CN109180889B - Preparation method and application of benzoxazine resin with full biological sources - Google Patents
Preparation method and application of benzoxazine resin with full biological sources Download PDFInfo
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Abstract
The invention relates to a preparation method and application of polybenzoxazine from all biological sources. The benzoxazine prepolymer with full biological sources provided by the invention has the advantages of simple process, high reaction efficiency, high product purity, narrow molecular weight distribution, uniform structure of a cured product and complete network structure. The benzoxazine curing resin with full biological sources obtained by final temperature programming and curing of the prepolymer has excellent heat resistance, mechanical property, flame retardant property and dielectric property, particularly excellent high-frequency dielectric property, and can be applied to the fields of high-frequency and high-speed circuit board substrates, microwave and millimeter wave communication, vehicle-mounted radars and the like. And because the cured resin has a developed cross-linked network and a high nitrogen content, the carbonized benzoxazine porous resin material with a full biological source can be used as a functional material and can be applied to the aspects of electricity storage, drug loading, pollutant treatment, gas adsorption and the like.
Description
Technical Field
The invention relates to the technical field of organic polymer materials, in particular to a preparation method and application of benzoxazine resin with a full biological source.
Background
Benzoxazine is a novel phenolic resin, and is a six-membered heterocyclic compound synthesized by taking a phenolic compound, an amine compound and aldehydes as raw materials through a Mannich reaction. The phenolic resin keeps excellent thermal property, flame retardance and electrical insulation of the traditional phenolic resin, and simultaneously has the advantages that the traditional phenolic resin does not have, such as no micromolecules are released in the processing and curing process, the prepared product is low in porosity, the volume is close to zero in shrinkage, the material has more excellent high-temperature thermal stability, flame retardance, mechanical property, chemical stability and the like, the water absorption is low, strong acid or strong base catalysis is not needed in the preparation process, and the damage to equipment is reduced. Therefore, the method has wide application prospect in the fields of electronic information, aerospace, friction materials, composite materials and the like, and arouses the research interest of people. With the development of research and the continuous expansion of ideas, researchers gradually develop benzoxazine resin from engineering materials to functional materials, such as fields related to high-frequency communication, energy storage, adsorption, separation, shape memory and the like, and have attracted extensive attention.
In the twenty-first century, information transmission has entered the era of high-frequency signal transmission. In order to increase the signal transmission speed, the high frequency of electronic information products has made higher demands on Copper Clad Laminate (CCL) as an information transmission carrier and polymer resin of important components thereof, and the dielectric properties of the matrix resin need to have both low dielectric constant and ultra-low dielectric loss at high frequency. However, the dielectric constant k of the traditional benzoxazine resin is generally 3.5, and the dielectric loss f is generally 0.02(1GHz), which cannot well meet the high requirements of high-frequency communication on the substrate resin. Therefore, it is worth the researchers to discuss how to design the chemical structure of benzoxazine resin by utilizing its flexible molecular design to reduce the polarity of the resin (Polymer Chemistry,2018,9(21), 2913) -2925).
In addition, the benzoxazine resin can also be used as a precursor of a carbon material, and the benzoxazine porous carbon material not only introduces various organic elements such as oxygen, nitrogen and the like, but also has various pore structures. The numerous micropores and the larger specific surface area are not only beneficial to improving the performances of adsorption (micro particles such as electrons, ions and gas molecules), ion transmission and the like of the material, but also beneficial to containing doping substances and improving the compatibility of the composite material, so that the composite material has application prospects in various fields such as gas adsorption and storage, catalysis, inductors, photoelectrons and the like (polymer material science and engineering, 2018, 34(1), 184-.
