A method of making a bio-based furan-acrylonitrile copolymer particle, pre-oxidized particle, and carbonized particle
By using the self-stabilizing precipitation polymerization of bio-based furan-acrylonitrile copolymers, the problem of concentrated exothermic reaction during the pre-oxidation process of polyacrylonitrile was solved, realizing an efficient and controllable pre-oxidation and carbonization process. This resulted in the preparation of carbon materials with uniform morphology and good thermal stability, which can be applied to energy storage electrode materials and electrocatalytic carriers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BEIJING UNIV OF CHEM TECH
- Filing Date
- 2026-05-15
- Publication Date
- 2026-06-30
Smart Images
Figure CN122302166A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer and carbon materials technology, and in particular to a method for preparing bio-based furan-acrylonitrile copolymer particles, pre-oxidized particles, and carbonized particles. Background Technology
[0002] The transition from fossil fuels to renewable resources has become one of the most critical development directions in modern polymer science. Among various biomass-derived monomers, furanyl monomers derived from cellulose and hemicellulose have attracted much attention. These monomers use low-cost agricultural byproducts such as corn cobs and rice straw as raw materials, and possess advantages such as renewability, multifunctionality, and versatility. In the past decade, their applications have gradually expanded from traditional resins to advanced fields such as optoelectronics, semiconductors, and composite materials.
[0003] High-performance carbon materials are fundamental materials for energy storage, environmental remediation, and functional composite materials. Among them, nitrogen-doped carbon materials, due to the introduction of active sites such as pyridine nitrogen and pyrrole nitrogen into the carbon framework, exhibit excellent conductivity, catalytic activity, and adsorption performance, showing broad application prospects. Polyacrylonitrile (PAN) is one of the most important precursors for preparing high-performance carbon materials, but its homopolymers exhibit significant concentrated exothermic phenomena during pre-oxidation, resulting in violent and difficult-to-control reactions that easily cause morphological damage and structural defects in materials, a problem particularly prominent in small-sized systems such as particles. Therefore, controlling the cyclization reaction of PAN through molecular structure design to make the pre-oxidation process more mild and controllable has become an important research direction in this field.
[0004] Currently, a common strategy is to introduce monomers such as itaconic acid and itaconic acid esters to improve the pre-oxidation behavior of PAN. However, these carboxylic acid monomers have limitations in terms of bio-based properties, structural functions, and compatibility with carbon materials. Although some studies have attempted to copolymerize bio-based monomers such as lignin and dopamine with acrylonitrile, these methods generally suffer from low copolymerization activity, poor binding efficiency, and limited ability to control morphology and thermal behavior, failing to simultaneously meet the multiple requirements of green renewability, controllable pre-oxidation process, preservation of carbonization morphology, and improved carbon yield. Therefore, developing a novel, highly efficient, and precisely controllable bio-based acrylonitrile copolymerization system is of great significance for promoting the development of green high-performance carbon materials. Summary of the Invention
[0005] The purpose of this invention is to provide a method for preparing bio-based furan-acrylonitrile copolymer particles, pre-oxidized particles, and carbonized particles, thereby solving the problems existing in the prior art. This invention uses furan derivatives as electron-rich components and acrylonitrile and its derivatives as electron-deficient components, and prepares submicron-sized copolymer particles with uniform morphology and narrow size distribution through self-stabilizing precipitation polymerization, thereby significantly improving the pre-oxidation behavior and carbonization performance of PAN.
[0006] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention provides a method for preparing bio-based furan-acrylonitrile copolymer particles, comprising the following steps: Bio-based furan monomers (electron-rich), acrylonitrile monomers (electron-deficient), and initiators are mixed in a solvent, and the mixture is subjected to a self-stabilizing precipitation polymerization reaction under an inert atmosphere to obtain copolymer particles. The bio-based furan monomer is selected from one or more of furfuryl alcohol (FA), furfuryl acetate (FMA), furoic acid (FAc), and glycidyl ether furfuryl (GEFA); The acrylonitrile monomer is selected from one or both of acrylonitrile (AN) and methacrylonitrile (MAN).
