CN113908813A - Cellulose derivative-silicon-based hybrid microsphere and preparation method thereof - Google Patents

Cellulose derivative-silicon-based hybrid microsphere and preparation method thereof Download PDF

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CN113908813A
CN113908813A CN202111234454.1A CN202111234454A CN113908813A CN 113908813 A CN113908813 A CN 113908813A CN 202111234454 A CN202111234454 A CN 202111234454A CN 113908813 A CN113908813 A CN 113908813A
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cellulose
silicon
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杨亦文
于晓晓
鲍宗必
张治国
杨启炜
苏云
任其龙
苏宝根
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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Quzhou Research Institute of Zhejiang University
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Abstract

The invention discloses a preparation method of a cellulose derivative-silicon-based hybrid microsphere, which comprises the following steps: firstly, carrying out derivatization reaction on hydroxyl on cellulose to obtain a cellulose-3, 5-dichlorophenyl carbamate chiral silane monomer, then carrying out cross-linking reaction on the monomer and a silane coupling agent, and combining a microfluidic technology to prepare a cellulose derivative-silicon with uniform particlesHybrid microspheres are disclosed. The method is based on a sol-gel method, the hybrid microspheres prepared by the droplet microfluidic technology are uniform in particle size distribution, and the precise control of the particle size of the microspheres can be realized by adjusting the flow velocity of two phases and the curing time; the utilization rate of raw materials is high, and the prepared cellulose derivative-silicon-based hybrid microspheres have large specific surface area which can reach 780m2(ii) in terms of/g. The cellulose derivative-silicon-based hybrid microsphere prepared by the invention has high chiral recognition performance, good mechanical property and solvent tolerance, and is suitable for being used as a chiral separation material for preparing a chromatogram.

Description

Cellulose derivative-silicon-based hybrid microsphere and preparation method thereof
Technical Field
The invention relates to the field of chiral stationary phases, in particular to a cellulose derivative-silicon-based hybrid microsphere and a preparation method thereof.
Background
The more complex the drug structure, the greater the probability of chiral centers in the molecule. However, for the same drug, not all the configuration molecules are beneficial to human body, and chiral drug separation has important significance in pharmaceutical industry.
The chromatographic separation method is the main chiral drug separation method with the advantages of simple operation, wide separation range, capability of simultaneously obtaining enantiomers with high optical purity and the like, and for the method, the key technology and core lies in developing a chiral stationary phase with strong chiral recognition capability, high mechanical strength and uniform particle size distribution. At present, more than 10 kinds of chiral stationary phases with different molecular structure types are developed internationally, wherein the chiral stationary phase of the long-chain polysaccharide cellulose derivative is widely applied to the separation and preparation of enantiomers by virtue of the advantages of wide chiral recognition range, large loading capacity, cheap and easily available raw materials and the like.
The existing commercial chiral stationary phase is mainly prepared by coating or bonding a chiral recognition body on the surface of macroporous silica gel by a coating method or a bonding method. The earliest chiral stationary phases were developed by the Japanese Yoshio Okamoto group, 1984-1987, which prepared a series of cellulose derivative chiral stationary phases by coating methods and successively developed chiral chromatographic commercial columns of Chiralcel OA, Chiralcel OD, Chiralcel OJ, and the like. Thereafter, in order to improve the disadvantages of the coated chiral stationary phase chiral identifier such as easy loss due to swelling or dissolution in the mobile phase, narrow solvent application range, etc., Shouwan Tang et al (Tang S, Ikai T, Tsuji M, et al.immobilization of3, 5-dimethyl-carbonates of cellulose and amylose on silicon gel using (3-glycidoxypropyl) triethoxy-silanes as linker [ j.sep.sci.,2010,33(9):1255 bonding 1263) prepared the cellulose derivative chiral stationary phase by intramolecular cross-linking polycondensation: after a small amount (2 wt%) of 3- (triethoxysilyl) propyl-derived cellulose derivative is coated on the surface of silica gel, triethoxysilylpropyl groups on different cellulose derivative molecules are subjected to intramolecular polycondensation, so that a stationary phase with stronger stability and better chiral recognition performance is formed. The cellulose-tri (3, 5-dichlorophenyl carbamate) chiral stationary phase can be slightly dissolved in a common solvent (such as a mixed solvent of normal hexane and isopropanol) of cellulose chiral stationary phase, cannot be stably used for a long time, and cannot be prepared by a coating method. With the development of the bonded chiral stationary phase, the bound cellulose-tris (3, 5-dichlorophenyl carbamate) chiral stationary phase was developed by the company Daicel, Japan, and a Chiralpak IC commercial column was introduced. However, due to the limited specific surface area and pore volume of the support, the bonded chiral stationary phase has some disadvantages of low bonding amount and loading amount, which limits its application in industrial chromatography.