The diphenolic acid and the furfuryl amine are both from natural resources, are rich in sources, can be regenerated and are low in cost. The preparation of benzoxazine based on diphenolic acid and furfuryl amine has been reported, but the existing preparation method is carried out in a non-polar solvent, the reaction time is long (10-15h), and the curing temperature is high (230 ℃.) (CN 201810013847-biomass diphenolic acid-furfuryl amine type benzoxazine resin and the preparation method thereof). Besides, the good thermal properties of the diphenolic acid furfuryl amine type benzoxazine are utilized, the common engineering application is broken through, the advantages of the structure and the performance of the diphenolic acid furfuryl amine type benzoxazine are fully utilized, and the functionalization application in the emerging fields of high-frequency communication, energy storage, adsorption and the like is found, so that the diphenolic acid furfuryl amine type benzoxazine is more urgent and important for improving the comprehensive performance and the added value of resin.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a benzoxazine prepolymer with a full biological source, a preparation method of a polymer resin and application of the polymer resin as a high-frequency dielectric material and an adsorption functional material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provides a benzoxazine prepolymer with full biological sources, which has the following general formula:
the synthetic route of the benzoxazine prepolymer with all biological sources is as follows:
the invention also provides a preparation method of the benzoxazine prepolymer with all biological sources, which is a solvent-free method and comprises the following steps: under the nitrogen atmosphere, firstly adding an aldehyde compound and furfuryl amine into a reaction container, reacting for 0.25-1 h at the temperature of 115-160 ℃ under the high-speed stirring condition, and then adding diphenolic acid to continue reacting for 0.75-3 h. Wherein the molar ratio of aldehyde groups in the aldehyde compounds to phenolic hydroxyl groups in the natural diphenolic acid and amino groups in furfuryl amine is 1-2: 1: 0.5-1, and performing post-treatment to obtain a benzoxazine prepolymer with a full biological source;
or a mixed solvent method, comprising the following steps: adding an aldehyde compound, a phenolic compound and a diamine compound into a reaction container in a step-by-step and multi-time feeding mode, wherein the step-by-step and multi-time feeding mode is that under a nitrogen atmosphere, the aldehyde compound and furfuryl amine are added into the reaction container, a polar/non-polar mixed solvent is added, diphenolic acid is added after the mixture is fully stirred, and the molar ratio of aldehyde groups in the aldehyde compound to phenolic hydroxyl groups in natural diphenolic acid and amino groups in furfuryl amine is 1-2: 1: 0.5-1, reacting for 4-8 h at 75-115 ℃, and performing post-treatment to obtain a benzoxazine prepolymer with full biological sources;
the reaction route is as follows:
according to the scheme, the aldehyde compound is formaldehyde or paraformaldehyde.
According to the scheme, the natural bisphenol is diphenolic acid, and the molecular structural formula is as follows:
according to the scheme, the non-polar solvent: toluene, butanone, xylene; polar solvent: cyclohexanone, acetone, ethyl acetate, diethyl ether, N' -dimethylformamide, dioxane, chloroform, ethanol, tetrahydrofuran, and the like. The volume ratio is 5: 1-1: 5.
according to the scheme, the post-treatment in the solvent-free method comprises the following steps: and after the reaction is finished, grinding the reactant into powder, pouring the powder into a methanol solution to remove unreacted reactant and impurities, standing the solution, removing supernatant liquid to obtain yellow powder, and drying the yellow powder to obtain the benzoxazine prepolymer with the full biological source.
The post-treatment in the mixed solvent method comprises the following steps: and after the reaction is finished, pouring the reaction product or the reaction liquid into a methanol solution to remove unreacted substances and impurities, drying the precipitate, and grinding to obtain the benzoxazine oligomer. Preferably, the concentration of the methanol solution is 50-95 wt%.
The benzoxazine resin with all biological sources is obtained by dissolving and curing a benzoxazine prepolymer.
The resin obtained by curing the benzoxazine prepolymer with full biological sources has the following general formula:
according to the scheme, the solvent for dissolving in the solidification can be any one or more of toluene, xylene, ethanol, trichloromethane, dimethylformamide and 1, 4-dioxane.
According to the scheme, the curing is carried out for 4-24 hours at 100-200 ℃ after the organic solvent is dissolved, so as to obtain the benzoxazine resin with full biological sources.
A full-biological-source benzoxazine porous resin material is prepared by curing the full-biological-source benzoxazine prepolymer, or mixing the full-biological-source benzoxazine prepolymer and nanoparticles according to a mass ratio of 10% -30%, then curing, and carbonizing in an inert atmosphere to obtain the full-biological-source benzoxazine resin-based porous material, wherein the carbonization is carried out at 600-800 ℃ for 5-15 hours.
According to the scheme, the nano particles are selected from zinc oxide, ferroferric oxide, titanium dioxide, zirconium oxide or aluminum hydroxide and the like.