[0007] The solvent is one or more of the following: organic acid alkyl esters, aromatic solvents, ether solvents, and ketone solvents; The organic acid alkyl esters include one or more of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, and isoamyl phenylacetate, preferably one or more of ethyl acetate, butyl acetate, amyl acetate, and isoamyl acetate. The aromatic solvent includes one or more of toluene, ethylbenzene, xylene, and cumene, preferably xylene; The ether solvent includes one or more of dimethyl ether, methyl ethyl ether, ethyl ether, ethyl propyl ether, dipropyl ether, dibutyl ether, methyl propyl ether, methyl butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopentyl ether, methyl tert-amyl ether, methyl cyclopentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane, preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and tetrahydrofuran; The ketone solvents include one or more of acetone, butanone, cyclohexanone, methyl isobutyl ketone, and methyl isopropyl ketone, preferably acetone or butanone.
[0008] Furthermore, the polymerization reaction is carried out at a temperature of 30-150°C, preferably 40-120°C, for a time of 1-12 hours.
[0009] Further, the molar ratio of the bio-based furan monomer to the acrylonitrile monomer is 0.01:1-1:1; the amount of the initiator added is 0.01 wt%-5 wt% of the total mass of the bio-based furan monomer and the acrylonitrile monomer, preferably 0.1-5 wt%, more preferably 0.5-5 wt%.
[0010] Furthermore, a crosslinking agent is added to the mixture; the amount of the crosslinking agent added is 0 wt%-50 wt% of the total mass of the bio-based furan monomer and acrylonitrile monomer, and is not 0 wt%, preferably 0–30 wt%, more preferably 0–20 wt%, and is not 0 wt%.
[0011] Furthermore, the initiator includes one or more of azo initiators, peroxide initiators, or oil-soluble redox initiation systems.
[0012] The peroxide initiator includes one or more of benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, ditert-butyl peroxide, dodecyl peroxide, and benzoic acid peroxide, preferably benzoyl peroxide; the azo initiator includes one or more of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, azoisobutylcyanoformamide, azobiscyclohexylformitrile, and dimethyl azobisisobutyrate, preferably azobisisobutyronitrile and / or azobisisoheptanenitrile.
[0013] Further, the crosslinking agent includes one or more of aromatic divinyl compounds, difunctional or polyfunctional (meth)acrylates, divinyl ether compounds, divinylsilane compounds, bismaleimide compounds, and conjugated dienes; preferably one or more of divinylbenzene, 1,3-diisopropenylbenzene, divinyl ether, divinyldimethylsilane, ethylene glycol diacrylate, butylene glycol diacrylate, and N,N'-(methylenediphenyl)bismaleimide.
[0014] Furthermore, the mass concentration of the bio-based furan monomer and acrylonitrile monomer in the mixed system is 0.1-50%, preferably 1-30 wt%, and more preferably 5-25 wt%.
[0015] The second technical solution of the present invention provides bio-based furan-acrylonitrile copolymer particles prepared by the above preparation method.
[0016] The bio-based furan-acrylonitrile copolymer particles prepared by this invention have the morphology of microspheres or flower-like nanostructures.
[0017] The third technical solution of the present invention provides a method for preparing the above-mentioned bio-based furan-acrylonitrile copolymer pre-oxidized particles, comprising the following steps: pre-oxidizing the above-mentioned bio-based furan-acrylonitrile copolymer particles at 170-300℃ to obtain the bio-based furan-acrylonitrile copolymer pre-oxidized particles.
[0018] Furthermore, the pre-oxidation treatment is carried out in an air atmosphere, with the heating rate controlled at 0.5-5℃ / min.
[0019] The fourth technical solution of the present invention provides pre-oxidized particles of bio-based furan-acrylonitrile copolymer prepared by the above preparation method.
[0020] The fifth technical solution of the present invention provides a method for preparing the above-mentioned bio-based furan-acrylonitrile copolymer carbonized particles, comprising the following steps: carbonizing the above-mentioned bio-based furan-acrylonitrile copolymer pre-oxidized particles in an inert atmosphere at 600-1200°C to obtain the bio-based furan-acrylonitrile copolymer carbonized particles.
[0021] The sixth technical solution of the present invention provides bio-based furan-acrylonitrile copolymer carbonized particles prepared by the above preparation method.