The organic-inorganic hybrid material integrates the performances of organic and inorganic materials, and can obtain an ideal material with excellent performance by adjusting the contents of organic and inorganic precursors. In 2008, Tomoyuki Ikai et al (Ikai T, Yamamoto C, Kamigaito M, et al, organic-inorganic hybrid materials for organic chemical separation using cellulose 3,5-dimethylphenylcarbamate and tetra ethyl ortho silicate [ J ]. chem.assistant.j., 2008,3(8-9):1494-1499.) prepared by a sol-gel method resulted in a cellulose-tris (3, 5-dimethylphenylcarbamate) hybrid microsphere chiral stationary phase with an organic-inorganic component ratio of about 70:30, which, while having high mechanical properties, also had a higher ability than a bonded-type Chiralpak IB column (the chiral recognition entity was cellulose-tris (3, 5-dimethylphenylcarbamate)).
Chinese patent publication No. CN102553550A discloses a hybrid chiral stationary phase based on cellulose derivatives and a preparation method thereof, wherein a series of cellulose derivative chiral stationary phases are prepared by a sol-gel method: 1) firstly, dissolving cellulose in N, N-dimethylacetamide/lithium chloride, and then carrying out derivatization reaction on hydroxyl on the cellulose and a derivatization reagent; 2) the prepared cellulose derivative containing a small amount of tri- (ethoxysilicon) propyl and a coupling agent 1, 2-di (triethoxysilyl) ethane are subjected to crosslinking polycondensation reaction in a high-pressure reaction kettle; 3) and then, dispersing the mixture obtained by the reaction in a surfactant aqueous solution, and curing to obtain the silicon-based-cellulose derivative hybrid chiral stationary phase.
Although the organic-inorganic hybrid stationary phase is suitable for chiral resolution in the aspects of mechanical strength, loading capacity and stability, the defect of the sol-gel method is that the particle size distribution of the prepared microspheres is not uniform, which leads to too wide chromatographic peak, and reduction of the separation degree and the theoretical plate number. Therefore, in order to realize the application of the stationary phase in the preparation of chromatography such as a simulated moving bed and the like, the key point is to prepare the microsphere stationary phase with uniform particles and controllable particle size on the basis.
Disclosure of Invention
The invention provides a preparation method of a cellulose derivative-silicon-based hybrid microsphere, and the prepared hybrid microsphere has controllable and uniform particle size, large specific surface area, and good mechanical strength and chiral resolution.
The technical scheme is as follows:
a preparation method of a cellulose derivative-silicon-based hybrid microsphere comprises the following steps:
(1) dissolving cellulose in an ultra-dry solvent, adding 3, 5-dichlorophenyl isocyanate and tri- (ethoxysilane) propyl isocyanate for derivatization reaction, adding a precipitator after the derivatization reaction is finished to precipitate a reaction product, filtering and drying to obtain a cellulose derivative; the ultra-dry solvent is N, N-dimethylacetamide, anhydrous lithium chloride and anhydrous pyridine;
(2) dissolving a cellulose derivative in an organic solvent or ionic liquid, adding a silane coupling agent for crosslinking reaction to obtain a crosslinked product, taking the crosslinked product or a mixture of the crosslinked product and a surfactant as a disperse phase, taking dimethyl silicone oil or a mixture of the dimethyl silicone oil and the surfactant as a continuous phase, mixing the disperse phase and the continuous phase in a microchannel by a microfluidic technology, and solidifying, filtering, washing and vacuum drying the obtained liquid drop to obtain the cellulose derivative-silicon-based hybrid microsphere.
The invention firstly performs derivatization reaction on hydroxyl on cellulose to obtain a cellulose-3, 5-dichlorophenyl carbamate chiral silane monomer, then performs crosslinking polycondensation reaction on the silane monomer and a silane coupling agent, and prepares the cellulose derivative-silicon-based hybrid microsphere with uniform particles by combining a microfluidic technology.
Preferably, the cellulose is microcrystalline cellulose with the polymerization degree of less than 200, and further preferably, the cellulose is subjected to vacuum drying treatment, so that subsequent derivatization reaction is facilitated.