The invention also provides a functional application of the benzoxazine resin with all biological sources, which comprises the following specific steps: the high-frequency dielectric material is applied to the fields of high-frequency and high-speed circuit board base materials, microwave and millimeter wave communication, vehicle-mounted radars and the like.
The invention also provides a functional application of the full-biological-source benzoxazine porous resin material, and particularly relates to the application of the carbonized full-biological-source benzoxazine porous resin material as a functional material in the aspects of electricity storage, drug loading, pollutant treatment, gas adsorption and the like.
The invention has the beneficial effects that:
1. the benzoxazine prepolymer with full biological sources provided by the invention has the advantages of simple process, environmental protection, high reaction efficiency, high product purity, narrow molecular weight distribution, uniform structure of a cured product and complete network structure, so that the resin has good dielectric property and great high-frequency communication application potential under high frequency.
Compared with the common bisphenol A aniline benzoxazine resin, the dielectric constant of the benzoxazine resin is 3.6, and the dielectric loss of the benzoxazine resin is 0.03, the high-frequency dielectric property of the benzoxazine resin is obviously improved, the dielectric constant of the benzoxazine resin is less than 3.0 under the high-frequency condition, and the dielectric loss is reduced to 0.02-0.01. On one hand, the introduction of carboxyl in diphenolic acid reacts to remove polar phenolic hydroxyl, so that polar groups in the cured resin are consumed to reduce the polarity, and the introduction of a low-polarity furan ring is also favorable for reducing the polarity and increasing the free volume, thereby improving the dielectric property. In addition, there is an extremely slight amount of decarboxylation of diphenolic acid resulting in the formation of fine pores, which further improves the dielectric properties due to the introduction of air. On the other hand, the important aspect is that the products obtained by the solvent-free method and the polar/nonpolar mixed solvent method have high purity, narrow molecular weight distribution, uniform structure and complete network structure, so that the resin has better dielectric property and larger high-frequency communication application potential under high frequency.
Specifically, the invention adopts a solvent-free method for preparation: the method comprises the steps of taking diphenolic acid as a phenol source, taking furfuryl amine as an amine source, controlling the adding process of raw materials by adjusting the proportion of diphenolic acid and furfuryl amine, controlling the temperature, and synthesizing the benzoxazine prepolymer with the full biological source by a solvent-free method in a nitrogen atmosphere. No reaction solvent is added in the whole process, the difficulty in removing the reaction solvent is eliminated, the defect of long reaction time in the solvent is overcome, the synthesis efficiency is high, the reaction time is short (1-4 h), the curing temperature (100-200 ℃) is also obviously reduced compared with the reported data, and the synthesized benzoxazine prepolymer with full biological sources has high purity, few side reactions, high yield (99%) and small molecular weight distribution; simple process and environmental protection.
Or using a polar/non-polar mixed solvent: the method comprises the steps of taking diphenolic acid as a phenol source, taking furfuryl amine as an amine source, controlling the adding process of raw materials by adjusting the proportion of diphenolic acid and furfuryl amine, controlling the temperature, and synthesizing the benzoxazine prepolymer with the full biological source by adopting a polar/nonpolar mixed solvent method under nitrogen atmosphere. The reaction efficiency is high, the reaction time (4-8 h) is remarkably shortened compared with that of a common solvent method, and the curing temperature (100-200 ℃) is remarkably reduced compared with reported data. And because the benzoxazine is firstly formed in the nonpolar solvent and then transferred into the polar solvent, the polar solvent plays a role in filtration and purification, so that the synthesized benzoxazine prepolymer has high purity and small molecular weight distribution. The preparation process is simple, the reaction efficiency is high, and the product purity is high.
2. The prepolymer contains a carboxyl functional group of diphenolic acid and a furan ring of furfuryl amine, and the curing peak temperature (184 ℃) of the prepolymer is reduced by 60 ℃ compared with the curing peak temperature (244 ℃) of common bisphenol A aniline benzoxazine resin due to the ring-opening catalysis of the carboxyl functional group and the furan ring on benzoxazine curing, so that the processing technology performance of the resin is remarkably improved (BA is bisphenol A aniline benzoxazine, FD is benzoxazine of a full biological source, and the processing technology performance is shown in figure 1).