[0022] The bio-based furan-acrylonitrile copolymer prepared by this invention has uniform morphology, adjustable pore structure and nitrogen content, and good thermal stability. It can be directly used as an energy storage electrode material for supercapacitors, an electrocatalytic carrier, and an adsorbent for water pollutants. It can also be used as a functional filler and separation membrane material. It is green and environmentally friendly, has a simple process, and has good prospects for industrial application.
[0023] The present invention discloses the following technical effects: The copolymer system constructed in this invention can significantly enhance the reactivity of bio-based furan monomers in free radical polymerization, promote their effective embedding into polyacrylonitrile molecular chains, and increase the copolymerization ratio. The bio-based furan-acrylonitrile copolymer prepared by this invention requires no addition of stabilizers or surfactants, has mild reaction conditions, a simple process, and high preparation efficiency, and avoids environmental pollution and safety risks; the copolymer particles exhibit excellent monodispersity, and the particle size can be flexibly controlled by parameters such as monomer concentration and reaction temperature.
[0024] The bio-based furan copolymerization strategy proposed in this invention can effectively regulate the cyclization mechanism, partially transform the free radical reaction pathway into an ionic mechanism, achieve a mild and controllable cyclization process, significantly reduce the cyclization energy barrier, suppress concentrated exothermic reactions during pre-oxidation, improve processing performance, and simultaneously increase carbon yield and material thermal stability.
[0025] In summary, this invention not only achieves the efficient utilization of bio-based furan monomers in polyacrylonitrile systems, but also provides a new approach for the development of green, high-performance nitrogen-doped carbon particles and carbon materials. Attached Figure Description
[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0027] Figure 1 SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 1, 2 and 3.
[0028] Figure 2 SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 4, 5 and 6.
[0029] Figure 3 SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 9, 10 and 11.
[0030] Figure 4 SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 17 and 18.
[0031] Figure 5 SEM images of the pre-oxidized particles of bio-based furan-acrylonitrile copolymers from Examples 19, 21, and 23.
[0032] Figure 6 SEM images of the bio-based furan-acrylonitrile copolymer carbonized particles prepared in Examples 24, 25 and 26.
[0033] Figure 7 TGA curves of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 9, 10 and 11.
[0034] Figure 8 The DSC curves are for the bio-based furan-acrylonitrile copolymer particles prepared in Examples 9, 10 and 11.
[0035] Figure 9 The images show the FTIR spectra of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 9 and 19. Detailed Implementation
[0036] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0037] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0038] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0039] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.
[0040] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.
[0041] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.
[0042] Example 1 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile and 0.09 g of azobisisobutyronitrile, dissolve them in 10 mL of ethyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with ethyl acetate and petroleum ether respectively, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0043] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 1.34 μm, and the yield is 20%.
[0044] Example 2 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile and 0.09 g of azobisisobutyronitrile, dissolve them in 10 mL of butyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with butyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0045] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 1.34 μm, and the yield is 27%.
[0046] Example 3 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, and 0.09 g of azobisisobutyronitrile (AIBN), dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0047] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this embodiment is 1.30 μm, and the yield is 30%.
[0048] SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 1, 2, and 3 are shown below. Figure 1 .
[0049] Example 4 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.34 g of methacrylonitrile and 0.09 g of azobisisobutyronitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 55 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0050] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.85 μm, and the yield is 28%.
[0051] Example 5 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 2.8 g of furfuryl acetate, 1.06 g of acrylonitrile and 0.16 g of azobisisoheptanenitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 55 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0052] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this embodiment is 1.3 μm, and the yield is 12%.
[0053] Example 6 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 3.08 g of furfuryl glycidyl ether, 1.06 g of acrylonitrile and 0.09 g of azobisisoheptanenitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 55 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0054] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this embodiment is 0.85 μm, and the yield is 18%.
[0055] SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 4, 5, and 6 are shown below. Figure 2 .
[0056] Example 7 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, and 0.03 g of azobisisobutyronitrile (AIBN), dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0057] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.9 μm, and the yield is 23%.
[0058] Example 8 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, and 0.03 g of azobisisobutyronitrile (AIBN), dissolve them in 5 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0059] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 1.5 μm, and the yield is 40%.
[0060] Example 9 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 0.06 g of furfuryl alcohol, 1.06 g of acrylonitrile and 0.035 g of azobisisobutyronitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 70 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0061] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.65 μm, and the yield is 76%.