Preferably, the process for adding 3, 5-dichlorophenyl isocyanate and tri- (ethoxysilicon) propyl isocyanate comprises the following steps: according to the hydroxyl mole number of the cellulose, 60-90 mol% of3, 5-dichlorophenyl isocyanate is added to carry out derivatization reaction, 2-5 mol% of tri- (ethoxysilane) propyl isocyanate is added to continue reaction, and finally 100-120 mol% of3, 5-dichlorophenyl isocyanate is added to ensure that the hydroxyl of the cellulose is completely subjected to derivatization reaction.
The process of adding 3, 5-dichlorophenyl isocyanate and tri- (ethoxysilane) propyl isocyanate is beneficial to the subsequent crosslinking polycondensation reaction of the cellulose derivative and the silane coupling agent and the regulation and control of the proportion of organic-inorganic components in the cellulose derivative-silicon-based hybrid microspheres.
Preferably, the temperature of the derivatization reaction is 60-100 ℃, and the reaction time is 24-40 h.
Preferably, the precipitant is anhydrous methanol.
In consideration of the solubility of the cellulose derivative, preferably, the organic solvent is tetrahydrofuran, dimethyl sulfoxide or dichloromethane, the ionic liquid is 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole tetrafluoroborate, and the cellulose derivative is dissolved in the organic solvent or the ionic liquid at 40-80 ℃.
Preferably, the silane coupling agent is 1, 2-bis (triethoxysilyl) ethane, and the ratio of the cellulose derivative to the silane coupling agent is 1 g: 4-10 mL. The silane coupling agent is selected and combined with the matching ratio of the cellulose derivative and the silane coupling agent, so that a synergistic effect can be achieved, the organic-inorganic component ratio of the cellulose derivative-silicon-based hybrid microsphere is adjusted, and the prepared cellulose derivative-silicon-based hybrid microsphere has excellent high-hand recognition performance, good mechanical performance and solvent tolerance.
Preferably, the temperature of the crosslinking reaction is 60-100 ℃, the pH value is 1-5, and the reaction time is 6-24 h.
Preferably, the surfactant is tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, RSN-0749 or Span 20. (ii) a
Preferably, in the mixture of the crosslinked product and the surfactant, the crosslinked product is stirred and mixed with a surfactant solution with the concentration of 0.1-0.5 wt% at the temperature of 50-100 ℃, the stirring speed is 800-4000 rpm, and the stirring time is 0.5-2 h. The parameters can ensure that the crosslinked product and the surfactant are uniformly mixed, so that the prepared cellulose derivative-silicon-based hybrid microsphere has uniform particle size distribution and the variation coefficient of less than 20 percent.
Preferably, in the mixture of the dimethyl silicone oil and the surfactant, the mass fraction of the surfactant is less than 5.0 wt%.
Preferably, in the microfluidic mixing process, the flow rate of the continuous phase is 450-1000 μ L/min; the flow rate of the dispersed phase is 10-50 mu L/min; the micro-channel is a T-shaped micro-channel and a Y-shaped micro-channel, and the size of the micro-channel is 100-200 mu m.
The dispersed phase and the continuous phase are introduced into the microchannel at a fixed flow rate, the two-phase fluid is converged at the junction, and the two-phase fluid is sheared and peeled off by the action of interfacial tension, shearing force and pressure of the fluid, so that emulsion droplets are formed, the size and the generation speed of the droplets can be controlled by adjusting the flow rate of the two phases, and the particle size of the microspheres can be controlled.
Preferably, the curing temperature is 40-120 ℃, and the curing time is 10-24 h.
The invention also provides the cellulose derivative-silicon-based hybrid microsphere prepared by the preparation method of the cellulose derivative-silicon-based hybrid microsphere.
The cellulose derivative-silicon-based hybrid microsphere particles are uniform, and the organic-inorganic ratio is as follows: 30-65: 35 to 70, an average particle diameter of 0.5 to 5 μm, and a specific surface area of 500 to 780m2(iv) g, mechanical strength and chiral resolution are good.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method of the invention is based on the sol-gel method, the cellulose derivative-silicon-based hybrid microspheres prepared by the droplet microfluidic technology have uniform particle size distribution, the precise and controllable particle size of the microspheres can be realized by adjusting the flow velocity of two phases and the curing time, and the operation is simple.