3. When the prepared benzoxazine prepolymer with all biological sources is subjected to ring-opening curing reaction, chemical crosslinking can be further performed in addition to the ring-opening crosslinking of benzoxazine (see the general formula of curing resin). On one hand, the furan ring of the furfuryl amine can form chemical bonding with a nitrogen atom on a Mannich bridge formed by the ring opening of the benzoxazine, and on the other hand, the carboxyl group of the diphenolic acid can form an ester bond with a phenolic hydroxyl group formed by the ring opening of the benzoxazine. Besides chemical bonding, abundant and diverse chemical hydrogen bonding effects are formed in the benzoxazine resin from all biological sources, and the effects are also beneficial to strengthening the intermolecular interaction in a network structure and improving the thermal property of the benzoxazine resin. Finally curing to obtain the total biogenic benzoxazine resin with a three-branched structure, wherein the total biogenic benzoxazine resin has higher crosslinking density and excellent heat resistance (carbon residue rate (30-40%), glass transition temperature (240-303 ℃) and flame retardant property (limited oxygen index is 30.3)) (PBA is bisphenol A aniline benzoxazine resin, PFD is total biogenic benzoxazine resin, the glass transition temperature is shown in an attached figure 2, and the thermal stability is shown in an attached figure 3).
4. The carbonized resin has a plurality of electroactive functional groups due to the introduction of the furan ring of the furfuryl amine and the carboxyl of the diphenolic acid in the benzoxazine resin with the full biological source, and the carbonized resin is easy to form a porous structure due to the increase of the crosslinking density of the resin material, so that the benzoxazine resin with the full biological source has good application prospects in the aspects of electricity storage, pollutant treatment, drug loading, gas adsorption and the like.
Drawings
FIG. 1 is a Differential Scanning Calorimetry (DSC) characterization of the curing polymerization behavior of benzoxazines. In view of the ring-opening catalysis effect of carboxyl functional groups and furan rings on benzoxazine curing, the curing peak temperature (184 ℃) of the benzoxazine prepolymer (FD) with a full biological source is reduced by 60 ℃ compared with the curing peak temperature (244 ℃) of common bisphenol A aniline Benzoxazine (BA), and the processing technology performance of the resin is obviously improved.
FIG. 2 is a graph of the thermal properties of resins tested by dynamic thermomechanical analysis (DMA) in which the peak temperature of the loss tangent represents the glass transition temperature of the resin. The glass transition temperature of the common bisphenol A aniline benzoxazine resin (PBA) is 167 ℃, while the glass transition temperature of the benzoxazine resin with the full biological source is 303 ℃, and the thermal property is obviously improved.
FIG. 3 shows thermogravimetric analysis (TGA) to test the high temperature thermal stability of the resin. At the high temperature of 800 ℃, the carbon residue rate of bisphenol A aniline benzoxazine resin (PBA) is 27%, while the carbon residue rate of benzoxazine resin with full biological sources is 40%, and the high-temperature thermal stability is obviously improved.
Detailed Description
The present invention is described in further detail in order to enable those skilled in the art to better understand the technical solution of the present invention.
Example 1
Preparing a benzoxazine prepolymer with a full biological source:
under nitrogen atmosphere and without solvent, 5.82g (0.06mol) of furfuryl amine and 3.60g (0.12mol) of paraformaldehyde are added into a 250mL three-neck flask provided with a condenser tube, a magneton stirrer and a thermometer, the mixture is uniformly mixed and heated to 160 ℃ for reaction for 0.25h, then 8.58g (0.03mol) of natural diphenolic acid is added, the mixture is uniformly mixed and then reacted for 0.75h at 160 ℃, and the molar ratio of aldehyde group, phenolic hydroxyl group and amino functional group is 2: 1:1, pouring the reaction liquid into a methanol solution (with the concentration of 85 wt%) after the reaction is finished, standing for 24 hours, removing supernatant liquid after standing to obtain yellow powder, drying the yellow powder in vacuum at the temperature of 60 ℃ for 8 hours, and finally drying to obtain a product, namely the benzoxazine prepolymer with the full biological source. The yield was 99.5% and the molecular weight distribution was 1.16.