[0062] Example 10 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 0.1 g of furfuryl alcohol, 1.06 g of acrylonitrile and 0.035 g of azobisisobutyronitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 70 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0063] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.7 μm, and the yield is 70%.
[0064] Example 11 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 0.2 g of furfuryl alcohol, 1.06 g of acrylonitrile and 0.038 g of azobisisobutyronitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 70 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0065] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.75 μm, and the yield is 60%.
[0066] SEM images of the copolymer particles prepared in Examples 9, 10, and 11 are shown below. Figure 3 .
[0067] The TGA curves of the copolymer particles prepared in Examples 9, 10, and 11 are shown below. Figure 7 As shown in the figure, the carbon residue of the copolymer increases significantly with the increase of furfuryl alcohol feed amount. The DSC curves of the copolymer particles prepared in Examples 9, 10, and 11 are shown below. Figure 8 As shown in the figure, the introduction of furfuryl alcohol can significantly broaden the width of the exothermic peak and avoid concentrated exothermic activity.
[0068] Example 12 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 0.1 g of furoic acid, 1.06 g of acrylonitrile and 0.035 g of azobisisobutyronitrile, dissolve them in 10 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 70 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0069] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.75 μm, and the yield is 68%.
[0070] Example 13 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, 0.3 g of divinylbenzene and 0.09 g of azobisisobutyronitrile, dissolve them in 30 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0071] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.75 μm, and the yield is 75%.
[0072] Example 14 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, 0.3 g of 1,3-diisopropenylbenzene and 0.09 g of azobisisobutyronitrile, dissolve them in 30 mL of isoamyl acetate, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0073] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 0.85 μm, and the yield is 71%.
[0074] Example 15 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, 0.6 g of divinyldimethylsilane, and 0.09 g of azobisisobutyronitrile (AIBN), dissolve them in a mixed solvent of 30 mL of isoamyl acetate and 15 mL of n-heptane, purge with nitrogen for 15 min to remove oxygen, and react at 75 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether successively, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0075] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 1.52 μm, and the yield is 75%.
[0076] Example 16 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh 1.96 g of furfuryl alcohol, 1.06 g of acrylonitrile, 0.6 g of N,N'-(methylenediphenyl)bismaleimide, and 0.09 g of dicumyl peroxide, dissolve them in a mixed solvent of 30 mL cyclohexanone and 15 mL n-nonane, purge with nitrogen for 15 min to remove oxygen, and react at 120 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with isoamyl acetate and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0077] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 1.38 μm, and the yield is 85%.
[0078] Example 17 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh out 0.1 g of furfuryl alcohol, 2.12 g of acrylonitrile, 0.06 g of azobisisobutyronitrile and 0.09 g of dicumyl peroxide, dissolve them in 20 mL of acetonitrile, purge with nitrogen for 15 min to remove oxygen, and react at 55 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with acetonitrile and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0079] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this embodiment is 0.82 μm, and the yield is 80%.
[0080] The FTIR spectra of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 9 and 17 are shown below. Figure 9 As shown.
[0081] Example 18 This embodiment provides a bio-based furan-acrylonitrile copolymer particle, and the preparation steps are as follows: Weigh out 0.1 g of furfuryl alcohol, 2.12 g of acrylonitrile, and 0.06 g of azobisisoheptanenitrile, dissolve them in 20 mL of methyl ethyl ketone, purge with nitrogen for 15 min to remove oxygen, and react at 55 °C for 12 h. After the reaction is complete, centrifuge the reaction solution at 10000 r / min for 5 min, wash with methyl ethyl ketone and petroleum ether in sequence, centrifuge, repeat three times, and vacuum dry to constant weight to obtain bio-based furan-acrylonitrile copolymer particles.
[0082] The average particle size of the bio-based furan-acrylonitrile copolymer particles obtained in this example is 1.35 μm, and the yield is 75%.
[0083] SEM images of the bio-based furan-acrylonitrile copolymer particles prepared in Examples 17 and 18 are shown below. Figure 4 .