(2) The method has high utilization rate of raw materials and high balling rate, and the prepared cellulose derivative-silicon-based hybrid microspheres have large specific surface area which can reach 780m2/g。
(3) The organic-inorganic component proportion of the hybrid microsphere prepared by the invention can be regulated and controlled according to requirements, and the hybrid microsphere has high chiral identification performance, good mechanical performance and excellent solvent tolerance, and is suitable for being used as a chiral separation material for preparing a chromatogram.
Drawings
FIG. 1 shows cellulose derivative-silicon-based hybrid microspheres prepared in examples 1 to 1513C nuclear magnetic resonance spectrum.
FIG. 2 is a liquid chromatogram of the cellulose derivative-silicon-based hybrid microsphere prepared in example 1 for resolving 2-phenylcyclohexanone chiral drug.
Detailed Description
The invention is further elucidated with reference to the figures and the examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by using the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain a cellulose derivative, namely the cellulose-3, 5-dichlorophenyl carbamate chiral silane monomer.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 2.0mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in an autoclave at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into an octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.1 wt% at 80 ℃ and stirred at a high speed (4000rpm), and the solution is stirred for 1 hour at a constant temperature to be used as a dispersion phase of a microfluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a T-shaped micro-channel at the flow rate of 450 mu L/min and the flow rate of 10 mu L/min at the same time, wherein the size of the micro-channel is 200 mu m, curing the obtained liquid drops at 80 ℃ for 16h, filtering the obtained product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
The determination shows that the hybrid microsphere synthesized in the embodiment has 85 percent of balling rate, 60:40 of organic-inorganic ratio, 3.0 mu m of average particle size, 10.5 percent of variation coefficient and 720m of specific surface area2/g。
Example 2
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 3.13g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed at 100 ℃ for 8 hours, then 0.09g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 100 ℃ for 12 hours, and finally 3.48g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 100 ℃ for 9 hours to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of dimethyl sulfoxide at 80 ℃ and then 2.5mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 100 ℃ for 9 hours in an autoclave at a reaction pH of 1. Slowly dripping the prepared sol reaction solution into tetradecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.2 wt% at 80 ℃ and stirred at a high speed (4000rpm), stirring at a constant temperature for 1h, taking the solution as a dispersion phase of a microfluidic device, and taking dimethyl silicone oil as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a Y-shaped micro-channel at the flow rate of 450 mu L/min and 15 mu L/min simultaneously, wherein the size of the micro-channel is 200 mu m, curing the obtained liquid drops at 90 ℃ for 12h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
The hybrid microsphere synthesized in the example has a balling rate of 90%, an organic-inorganic ratio of 61:39, an average particle size of 2.9 μm, a coefficient of variation of 10.1%, and a specific surface area of 703m2/g。
Example 3
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 150) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of methylene chloride at 40 ℃ and then 1.0mL of 1, 2-bis (triethoxysilyl) ethane was added and the crosslinking reaction was carried out in an autoclave at 70 ℃ for 12 hours at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into an octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.2 wt% at 80 ℃ and stirred at a high speed (4000rpm), and the solution is stirred for 2 hours at a constant temperature to be used as a dispersion phase of a microfluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a T-shaped micro-channel at the flow rate of 450 mu L/min and the flow rate of 10 mu L/min at the same time, wherein the size of the micro-channel is 100 mu m, curing the obtained liquid drops at 80 ℃ for 18h, filtering the obtained product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
Through determination, the hybrid microsphere synthesized in the embodiment has the balling rate of 90 percent, the organic-inorganic ratio of 50:50, the average particle size of 2.0 mu m, the coefficient of variation of 15.5 percent and the specific surface area of 640m2/g。
Example 4
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.09g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed at 90 ℃ for 7 hours, then 0.23g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 90 ℃ for 12 hours, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 90 ℃ for 9 hours to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 2.1mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 100 ℃ for 11 hours in an autoclave at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into 0.2 wt% hexadecyl trimethyl ammonium bromide aqueous solution with high-speed stirring (2000rpm) at 80 ℃, and is stirred for 1h at constant temperature to be used as a dispersion phase of a micro-fluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a T-shaped micro-channel at the flow rate of 450 mu L/min and the flow rate of 10 mu L/min at the same time, wherein the size of the micro-channel is 150 mu m, curing the obtained liquid drops at 120 ℃ for 24h, filtering the obtained product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