Example 2
Preparing a benzoxazine prepolymer with a full biological source:
under nitrogen atmosphere and without solvent, 4.85g (0.05mol) of furfuryl amine and 3.00g (0.10mol) of paraformaldehyde are added into a 250mL three-neck flask provided with a condenser tube, a magneton stirrer and a thermometer, the mixture is uniformly mixed and heated to 115 ℃ for reaction for 1h, then 8.58g (0.03mol) of natural diphenolic acid is added, the mixture is uniformly mixed and reacted at 115 ℃ for 3h, and the molar ratio of aldehyde group, phenolic hydroxyl group and amino functional group is 1.67: 1: 0.83, after the reaction is finished, pouring the reaction solution into a methanol solution (with the concentration of 50 wt%) for standing for 24 hours, removing supernatant after standing to obtain yellow powder, drying the yellow powder in vacuum for 8 hours at the temperature of 60 ℃, and finally drying the yellow powder to obtain the product, namely the benzoxazine prepolymer with the full biological source. The yield was 99.2% and the molecular weight distribution was 1.12.
Example 3
Preparing a benzoxazine prepolymer with a full biological source:
under nitrogen atmosphere and without solvent, 3.88g (0.04mol) of furfuryl amine and 2.4g (0.08mol) of paraformaldehyde are added into a 250mL three-neck flask provided with a condenser tube, a magneton stirrer and a thermometer, the mixture is uniformly mixed and heated to 140 ℃ for reaction for 0.75h, 8.58g (0.03mol) of natural diphenolic acid is added, the mixture is uniformly mixed and then reacted for 2h at 140 ℃, and the molar ratio of aldehyde group, phenolic hydroxyl group and amino functional group is 1.33: 1: 0.67, after the reaction is finished, pouring the reaction solution into a methanol solution (with the concentration of 95 wt%) for standing for 24 hours, removing supernatant after standing to obtain yellow powder, drying the yellow powder in vacuum at 60 ℃ for 8 hours, and finally drying to obtain the product, namely the benzoxazine prepolymer with the full biological source. The yield was 99.6% and the molecular weight distribution was 1.14.
Example 4
Preparing a benzoxazine prepolymer with a full biological source:
under nitrogen atmosphere and without solvent, 2.91g (0.03mol) of furfuryl amine and 1.8g (0.06mol) of paraformaldehyde are added into a 250mL three-neck flask provided with a condenser tube, a magneton stirrer and a thermometer, the mixture is uniformly mixed and heated to 130 ℃ for reaction for 0.5h, then 8.58g (0.03mol) of natural diphenolic acid is added, the mixture is uniformly mixed and then reacted for 2.5h at 130 ℃, and the molar ratio of aldehyde group, phenolic hydroxyl group and amino functional group is 1: 1: 0.5, after the reaction is finished, pouring the reaction solution into a methanol solution (with the concentration of 65 wt%) and standing for 24 hours, removing supernatant after standing to obtain yellow powder, drying the yellow powder in vacuum at 60 ℃ for 8 hours, and finally drying to obtain the product, namely the benzoxazine prepolymer with the full biological source. The yield was 99.3%, and the molecular weight distribution was 1.21.
Example 5
Preparing a benzoxazine prepolymer with a full biological source:
adding 5.82g (0.06mol) of furfuryl amine and 3.60g (0.12mol) of paraformaldehyde into a three-neck flask provided with a condenser tube, a magnetic stirrer and a thermometer, adding 75mL of a toluene/ethanol mixed solvent (the volume ratio of toluene to ethanol is 2:1), heating to 80 ℃, stirring for 60min, introducing nitrogen, adding 8.58g (0.03mol) of natural bisphenol, and enabling the molar ratio of aldehyde groups, phenolic hydroxyl groups and amino functional groups to be 2: 1:1, continuing to react for 7 hours, pouring the reaction solution into a methanol solution (with the concentration of 85 wt%) after the reaction is finished, standing for 24 hours to obtain a precipitate, drying the precipitate at 60 ℃ in vacuum for 6 hours, and finally grinding the dried product to obtain brown yellow powder, namely the benzoxazine prepolymer with the full biological source. The yield was 95%, and the molecular weight distribution was 1.15.
