CN113786823A - Preparation method of ultra-small particle size hydrothermal carbon sphere latex agglomeration type high-efficiency ion chromatographic packing - Google Patents
Preparation method of ultra-small particle size hydrothermal carbon sphere latex agglomeration type high-efficiency ion chromatographic packing Download PDFInfo
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Abstract
The invention belongs to the field of analytical chemistry, and relates to a preparation method of an ultra-small particle size hydrothermal carbon sphere latex agglomeration type high-efficiency ion chromatography stationary phase. The method comprises the steps of firstly realizing single high-yield and amplified production of carbon nanospheres with the particle size of less than 100 nm by using a cationic polyelectrolyte-assisted fructose hydrothermal carbonization reaction, then carrying out quaternary ammonium functional modification on the carbon nanospheres by using a thiol-olefin click chemistry-based hyperbranched reaction to enable the carbon nanospheres to have controllable anion exchange capacity, and finally agglomerating quaternized hydrothermal carbon spheres on the surfaces of sulfonated polystyrene-divinyl phenyl microspheres in an ion bonding manner to obtain the ion chromatography filler. The method is simple, green and environment-friendly, high in yield and low in cost, the prepared stationary phase has extremely strong hydrophilicity and good chromatographic stability, can tolerate a wide pH value range, can efficiently separate conventional anions, easily-polarized anions, organic acids and saccharides, and the column efficiency and symmetry of chromatographic peaks are not inferior to those of common commercial latex agglomeration type chromatographic columns.
Description
Technical Field
The invention belongs to the field of analytical chemistry, relates to a high-efficiency anion chromatographic column and a preparation process thereof, and particularly relates to a preparation method of an ultra-small particle size hydrothermal carbon sphere latex agglomeration type high-efficiency ion chromatographic stationary phase.
Background
Ion chromatography is developed rapidly since the first proposal in 1975, has become a necessary chromatographic technology for analyzing anions and cations at present, and is widely applied to the fields of environmental monitoring, electronics, food, chemical engineering and the like. As a decisive influence on the ion separation process, the study of stationary phases has received increasing attention over the last two decades. Ion chromatography stationary phases are typically based on polymers (especially aromatic hydrocarbons) because of their good chemical stability over a wide pH range compared to silica gel packing commonly used in liquid chromatography, which is not resistant to strong acids and bases commonly used in ion chromatography mobile phases. Ion chromatography stationary phases can be simply divided into two categories: stationary phases based on single microspheres and latex agglomeration type stationary phases. The former directly carries out surface modification and ion exchange on polymer matrix microspheres, while the latter is that charged nano latex (less than or equal to 100 nm) is adsorbed on the surface of a large-size polymer matrix (more than or equal to 5 mu m) through electrostatic interaction, wherein the latex is an active part with ion exchange capacity. In contrast, the core-shell structure of the latex-agglomerated stationary phase is easier to achieve high efficiency and rapid separation, because the extremely small nano size of the latex can greatly shorten the ion exchange path and avoid the complex mass transfer process of the analyte in the matrix porous structure (analysis 2011, 136, 3113-3120; anal. Chim. Acta 2016, 904, 33-50), and thus becomes a column packing material most commonly used in the current commercial inhibitory ion chromatography apparatus. Generally, the latex is commonly used aromatic polymer nanospheres with a low degree of crosslinking such as polystyrene and copolymers thereof. However, this low degree of crosslinking leads to insufficient mechanical strength, and the preparation of the latex also requires the consumption of large amounts of environmentally harmful agents. Meanwhile, the hydrophobicity of the polymer surface easily causes strong retention and peak tailing of easily polarizable anions (such as iodide ions and perchlorate ions) (j. chromatogr. a 2010, 1217, 8154-8160).