[0084] Example 19 This embodiment provides a bio-based furan-acrylonitrile copolymer pre-oxidized particle, and the preparation steps are as follows: Take the bio-based furan-acrylonitrile copolymer particles prepared in Example 9, heat them from room temperature to 300°C at a heating rate of 5°C / min in air atmosphere, and hold them at that temperature for 30 min to obtain bio-based furan-acrylonitrile copolymer pre-oxidized particles.
[0085] The average particle size of the bio-based furan-acrylonitrile copolymer pre-oxidized particles obtained in this example is 0.51 μm, and the yield is 83%.
[0086] The FTIR spectra of the bio-based furan-acrylonitrile copolymer particles prepared in Example 9 and the bio-based furan-acrylonitrile copolymer pre-oxidized particles prepared in Example 19 are shown below. Figure 9 As can be seen from the figure, the characteristic peak of the cyano group in the pre-oxidized product decreases significantly, while the characteristic absorption peak of C=N appears, indicating the occurrence of cyclization reaction and the formation of ladder structure.
[0087] Example 20 This embodiment provides a bio-based furan-acrylonitrile copolymer pre-oxidized particle, and the preparation steps are as follows: Take the bio-based furan-acrylonitrile copolymer particles prepared in Example 9, heat them from room temperature to 200°C at a heating rate of 3°C / min in air atmosphere, hold for 30 min, then heat them to 300°C at a heating rate of 1°C / min and hold for 30 min to obtain bio-based furan-acrylonitrile copolymer pre-oxidized particles.
[0088] The average particle size of the bio-based furan-acrylonitrile copolymer pre-oxidized particles obtained in this embodiment is 0.52 μm, and the yield is 86%.
[0089] Example 21 This embodiment provides a bio-based furan-acrylonitrile copolymer pre-oxidized particle, and the preparation steps are as follows: Take the bio-based furan-acrylonitrile copolymer particles prepared in Example 10, heat them from room temperature to 200°C at a heating rate of 10°C / min in air atmosphere, hold for 30 min, then heat them to 300°C at a heating rate of 1°C / min and hold for 30 min to obtain bio-based furan-acrylonitrile copolymer pre-oxidized particles.
[0090] The average particle size of the bio-based furan-acrylonitrile copolymer pre-oxidized particles obtained in this example is 0.58 μm, and the yield is 85%.
[0091] Example 22 This embodiment provides a bio-based furan-acrylonitrile copolymer pre-oxidized particle, and the preparation steps are as follows: Take the bio-based furan-acrylonitrile copolymer particles prepared in Example 13, heat them from room temperature to 200°C at a heating rate of 10°C / min in an air atmosphere, hold for 30 min, then heat them to 300°C at a heating rate of 1°C / min and hold for 30 min to obtain bio-based furan-acrylonitrile copolymer pre-oxidized particles.
[0092] The average particle size of the bio-based furan-acrylonitrile copolymer pre-oxidized particles obtained in this example is 0.65 μm, and the yield is 92%.
[0093] Example 23 This embodiment provides a bio-based furan-acrylonitrile copolymer pre-oxidized particle, and the preparation steps are as follows: Take the bio-based furan-acrylonitrile copolymer particles prepared in Example 15, heat them from room temperature to 200°C at a heating rate of 10°C / min in air atmosphere, hold for 30 min, then heat them to 300°C at a heating rate of 1°C / min and hold for 30 min to obtain bio-based furan-acrylonitrile copolymer pre-oxidized particles.
[0094] The average particle size of the bio-based furan-acrylonitrile copolymer pre-oxidized particles obtained in this embodiment is 1.32 μm, and the yield is 88%.
[0095] SEM images of the pre-oxidized copolymer particles prepared in Examples 19, 21, and 23 are shown below. Figure 5 .
[0096] Example 24 This embodiment provides a bio-based furan-acrylonitrile copolymer carbonized particle, and the preparation steps are as follows: The pre-oxidized particles of the bio-based furan-acrylonitrile copolymer prepared in Example 19 were heated from room temperature to 800°C at a heating rate of 3°C / min under a nitrogen atmosphere and held at this temperature for 2 hours to obtain carbonized particles of the bio-based furan-acrylonitrile copolymer. The yield of the carbonized particles of the bio-based furan-acrylonitrile copolymer obtained in this example was 56%.