According to the determination, the hybrid microsphere synthesized in the embodiment has the balling rate of 80 percent, the organic-inorganic ratio of 30:70, the average grain diameter of 1.9 mu m, the variation coefficient of 14.3 percent and the specific surface area of 780m2/g。
Example 5
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 24h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40g of 1-butyl-3-methylimidazolium chloride at 80 ℃ and then 2.5mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in a high-pressure autoclave at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into tetradecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.2 wt% at 80 ℃ and stirred at high speed (800rpm), and is stirred for 0.5h at constant temperature to be used as a dispersion phase of a microfluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a Y-shaped micro-channel at the flow rate of 550 mu L/min and 10 mu L/min simultaneously, wherein the size of the micro-channel is 180 mu m, curing the obtained liquid drops at 80 ℃ for 12h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform granular cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
The determination shows that the hybrid microsphere synthesized in the embodiment has 85 percent of balling rate, 40:60 of organic-inorganic ratio, 2.3 mu m of average particle diameter, 19.4 percent of variation coefficient and 670m of specific surface area2/g。
Example 6
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in (40g) 1-ethyl-3-methylimidazolium chloride at 80 ℃ and then 1.8mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in a high-pressure autoclave at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into an octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.3 wt% at 80 ℃ and stirred at a high speed (4000rpm), the solution is stirred for 1 hour at a constant temperature and is used as a dispersion phase of a microfluidic device, and dimethyl silicone oil containing 1.0 wt% of surfactant octadecyl trimethyl ammonium chloride is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a T-shaped micro-channel at the flow rate of 700 mu L/min and 15 mu L/min simultaneously, wherein the size of the micro-channel is 130 mu m, solidifying the obtained liquid drops at 40 ℃ for 12h, filtering the solidified product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform granular cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
According to the determination, the hybrid microsphere synthesized in the example has the balling rate of 83 percent, the organic-inorganic ratio of 51:49, the average particle size of 1.7 mu m, the coefficient of variation of 13.5 percent and the specific surface area of 540m2/g。
Example 7
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed at 90 ℃ for 7 hours, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 90 ℃ for 12 hours, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 90 ℃ for 9 hours to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 1.5mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in a high-pressure autoclave at a reaction pH of 3. The prepared sol reaction solution is slowly dripped into 0.3 wt% hexadecyl trimethyl ammonium bromide aqueous solution with high-speed stirring (3000rpm) at 80 ℃, and is stirred for 1h at constant temperature, so that the solution is used as a dispersion phase of a micro-fluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a Y-shaped micro-channel at the flow rate of 800 mu L/min and 20 mu L/min simultaneously, wherein the size of the micro-channel is 110 mu m, curing the obtained liquid drops at 80 ℃ for 12h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
The determination shows that the hybrid microsphere synthesized in the example has 85 percent of balling rate, 45:55 of organic-inorganic ratio, 1.0 mu m of average particle diameter, 17.6 percent of variation coefficient and 710m of specific surface area2/g。
Example 8
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7 hours at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12 hours, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 12 hours to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 2.3mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 60 ℃ for 24 hours in an autoclave at a reaction pH of 5. The prepared sol reaction solution is slowly dripped into an octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.2 wt% at 80 ℃ and stirred at a high speed (4000rpm), and the solution is stirred for 1 hour at a constant temperature to be used as a dispersion phase of a microfluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a T-shaped micro-channel at the flow rates of 900 mu L/min and 30 mu L/min, respectively, wherein the size of the micro-channel is 180 mu m, curing the obtained liquid drops at 120 ℃ for 10h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform granular cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
The hybrid microsphere synthesized in the example has a balling rate of 80%, an organic-inorganic ratio of 65:35, an average particle size of 0.9 μm, a coefficient of variation of 13.7%, and a specific surface area of 693m2/g。
Example 9