The ultra-small particle size hydrothermal carbon spheres are nano-sized carbon spheres (< 100 nm) prepared from biomass and derivatives thereof through hydrothermal carbonization reaction, show attractive prospects in cell imaging, drug transportation, adsorbents and the like in recent years, and have attracted wide interests. Compared with polymer latex and other carbon nano-latex reported in the literature, the ultra-small particle size hydrothermal carbon spheres are likely to be a competitive stationary phase latex due to simple green synthetic route, low-cost Sustainable raw materials, high surface hydrophilicity, good mechanical properties and acid and alkali resistance (ACS Sustainable chem. Eng. 2019, 7, 7486-. And the surface hydrophilicity of the hydrothermal carbon spheres can obviously improve the symmetry of chromatographic peaks and weaken the nonspecific effect between a stationary phase and an analyte (J. chromatogr. A2016, 1468, 73-78). However, the batch preparation of ultra-small particle size hydrothermal carbon sphere agglomerated stationary phases still presents two major difficulties. On one hand, the synthesis of the current ultra-small particle size hydrothermal carbon spheres generally adopts a low-concentration carbon source or shorter reaction time, which severely limits the yield, and simultaneously causes the poor repeatability of the method and is difficult to be applied on a large scale. How to prepare the ultra-small particle size hydrothermal carbon spheres efficiently and in batches still has a challenging problem. On the other hand, the traditional modification method based on polycondensation reaction easily causes the hydrothermal carbon nanospheres to agglomerate, so that the hydrothermal carbon nanospheres are unevenly and insufficiently covered on the surface of the polymer matrix, the ion exchange capacity of the chromatographic column is seriously reduced, and the column efficiency is easily and adversely affected (J. chromatogr. A2016, 1468, 73-78). This agglomeration phenomenon can also be observed with other Carbon nano-latex particles using similar modification methods (Chinese chem. Lett. 2019, 30, 465-one 469; Carbon 2013, 62, 127-one 134). Therefore, there is a need to develop a new modification method that can provide ion exchange groups and reduce the agglomeration of the latex.
At present, the high-performance ion chromatographic column on the market is mainly of foreign manufacturer models (such AS the American thermolisher IonPac AS series), and China is relatively lagged behind in the field. The column efficiency and the application range of the domestic ion chromatographic column have great difference compared with the prior art, and the method becomes a great obstacle for restricting the development of the ion chromatographic instrument in China. Particularly, under the circumstance that the trade war of China and America can be long-term and normalized, the research of the high-performance domestic latex agglomeration type ion chromatographic packing has certain practical significance.
Disclosure of Invention
The invention aims to provide a novel preparation method of a hydrothermal carbon sphere latex agglomeration type high-efficiency ion chromatographic packing with ultra-small particle size, which has the advantages of simple and green process, low cost, uniform packing particle size, high separation column efficiency, high analysis speed and the like. The preparation method of the chromatographic packing comprises the synthesis and the functional modification of the hydrothermal carbon spheres with the ultra-small particle size and the preparation of the hydrothermal carbon sphere agglomeration type ion chromatographic packing with the ultra-small particle size.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a novel ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatographic packing comprises the following steps:
(1) preparing ultra-small particle size hydrothermal carbon spheres: synthesizing monodisperse ultra-small particle size hydrothermal carbon spheres in batch through a hydrothermal carbonization reaction of fructose;
(2) functional modification of ultra-small particle size hydrothermal carbon spheres: introducing amino based on click reaction, and then reacting with diglycidyl ether compound and methylamine in sequence to obtain quaternized ultra-small particle size hydrothermal carbon spheres with ion exchange capacity;
(3) preparation of latex-agglomerated ion exchange chromatography packing: and then, agglomerating the quaternized hydrothermal carbon spheres with ultra-small particle sizes on the surface of the sulfonated matrix microsphere in an ion bonding manner by using the quaternized hydrothermal carbon spheres as latex to obtain the target ion exchange chromatographic filler.
Preferably, after the target ion exchange chromatography packing is obtained, the chromatography packing is subjected to column packing by a homogenization method.
Preferably, the method specifically comprises the following steps:
(1) method for preparing ultra-small particle size hydrothermal carbon spheres by fructose hydrothermal carbonization method
Adding fructose and polycation electrolyte into water, fully stirring to obtain a clear and transparent solution, transferring the solution into a hydrothermal kettle with a lining, then putting the hydrothermal kettle into an oven to react at a certain temperature, and treating after the reaction is finished to obtain ultra-small particle size hydrothermal carbon spheres;
(2) functional modification of ultra-small particle size hydrothermal carbon spheres
Dispersing ultra-small particle size hydrothermal carbon spheres in deionized water to form a colloidal solution, adding a water-soluble initiator and a sulfydryl amine compound under the protection of nitrogen and magnetic stirring, carrying out click reaction on double bonds on the surface of the hydrothermal carbon spheres and sulfydryl of the sulfydryl amine compound to obtain aminated carbon spheres, and then reacting with a diglycidyl ether compound and methylamine in sequence to obtain quaternary ammonium functionalized ultra-small particle size hydrothermal carbon spheres;
(3) preparation of latex agglomeration type chromatographic packing
Sulfonating the base spheres to enable the surfaces of the base spheres to have negative charges, and agglomerating the quaternized ultra-small particle size hydrothermal carbon spheres with the positive charges on the surfaces of the base spheres as latex through ionic bonds under reaction conditions to obtain the target ion exchange chromatographic packing.
