 (m, 4H, CH2), 1.56-1.53 (m, 4H, CH2), 1.32-1.21 (m, 12H, CH2)。
the benzoxazine monomer 2 (5.24 g, 1 mmol) and the polyetheramine D-400 (4 g, 1 mmol) are melted and stirred at 150 ℃ for 10min and then defoamed for 10min, and then the benzoxazine resin 2 containing Schiff base bonds is prepared through a curing procedure of 160 ℃/2h +180 ℃/2h +200 ℃/2h, the obtained resin has poor remolding performance, and is crushed and then hot-pressed and cured, so that a complete resin plate cannot be obtained, cracks are very many, and the resin cannot be degraded under any acidic condition by adopting the same degradation conditions.
Comparative example 2
See CN2020104448544, example 1 discloses shape memory resin based on biomass benzoxazine, and by the same degradation method, it was found that neither acetic acid, water, nor acetic acid/water can degrade the resin, nor can hydrochloric acid or sulfuric acid system degrade the resin.
Example 2
(1) Preparation of benzoxazine monomers
3.28g of isoeugenol, 1.20g of paraformaldehyde (CAS #: 30525-89-4) and 1.72g of decamethylenediamine are added into a 50mL round-bottom flask, and the reaction liquid is heated to 100 ℃, kept warm and stirred for 5 hours and then cooled to room temperature to obtain a crude product; the crude product was recrystallized from ethyl acetate (20 mL) to give a white solid, designated as benzoxazine monomer.
(2) Preparation of remoldable and degradable biomass benzoxazine resin
Melting 10.0g of biomass benzoxazine monomer/Schiff base (V-oda) blend (the molar ratio is 1: 1), stirring for 15min at 160 ℃, pouring resin into a mold, defoaming in an oven (10 min at 150 ℃), then putting the mold into a forced air drying oven, and curing according to the processes of 160 ℃/3h +180 ℃/3h +200 ℃/3h in sequence; and after the solidification is finished, naturally cooling the solidified material along with an oven to obtain the remoldable and degradable biomass benzoxazine resin.
Pulverizing the remoldable and degradable biomass benzoxazine resin, and mixing the pulverized resin with the solventT g And hot pressing for 5min at the temperature of 10 ℃ and the pressure of 5MPa to obtain the recycled biomass benzoxazine resin, wherein the surface of the regular sheet has no macroscopic cracks.
Adding the remolding and degrading biomass benzoxazine resin into a mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 2/1), the resin degradation is complete.
Example 3
(1) Preparation of benzoxazine monomers
3.28g of isoeugenol, 1.32g of paraformaldehyde (CAS #: 30525-89-4) and 1.72g of decamethylenediamine are added into a 50mL round-bottom flask, and the reaction solution is heated to 100 ℃, kept warm and stirred for 8 hours, and then cooled to room temperature to obtain a crude product; the crude product was recrystallized from ethyl acetate (20 mL) to give a white solid, designated as benzoxazine monomer.
(2) Preparation of remoldable and degradable biomass benzoxazine resin
Melting 10.0g of biomass benzoxazine monomer/Schiff base (V-oda) blend (the molar ratio is 1: 1), stirring for 15min at 150 ℃, pouring resin into a mold, defoaming in an oven (10 min at 150 ℃), then putting the mold into a forced air drying oven, and curing according to the processes of 160 ℃/1h +180 ℃/1h +200 ℃/1h in sequence; and after the solidification is finished, naturally cooling the solidified material along with an oven to obtain the remoldable and degradable biomass benzoxazine resin.
Pulverizing the remoldable and degradable biomass benzoxazine resin, and mixing the pulverized resin with the solventT g And hot pressing for 10min at the temperature of 10 ℃ and the pressure of 5MPa to obtain the recycled biomass benzoxazine resin. The surface of the obtained structured sheet has no visible cracks.
Adding the remoldable and degradable biomass benzoxazine resin into a mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 2/1), the resin degradation is complete.
Example 4
(1) Preparation of benzoxazine monomers
3.28g of isoeugenol, 1.20g of paraformaldehyde (CAS #: 30525-89-4) and 1.72g of decamethylenediamine are added into a 50mL round-bottom flask, and the reaction liquid is heated to 100 ℃, kept warm and stirred for 5 hours and then cooled to room temperature to obtain a crude product; the crude product was recrystallized from ethanol (20 mL) to give a white solid, designated as benzoxazine monomer.
(2) Preparation of remoldable and degradable biomass benzoxazine resin
Melting 10.0g of biomass benzoxazine monomer/Schiff base (V-oda) blend (the molar ratio is 1: 1), stirring for 15min at 150 ℃, pouring resin into a mold, defoaming in an oven (10 min at 150 ℃), then putting the mold into a forced air drying oven, and curing according to the processes of 160 ℃/3h +180 ℃/3h +200 ℃/3h in sequence; and after the solidification is finished, naturally cooling the solidified material along with an oven to obtain the remoldable and degradable biomass benzoxazine resin.
Pulverizing the remoldable and degradable biomass benzoxazine resin, and mixing the pulverized resin with the solventT g And hot pressing for 30min at the temperature of 15 ℃ and the pressure of 5MPa to obtain the recycled biomass benzoxazine resin. The surface of the obtained structured sheet has no visible cracks.
The remolding and degrading biomass benzoxazine resinAdding into mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 1/1), the degradation condition is normal temperature 100W ultrasonic, the resin can not be degraded completely; adding into mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 2/1), the resin degradation is complete.