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 180) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 1.2mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in a high-pressure autoclave at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into an octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.2 wt% at 80 ℃ and stirred at a high speed (4000rpm), and the solution is stirred for 1 hour at a constant temperature to be used as a dispersion phase of a microfluidic device, and dimethyl silicone oil is used as a continuous phase. And respectively filling the continuous phase and the dispersed phase into an injector, respectively introducing the continuous phase and the dispersed phase into a T-shaped micro-channel at the flow rate of 1000 mu L/min and 50 mu L/min at the same time, wherein the size of the micro-channel is 160 mu m, curing the obtained liquid drops at 90 ℃ for 16h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform granular cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
The hybrid microsphere synthesized in the example has 85 percent of balling rate, 41:59 of organic-inorganic ratio, 0.5 mu m of average particle diameter, 18.2 percent of coefficient of variation and 519m of specific surface area2/g。
Example 10
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 8h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued for 16h at 80 ℃, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued for 12h at 80 ℃ to ensure that the hydroxyl groups on the cellulose were completely substituted. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 20g of 1-butyl-3-methylimidazolium tetrafluoroborate at 80 ℃ and then 2.5mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in a high pressure autoclave at a reaction pH of 1. Taking the solution after the crosslinking reaction as a dispersion phase, taking dimethyl silicone oil containing 3.0 wt% of surfactant RSN-0749 as a continuous phase, respectively filling the continuous phase and the dispersion phase into an injector, respectively introducing the continuous phase and the dispersion phase into a Y-shaped micro-channel at the flow rate of 450 mu L/min and the flow rate of 10 mu L/min, respectively, wherein the size of the micro-channel is 150 mu m, curing the obtained liquid drops at 60 ℃ for 24 hours, filtering the obtained product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8 hours to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
According to the determination, the hybrid microsphere synthesized in the embodiment has the balling rate of 90 percent, the organic-inorganic ratio of 55:45, the average particle size of 5.0 mu m, the coefficient of variation of 12.8 percent and the specific surface area of 560m2/g。
Example 11
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40g of 1-butyl-3-methylimidazolium chloride at 80 ℃ and then 2.0mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct a crosslinking reaction at 80 ℃ for 9 hours in a high-pressure autoclave at a reaction pH of 1. Taking the solution after the crosslinking reaction as a dispersion phase, taking dimethyl silicone oil containing 3.0 wt% of surfactant RSN-0749 as a continuous phase, respectively filling the continuous phase and the dispersion phase into an injector, respectively introducing the continuous phase and the dispersion phase into a Y-shaped micro-channel at the flow rate of 600 mu L/min and 10 mu L/min, respectively, wherein the size of the micro-channel is 130 mu m, curing the obtained liquid drop at 80 ℃ for 12h, filtering the obtained product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microsphere.
The hybrid microsphere synthesized in the example has a balling rate of 90%, an organic-inorganic ratio of 51:49, an average particle size of 2.1 μm, a coefficient of variation of 15.5%, and a specific surface area of 711m2/g。
Example 12
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed at 90 ℃ for 7 hours, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 90 ℃ for 12 hours, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 90 ℃ for 9 hours to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 25g of 1-butyl-3-methylimidazolium chloride at 80 ℃ and then, 2.3mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct a crosslinking reaction at 90 ℃ for 10 hours in a high-pressure autoclave at a reaction pH of 1. Taking the solution after the crosslinking reaction as a dispersion phase, taking dimethyl silicone oil containing 3.0 wt% of surfactant Span 20 as a continuous phase, respectively filling the continuous phase and the dispersion phase into a syringe, respectively introducing the syringe and the T-shaped microchannel into the syringe at the flow rates of 750 mu L/min and 10 mu L/min at the same time, wherein the size of the microchannel is 100 mu m, curing the obtained liquid drop at 80 ℃ for 12h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate chiral hybrid microsphere.
The hybrid microsphere synthesized in the example has a balling rate of 85%, an organic-inorganic ratio of 46:54, an average particle size of 1.5 μm, a coefficient of variation of 14.7% and a specific surface area of 570m2/g。
Example 13
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 20g of 1-butyl-3-methylimidazolium chloride at 80 ℃ and then 1.2mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct crosslinking reaction at 80 ℃ for 9 hours in a high-pressure autoclave at a reaction pH of 1. Taking the solution after the crosslinking reaction as a dispersion phase, taking dimethyl silicone oil containing 5.0 wt% of surfactant RSN-0749 as a continuous phase, respectively filling the continuous phase and the dispersion phase into an injector, respectively introducing the continuous phase and the dispersion phase into a Y-shaped micro-channel at the flow rate of 800 mu L/min and 10 mu L/min simultaneously, wherein the size of the micro-channel is 120 mu m, curing the obtained liquid drop at 80 ℃ for 12h, filtering the obtained product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microsphere.