[0097] Example 25 This embodiment provides a bio-based furan-acrylonitrile copolymer carbonized particle, and the preparation steps are as follows: Take the pre-oxidized particles of bio-based furan-acrylonitrile copolymer prepared in Example 21, heat them from room temperature to 1200°C at a heating rate of 5°C / min under a nitrogen atmosphere, and hold for 1 hour to obtain carbonized particles of bio-based furan-acrylonitrile copolymer.
[0098] The average particle size of the bio-based furan-acrylonitrile copolymer carbonized particles obtained in this embodiment is 0.68 μm, and the yield is 55%.
[0099] Example 26 Take the pre-oxidized particles of bio-based furan-acrylonitrile copolymer prepared in Example 23, heat them from room temperature to 1200°C at a heating rate of 5°C / min under a nitrogen atmosphere, and hold for 1 hour to obtain carbonized particles of bio-based furan-acrylonitrile copolymer.
[0100] The average particle size of the bio-based furan-acrylonitrile copolymer carbonized particles obtained in this embodiment is 0.62 μm, and the yield is 58%.
[0101] SEM images of the carbonized copolymer particles prepared in Examples 24, 25, and 26 are shown below. Figure 6 .
[0102] Example 27 The obtained carbonized copolymer particles can be used for the selective adsorption of basic dyes. Taking methylene blue as an example: take 10 mg of the carbonized copolymer powder prepared in Example 26, add 20 mL of methylene blue aqueous solution (200 mg / L), and disperse it evenly by ultrasonication. The saturated adsorption capacity is 128 mg / g under the condition of pH 10.
[0103] Example 28 The obtained carbonized copolymer particles can be used for the selective adsorption of basic dyes. Taking crystal violet as an example: take 10 mg of the carbonized copolymer powder prepared in Example 26, add 20 mL of crystal violet aqueous solution (200 mg / L), and disperse evenly by ultrasonication. The saturated adsorption capacity is 152 mg / g under pH 10 conditions.
[0104] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims
1. A method for preparing bio-based furan-acrylonitrile copolymer particles, characterized in that, Includes the following steps: Bio-based furan monomers, acrylonitrile monomers, and initiators are mixed in a solvent, and the mixture is polymerized under an inert atmosphere to obtain copolymer particles. The bio-based furan monomer is selected from one or more of furfuryl alcohol, furfuryl acetate, furoic acid, and furfuryl glycidyl ether; The acrylonitrile monomer is selected from one or both of acrylonitrile and methacrylonitrile.
2. The preparation method according to claim 1, characterized in that, The polymerization reaction is carried out at a temperature of 30-150℃ for 1-12 hours.
3. The preparation method according to claim 1, characterized in that, The molar ratio of the bio-based furan monomer to the acrylonitrile monomer is 0.01:1 to 1:1; the amount of the initiator added is 0.01 wt% to 5 wt% of the total mass of the bio-based furan monomer and the acrylonitrile monomer.
4. The preparation method according to claim 1, characterized in that, The mixture also contains a crosslinking agent; the amount of the crosslinking agent added is 0 wt%-50 wt% of the total mass of the bio-based furan monomer and acrylonitrile monomer, and is not 0 wt%.
5. The preparation method according to claim 1, characterized in that, The bio-based furan monomer and acrylonitrile monomer have a mass concentration of 0.1-50% in the mixed system.
6. Bio-based furan-acrylonitrile copolymer particles prepared by the preparation method according to any one of claims 1-5.
7. A method for preparing pre-oxidized particles of a bio-based furan-acrylonitrile copolymer, characterized in that, The process includes the following steps: pre-oxidizing the bio-based furan-acrylonitrile copolymer particles according to claim 6 at 170-300°C to obtain the pre-oxidized bio-based furan-acrylonitrile copolymer particles.
8. Bio-based furan-acrylonitrile copolymer pre-oxidized particles prepared by the preparation method according to claim 7.
9. A method for preparing bio-based furan-acrylonitrile copolymer carbonized particles, characterized in that, The process includes the following steps: carbonizing the pre-oxidized particles of the bio-based furan-acrylonitrile copolymer as described in claim 8 in an inert atmosphere at 600-1200 °C to obtain the carbonized particles of the bio-based furan-acrylonitrile copolymer.
10. The bio-based furan-acrylonitrile copolymer carbonized particles prepared by the preparation method according to claim 9.