Example 6
Preparing a benzoxazine prepolymer with a full biological source:
adding 2.91g (0.03mol) of furfuryl amine and 1.8g (0.06mol) of paraformaldehyde into a three-neck flask provided with a condenser, a magnetic stirrer and a thermometer, adding 60mL of a toluene/N, N' -dimethylformamide mixed solvent (the volume ratio is 1:1), heating to 115 ℃, stirring for 30min, introducing nitrogen, adding 8.58g (0.03mol) of natural diphenolic acid, and adding a mixture of aldehyde group, phenolic hydroxyl group and amino functional group in a molar ratio of 1: 1: 0.5, continuing to react for 3.5 hours, pouring the reaction solution into a methanol solution (with the concentration of 50 wt%) after the reaction is finished, standing for 24 hours to obtain a precipitate, drying the precipitate in vacuum at 60 ℃ for 6 hours, and finally grinding the dried product to obtain brown yellow powder, namely the benzoxazine prepolymer with the full biological source. The yield was 96%, and the molecular weight distribution was 1.19.
Example 7
Preparing a benzoxazine prepolymer with a full biological source:
adding 4.85g (0.05mol) of furfuryl amine and 3.00g (0.10mol) of paraformaldehyde into a three-neck flask provided with a condenser, a magnetic stirrer and a thermometer, adding 60mL of a toluene/ethanol mixed solvent (the volume ratio is 1:5), heating to 80 ℃, stirring for 30min, introducing nitrogen, adding 8.58g (0.03mol) of natural diphenolic acid, and enabling the molar ratio of aldehyde groups, phenolic hydroxyl groups and amino functional groups to be 1.67: 1: 0.83, continuing to react for 5 hours, pouring the reaction solution into a methanol solution (with the concentration of 95 wt%) after the reaction is finished, standing for 24 hours to obtain a precipitate, drying the precipitate in vacuum at 60 ℃ for 6 hours, and finally grinding the dried product to obtain brown yellow powder, namely the benzoxazine prepolymer with full biological source. The yield was 95%, and the molecular weight distribution was 1.17.
Example 8
Preparing a benzoxazine prepolymer with a full biological source:
adding 3.88g (0.04mol) of furfuryl amine and 2.4g (0.08mol) of paraformaldehyde into a three-neck flask provided with a condenser, a magnetic stirrer and a thermometer, adding 60mL of a toluene/ethyl acetate mixed solvent (the volume ratio is 5:1), heating to 75 ℃, stirring for 60min, introducing nitrogen, adding 8.58g (0.03mol) of natural bisphenol, and enabling the molar ratio of aldehyde groups, phenolic hydroxyl groups and amino functional groups to be 1.33: 1: 0.67, continuing to react for 4 hours, pouring the reaction solution into a methanol solution (with the concentration of 60 wt%) after the reaction is finished, standing for 24 hours to obtain a precipitate, drying the precipitate in vacuum at 60 ℃ for 6 hours, and finally grinding the dried product to obtain brown yellow powder, namely the benzoxazine prepolymer with full biological source. The yield was 95%, and the molecular weight distribution was 1.20.
Example 9
Preparing polybenzoxazine resin with full biological sources:
the benzoxazine prepolymer of the total biological source prepared in the embodiment 1 is dissolved in a dimethylformamide solvent, poured into a curing mold, placed in a vacuum drying oven, heated at 80 ℃ for 12 hours, and then cured at 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 ℃ for 2 hours respectively to obtain the benzoxazine resin of the total biological source, wherein the glass transition temperature is 303 ℃, the carbon residue rate at 800 ℃ can reach 40%, the limiting oxygen index can reach 33.5, the dielectric constant is 2.8, and the dielectric loss is 0.01.
Example 10
Preparing the all-natural polybenzoxazine resin:
the all-natural benzoxazine prepolymer prepared in the embodiment 2 is placed in a curing mould and is cured for 4 hours at 200 ℃ in a vacuum drying oven to obtain the all-natural benzoxazine resin, the glass transition temperature of the all-natural benzoxazine resin is 290 ℃, the carbon residue rate at 800 ℃ can reach 37 percent, the limiting oxygen index can reach 32.3, the dielectric constant is 2.85, and the dielectric loss is 0.016.