The determination shows that the hybrid microsphere synthesized in the embodiment has 85 percent of balling rate, 34:66 of organic-inorganic ratio, 1.3 mu m of average particle diameter, 10.9 percent of variation coefficient and 590m of specific surface area2/g。
Example 14
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 20g of 1-ethyl-3-methylimidazolium chloride at 80 ℃ and then 2.0mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct a crosslinking reaction at 80 ℃ for 6 hours in a high-pressure reactor at a reaction pH of 1. Taking the solution after the crosslinking reaction as a dispersion phase, taking dimethyl silicone oil containing 3.0 wt% of surfactant Span 20 as a continuous phase, respectively filling the continuous phase and the dispersion phase into an injector, respectively introducing into a T-shaped micro-channel at the flow rate of 850 mu L/min and 10 mu L/min, wherein the size of the micro-channel is 190 mu m, curing the obtained liquid drop at 80 ℃ for 12h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microsphere.
The hybrid microsphere synthesized in the example has a balling rate of 80%, an organic-inorganic ratio of 47:53, an average particle diameter of 1.0 μm, a coefficient of variation of 16.8%, and a specific surface area of 641m2/g。
Example 15
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the cellulose derivative.
(2) Synthesis of cellulose derivative-silicon-based hybrid microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 1.4mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct a crosslinking reaction at 90 ℃ for 12 hours in an autoclave at a reaction pH of 1. Taking the solution after the crosslinking reaction as a dispersion phase, taking dimethyl silicone oil containing 3.0 wt% of surfactant RSN-0749 as a continuous phase, respectively filling the continuous phase and the dispersion phase into an injector, respectively introducing into a T-shaped micro-channel at the flow rates of 900 mu L/min and 10 mu L/min, wherein the size of the micro-channel is 110 mu m, curing the obtained liquid drops at 80 ℃ for 24h, filtering the cured product, sequentially washing n-hexane, ethanol and water, and drying in vacuum for 8h to obtain the uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microspheres.
According to the determination, the hybrid microsphere synthesized in the embodiment has the balling rate of 90 percent, the organic-inorganic ratio of 37:63, the average particle size of 0.7 mu m, the coefficient of variation of 11.9 percent and the specific surface area of 623m2/g。
Comparative example 1
(1) Synthesis of cellulose derivatives
1.0g of dried microcrystalline cellulose (degree of polymerization 110) was weighed into a three-necked flask, 40mL of an ultra-dry solvent N, N-dimethylacetamide was added and stirred under reflux at 150 ℃ for 1 hour. The temperature is reduced to 100 ℃, 4.0g of anhydrous lithium chloride is added and the mixture is fully stirred and refluxed at the temperature of 50 ℃ until the cellulose is dissolved. Subsequently, 20mL of pyridine, an ultra-dry solvent, and 2.79g of3, 5-dichlorophenyl isocyanate were added and the mixture was refluxed for 7h at 80 ℃, then 0.16g of tris- (ethoxysilyl) propyl isocyanate was added and the reaction was continued at 80 ℃ for 12h, and finally 4.18g of3, 5-dichlorophenyl isocyanate was added and the reaction was continued at 80 ℃ for 9h to ensure complete substitution of the hydroxyl groups on the cellulose. The reaction is carried out under the protection of nitrogen, and anhydrous and oxygen-free reaction conditions are controlled. After the reaction is finished, adding anhydrous methanol into the reaction liquid to precipitate a white product, filtering, washing the white product by using the anhydrous methanol, and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain a cellulose derivative, namely the cellulose-3, 5-dichlorophenyl carbamate chiral silane monomer.
(2) Synthesis of cellulose derivative-silicon-based microspheres
0.25g of the cellulose derivative was dissolved in 40mL of tetrahydrofuran at 60 ℃ and then 1.5mL of 1, 2-bis (triethoxysilyl) ethane and 1mL of water were added to conduct a crosslinking reaction at 90 ℃ for 12 hours in an autoclave at a reaction pH of 1. The prepared sol reaction solution is slowly dripped into an octadecyl trimethyl ammonium chloride aqueous solution with the concentration of 0.2 wt% at 80 ℃ and stirred at high speed (4000rpm), and the solution is stirred for 1 hour at constant temperature. Subsequently, the mixture was allowed to stand at a constant temperature of 80 ℃ for 36 hours. Centrifuging, washing the obtained product with water and anhydrous ethanol in sequence, and vacuum drying at 80 deg.C for 6h to obtain cellulose derivative-silicon-based microsphere.