Example 5
(1) Preparation of benzoxazine monomers
3.28g of isoeugenol, 1.30g of paraformaldehyde (CAS #: 30525-89-4) and 1.72g of decamethylenediamine are added into a 50mL round-bottom flask, and the reaction liquid is heated to 100 ℃, kept warm and stirred for 5 hours and then cooled to room temperature to obtain a crude product; the crude product was recrystallized from ethanol (20 mL) to give a white solid, designated as benzoxazine monomer.
(2) Preparation of remoldable and degradable biomass benzoxazine resin
Melting 10.0g of biomass benzoxazine monomer/Schiff base (V-oda) blend (the molar ratio is 1: 1), stirring for 15min at 150 ℃, pouring resin into a mold, defoaming in an oven (10 min at 150 ℃), then putting the mold into a forced air drying oven, and curing according to the processes of 160 ℃/4h +180 ℃/4h +200 ℃/4h in sequence; and after the solidification is finished, naturally cooling the solidified material along with an oven to obtain the remoldable and degradable biomass benzoxazine resin.
Crushing the remoldable and degradable biomass benzoxazine resin, and putting the crushed resin in a containerT g And hot pressing for 30min at the temperature of 20 ℃ and the pressure of 5MPa to obtain the recycled biomass benzoxazine resin. The surface of the obtained structured sheet has no visible cracks.
Adding the remoldable and degradable biomass benzoxazine resin into a mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 1/2), normal temperature 100W ultrasound, resin can not be degraded completely; adding into mixed solvent of acetic acid and water (V)Acetic acid/VWater (W)= 2/1), the resin degradation is complete.
The invention discloses a preparation method, a recovery method and a degradation method of remoldable and degradable biomass benzoxazine resin, which take full biomass decamethylene diamine, paraformaldehyde and isoeugenol as raw materials under suitable conditionsObtaining a full biomass benzoxazine monomer through a Mannich reaction; the benzoxazine resin is copolymerized with Schiff base monomers and solidified to obtain the biomass benzoxazine resin with remodeling and degradation functions. The preparation method has the advantages of simple preparation process, green synthetic process and high yield, and greatly reduces the dependence of high polymer materials on fossil resources. Compared with the prior art, the remoldable and degradable biomass benzoxazine resin has excellent thermal performance (a)T g At a temperature of 129 c,T di 315 deg.c), high storage modulus (3.47 GPa), tensile modulus (1.87 GPa), and strength (65.8 MPa). The remoldable and degradable biomass benzoxazine resin obtained by the method can be recycled after being broken, and the waste resin can be subjected to degradation treatment, so that the environmental requirements of sustainable development can be met, and the requirements of high-performance resin in high-end fields can also be met.
Claims (10)
1. A preparation method of a remoldable biomass benzoxazine resin is characterized by comprising the following steps:
(1) heating decamethylenediamine, a formaldehyde compound and isoeugenol for reaction and then recrystallizing to obtain a full-biomass benzoxazine monomer;
(2) preparing Schiff base monomers by taking vanillin and diaminodiphenyl ether as raw materials; melting and mixing the full biomass benzoxazine monomer and the Schiff base monomer, and then solidifying to obtain the remoldable and degradable biomass benzoxazine resin.
2. A method for preparing a remolding and degrading biomass benzoxazine resin according to claim 1, wherein in step (1), the formaldehyde compound is formaldehyde and/or paraformaldehyde; the molar ratio of the decamethylene diamine to the formaldehyde compound to the isoeugenol is 100: 400-440: 200.
3. A preparation method of a remoldable biomass benzoxazine resin according to claim 1, wherein in the step (1), the heating reaction temperature is 90-110 ℃ and the time is 3-12 h; recrystallizing with ethanol or ethyl acetate.
4. A method for preparing a remoldable biomass benzoxazine resin according to claim 1, wherein in step (2), vanillin and diaminodiphenyl ether are subjected to reflux reaction in ethanol to obtain the schiff base monomer.
5. A preparation method of a remoldable biomass benzoxazine resin according to claim 4, wherein in the step (2), the molar ratio of vanillin to diaminodiphenyl ether is (2-2.2) to 1, and the reflux reaction time is 2-4 hours.
6. A preparation method of the remoldable biomass benzoxazine resin according to claim 1, wherein in the step (2), the molar ratio of the full biomass benzoxazine monomer to the Schiff base monomer is 1 to (0.95-1.1).
7. A preparation method of a remoldable biomass benzoxazine resin according to claim 1, wherein in the step (2), the temperature of the melt mixing is 150-160 ℃ and the time is 5-15 min; the curing temperature is 160-200 ℃, and the curing time is 3-12 h.
8. A preparation method of a remoldable and degradable biomass benzoxazine resin according to claim 7, wherein in the step (2), the curing is performed in a step heating manner, the temperature of each step is kept for not less than 1h, and the temperature difference between adjacent steps is not more than 30 ℃.
9. A remodelable and degradable biomass benzoxazine resin prepared by the preparation method of remodelable and degradable biomass benzoxazine resin according to claim 1.
10. Use of the remodelable and degradable biomass benzoxazine resin according to claim 9 in the preparation of a remodelable and degradable material.
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| PCT/CN2021/144072 WO2023010800A1 (en) | 2021-08-06 | 2021-12-31 | Remodelable and degradable biomass benzoxazine resin and preparation method therefor |
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| WO2023010800A1 (en) | 2023-02-09 |
| CN113336909B (en) | 2021-10-08 |
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