Example 11
Preparing polybenzoxazine resin with full biological sources:
the benzoxazine prepolymer of the total biological source prepared in the example 5 is dissolved in a toluene/ethanol mixed solvent (the volume ratio of toluene to ethanol is 2:1), poured into a curing mold, placed in a vacuum drying oven and heated at 80 ℃ for 12 hours, and then cured for 2 hours at 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 ℃ respectively to obtain the benzoxazine resin of the total biological source, wherein the glass transition temperature of the benzoxazine resin is 300 ℃, the carbon residue rate of 800 ℃ can reach 40%, the limiting oxygen index can reach 33, the dielectric constant is 2.83, and the dielectric loss is 0.019.
Example 12
Preparing polybenzoxazine resin with full biological sources:
the benzoxazine prepolymer of the total biological source prepared in the embodiment 8 is dissolved in a toluene solvent and poured into a curing mold, and then cured at 100 ℃ for 24 hours to obtain the benzoxazine resin of the total biological source, wherein the glass transition temperature is 265 ℃, the carbon residue rate at 800 ℃ can reach 27%, the limiting oxygen index can reach 28.7, the dielectric constant is 2.95, and the dielectric loss is 0.019.
Example 13
By improving the preparation process, the resin can also be prepared into a porous carbon material for magnetic separation of water pollutants, photocatalytic degradation of pollutants and the like.
Dissolving the full-biological-source benzoxazine prepolymer prepared in example 1 and ferroferric oxide in a dimethylformamide solvent (the concentration of the dimethyl formamide prepolymer is 20%), pouring the mixture into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a vacuum drying oven, heating the mixture for 8 hours at 130 ℃, then respectively curing the mixture for 2 hours at 140 ℃, 160 ℃, 180 ℃ and 200 ℃ to obtain a full-biological-source benzoxazine resin/zinc oxide porous material, placing the resin in a tube furnace for carbonization for 2 hours at 700 ℃ under the protection of nitrogen to obtain the porous material based on the full-biological-source benzoxazine resin and the ferroferric oxide, wherein the specific surface area of the porous material is 51m2(ii) in terms of/g. The obtained porous material is ground into powder and put into water, and pollutants such as methylene blue and the like in the water can be effectively adsorbed and decomposed.
Example 14
The benzoxazine prepolymer of the whole biological source prepared in example 5 and zinc oxide were dissolved in dimethylformamide (30% concentration) and poured into a hydrothermal reaction vessel, and the vessel was placed under vacuumHeating at 130 deg.C for 8h in a drying oven, respectively curing at 140 deg.C, 160 deg.C, 180 deg.C, and 200 deg.C for 2h to obtain the benzoxazine resin/zinc oxide porous material, carbonizing the resin at 700 deg.C for 1h in a tubular furnace under the protection of nitrogen gas to obtain porous material based on benzoxazine resin and zinc oxide with specific surface area of 66m2(ii) in terms of/g. The obtained porous material is ground into powder and put into water, pollutants such as formaldehyde and the like in the water can be effectively degraded through ultraviolet irradiation, and the removal rate in a formaldehyde solution with the concentration of 12ppm is 96%.
Claims (10)
1. A benzoxazine resin with full biological sources is characterized in that: the structure is as follows:
2. the fully biogenic benzoxazine resin according to claim 1, wherein: the benzoxazine prepolymer is obtained by dissolving and curing a benzoxazine prepolymer with a full biological source;
the solvent used for dissolving in the solidification is any one or more of toluene, xylene, ethanol, chloroform, dimethylformamide and 1, 4-dioxane,
the benzoxazine prepolymer with all biological sources has the following general formula:
3. the fully biogenic benzoxazine resin according to claim 2, wherein: the curing is carried out for 4-24 hours at 100-200 ℃ after the organic solvent is dissolved, so as to obtain the benzoxazine resin with the full biological source.
4. The use of the full biogenic benzoxazine resin according to claim 1, wherein: the high-frequency dielectric material is applied to the fields of high-frequency and high-speed circuit board base materials, microwave and millimeter wave communication and vehicle-mounted radars.