Determined to be synthetic in this comparative exampleThe microsphere balling rate is 95 percent, the organic-inorganic ratio is 38:62, the average grain diameter is 3.1 mu m, the grain diameter is not uniform, the variation coefficient is 99.0 percent, and the specific surface area is 580m2/g。
Sample analysis
FIG. 1 shows cellulose derivative-silicon-based hybrid microspheres prepared in examples 1 to 1513C NMR spectrum of-NHCO-group and-Si-CH2CH2The appearance of characteristic peaks of the radicals proves the successful synthesis of said hybrid microspheres based on cellulose derivatives and silicon
The uniform particle cellulose-3, 5-dichlorophenyl carbamate-silicon-based chiral hybrid microsphere prepared in example 1 is packed into a column, and the prepared chiral column is used for resolving (2-phenylcyclohexanone) chiral drugs, and the chiral drugs can be effectively separated under the liquid chromatography condition that the flow rate is 1mL/min, the mobile phase is n-hexane/isopropanol/triethylamine (95/5/0.5, v/v/v), the column temperature is 30 ℃ and the detection wavelength is 254nm, as shown in figure 2.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a cellulose derivative-silicon-based hybrid microsphere comprises the following steps:
(1) dissolving cellulose in an ultra-dry solvent, adding 3, 5-dichlorophenyl isocyanate and tri- (ethoxysilane) propyl isocyanate for derivatization reaction, adding a precipitator after the derivatization reaction is finished to precipitate a reaction product, filtering and drying to obtain a cellulose derivative; the ultra-dry solvent is N, N-dimethylacetamide, anhydrous lithium chloride and anhydrous pyridine;
(2) dissolving a cellulose derivative in an organic solvent or ionic liquid, adding a silane coupling agent for crosslinking reaction to obtain a crosslinked product, taking the crosslinked product or a mixture of the crosslinked product and a surfactant as a disperse phase, taking dimethyl silicone oil or a mixture of the dimethyl silicone oil and the surfactant as a continuous phase, mixing the disperse phase and the continuous phase in a microchannel by a microfluidic technology, and solidifying, filtering, washing and drying the obtained liquid drop to obtain the cellulose derivative-silicon-based hybrid microsphere.
2. The method for preparing the cellulose derivative-silicon-based hybrid microsphere according to claim 1, wherein the cellulose is microcrystalline cellulose with a degree of polymerization of less than 200.
3. The method for preparing the cellulose derivative-silicon-based hybrid microsphere according to claim 1, wherein the process for adding 3, 5-dichlorophenyl isocyanate and tri- (ethoxysilicon) propyl isocyanate comprises the following steps: according to the hydroxyl mole number of the cellulose, 60-90 mol% of3, 5-dichlorophenyl isocyanate is added to carry out derivatization reaction, 2-5 mol% of tri- (ethoxysilane) propyl isocyanate is added to continue reaction, and finally 100-120 mol% of3, 5-dichlorophenyl isocyanate is added.
4. The method of claim 1, wherein the organic solvent is tetrahydrofuran, dimethyl sulfoxide or dichloromethane, and the ionic liquid is 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium tetrafluoroborate.
5. The method for preparing the cellulose derivative-silicon-based hybrid microsphere according to claim 1, wherein the silane coupling agent is 1, 2-bis (triethoxysilyl) ethane; the ratio of the cellulose derivative to the silane coupling agent is 1 g: 4-10 mL.
6. The method of claim 1, wherein the surfactant is tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, RSN-0749 or Span 20.
7. The preparation method of the cellulose derivative-silicon-based hybrid microsphere as claimed in claim 1, wherein in the mixture of the cross-linked product and the surfactant, the cross-linked product is stirred and mixed with a surfactant solution with a concentration of 0.1-0.5 wt%; in the mixture of the dimethyl silicone oil and the surfactant, the mass fraction of the surfactant is less than 5.0 wt%.
8. The preparation method of the cellulose derivative-silicon-based hybrid microsphere according to claim 1, wherein the flow rate of the continuous phase is 450-1000 μ L/min during the mixing process of the microfluidic technology; the flow rate of the dispersed phase is 10-50 mu L/min; the micro-channel is a T-shaped micro-channel and a Y-shaped micro-channel, and the size of the micro-channel is 100-200 mu m.
9. The preparation method of the cellulose derivative-silicon-based hybrid microsphere according to claim 1, wherein the curing temperature is 40-120 ℃ and the curing time is 10-24 h.
10. Cellulose derivative-silicon-based hybrid microspheres prepared by the method for preparing cellulose derivative-silicon-based hybrid microspheres according to any one of claims 1 to 9.
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