5. A full-biological-source benzoxazine porous resin material is prepared by curing full-biological-source benzoxazine prepolymer, or mixing the full-biological-source benzoxazine prepolymer and nanoparticles according to the mass ratio of 10% -30%, then curing, and carbonizing in an inert atmosphere to obtain the full-biological-source benzoxazine resin-based porous material, wherein the carbonization is carried out at the temperature of 600-800 ℃ for 5-15 hours; the nano particles are selected from zinc oxide, ferroferric oxide, titanium dioxide, zirconium oxide or aluminum hydroxide, and the benzoxazine prepolymer with a full biological source has the following general formula:
6. the application of the benzoxazine porous resin material derived from all living things as claimed in claim 5, in particular to the application of the carbonized benzoxazine resin porous material as a functional material in the aspects of electricity storage, drug loading, pollutant treatment and gas adsorption.
7. The method for preparing benzoxazine resin of complete biological origin according to claim 1, wherein:
preparing a benzoxazine prepolymer with a full biological source by adopting a solvent-free method or a mixed solvent method, wherein: the solvent-free method comprises the following steps: under the nitrogen atmosphere, firstly adding an aldehyde compound and furfuryl amine into a reaction container, reacting for 0.25-1 h at the temperature of 115-160 ℃ under the condition of high-speed stirring, then adding diphenolic acid, and continuing to react for 0.75-3 h, wherein the molar ratio of aldehyde groups in the aldehyde compound to phenolic hydroxyl groups in the diphenolic acid and amino groups in furfuryl amine is 1-2: 1: 0.5-1, and performing post-treatment to obtain a benzoxazine prepolymer with a full biological source;
the mixed solvent method comprises the following steps: adding an aldehyde compound, diphenolic acid and furfuryl amine into a reaction container in a step-by-step and multi-time feeding mode, wherein the step-by-step and multi-time feeding mode is that under the nitrogen atmosphere, the aldehyde compound and the furfuryl amine are added into the reaction container, a polar/non-polar mixed solvent is added, diphenolic acid is added after the mixture is fully stirred, and the molar ratio of aldehyde groups in the aldehyde compound to phenolic hydroxyl groups in the diphenolic acid and amino groups in the furfuryl amine is 1-2: 1: 0.5-1, reacting for 4-8 h at 75-115 ℃, and performing post-treatment to obtain a benzoxazine prepolymer with full biological sources;
and dissolving the benzoxazine prepolymer and then curing to obtain the benzoxazine resin with full biological sources.
8. The method of claim 7, wherein: the aldehyde compound is formaldehyde or paraformaldehyde;
the diphenolic acid has the following molecular structural formula:
9. the method of claim 7, wherein: the non-polar solvent: toluene, butanone, xylene; polar solvent: cyclohexanone, acetone, ethyl acetate, diethyl ether, N' -dimethylformamide, dioxane, chloroform, ethanol and tetrahydrofuran, wherein the volume ratio of the cyclohexanone to the acetone to the ethyl acetate is 5: 1-1: 5.
10. the method of claim 7, wherein: the post-treatment in the solvent-free method comprises the following steps: after the reaction is finished, grinding the reactant into powder, pouring the powder into a methanol solution to remove unreacted reactant and impurities, standing the solution, removing supernatant to obtain yellow powder, and drying the yellow powder to obtain the benzoxazine prepolymer with the full biological source;
the post-treatment in the mixed solvent method comprises the following steps: and after the reaction is finished, pouring the reaction product or the reaction liquid into a methanol solution to remove unreacted substances and impurities, drying the precipitate, and grinding to obtain the benzoxazine oligomer, wherein the concentration of the methanol solution is 50-95 wt%.
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| CN111234211A (en) * | 2020-03-16 | 2020-06-05 | 淮北绿洲新材料有限责任公司 | Benzoxazine intrinsic flame-retardant resin and preparation method thereof |
| CN112707932B (en) * | 2020-12-30 | 2021-12-28 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
| CN113149856B (en) * | 2021-01-13 | 2022-12-02 | 浙江理工大学 | Amide-containing bio-based benzoxazine resin and preparation method thereof |
| CN113201109B (en) * | 2021-05-08 | 2022-05-24 | 中北大学 | Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material |
| CN113416289B (en) * | 2021-07-15 | 2022-10-11 | 中国科学院宁波材料技术与工程研究所 | Bio-based benzoxazine organic phase change material and preparation method and application thereof |
| CN115449045A (en) * | 2022-10-14 | 2022-12-09 | 四川金象赛瑞化工股份有限公司 | Synthesis of melamine modified bisphenol-furan benzoxazine resin and preparation method of composite material thereof |
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