Preferably, the concentration of fructose in the solution in the step (1) is 0.08-0.5 g/mL
Preferably, the polycationic electrolyte in the step (1) is any one or a combination of more than one of poly (diallyldimethylammonium chloride), poly (quaternary ammonium salt-11), poly (quaternary ammonium salt-7), poly (quaternary ammonium salt-28), poly (methacrylamidopropyltrimethylammonium chloride) and the like, and more preferably poly (diallyldimethylammonium chloride).
Preferably, the mass ratio of the feeding mass of the polycation electrolyte to the fructose in the step (1) is 1: 50-1: 400, more preferably 1: 200-1: 300.
preferably, the oven reaction temperature in the step (1) is 120-150 ℃, and the reaction time is 4-24 hours.
Preferably, the ratio of the volume of the hydrothermal solution to the volume of the hydrothermal kettle in the step (1) is 1: 1.1-1: 2.5, more preferably 1: 1.3-1: 1.8; the hydrothermal solution is obtained by adding fructose and polycation electrolyte into water.
Preferably, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the deionized water in the step (2) is 1: 10-1: 100, more preferably 1: 40-1: 70.
preferably, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the water-soluble initiator in the step (2) is 10: 1-100: 1, more preferably 30: 1-60: 1.
preferably, the water-soluble initiator in step (2) includes, but is not limited to, any one or combination of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride, azodicyano valeric acid, azodiisopropyl imidazoline, and the like.
Preferably, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the mercaptoamine compound in the step (2) is 1: 1-5: 1, more preferably 2: 1-3.5: 1.
preferably, the mercaptoamines in step (2) include, but are not limited to, mercaptoethylamine, mercaptopropylamine, cysteamine, cysteine, and any one or a combination of several thereof.
Preferably, the click reaction temperature in the step (2) is 60-90 ℃, the reaction time is 6-24 h, and the nitrogen atmosphere is protected (the nitrogen flow rate is 10-30 mL/min).
Preferably, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the methylamine in the step (2) is 0.5: 1-5: 1, more preferably 1: 1-2: 1.
preferably, the diglycidyl ether compound in step (2) includes, but is not limited to, any one or a combination of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, resorcinol diglycidyl ether, bisphenol a diglycidyl ether, and the like.
Preferably, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the diglycidyl ether compound in the step (2) is 0.5: 1-5: 1, more preferably 1: 1-2: 1.
preferably, in the step (2), the reaction temperature of the aminated carbon spheres with the diglycidyl ether compound and methylamine is 60-70 ℃, and the reaction time is 1-3 h; more preferably, the reaction temperature is 65 ℃ and the reaction time is 1.5 h.
Preferably, the reaction conditions in the step (3) are that the reaction temperature is 25-50 ℃ and the reaction time is 2-5 hours.
Preferably, the reaction in step (3) is carried out in water, and the hydrothermal carbon spheres with ultra-small particle size and the base spheres are fully fused by stirring.
Preferably, the base sphere in the step (3) is polystyrene-divinylbenzene.
Preferably, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the base spheres in the step (3) is 1: 3-1: 20, more preferably 1: 5.5-1: 10.
preferably, the excessive hydrothermal carbon sphere latex with ultra-small particle size in the step (3) can be removed by a sedimentation method: standing the solution after the reaction for 0.5-3 hours, then pouring out the upper layer latex solution, adding deionized water for dilution, and performing ultrasonic dispersion for 5-30 minutes; repeating the above operation for 3-10 times to remove the free latex which is not combined with the base ball, prevent column blockage, reduce column pressure, and improve the stability of chromatographic column.
Compared with the prior art, the invention has the following advantages:
the preparation method of the ultra-small particle size hydrothermal carbon sphere latex provided by the invention is green and sustainable, simple and convenient to operate, low in cost, uniform in latex particles, good in monodispersity and strong in hydrophilicity; the ultra-small particle size hydrothermal carbon sphere latex provided by the invention has controllable ion exchange capacity and is used for preparing chromatographic columns with different column capacities; the hydrothermal carbon sphere agglomeration type anion exchange chromatographic column with the ultra-small particle size, which is prepared by the invention, can tolerate a wider pH range, has good chromatographic stability, can effectively separate anions, easily-polarized anions, organic acids and saccharides, has the separation column efficiency which is not inferior to that of common commercial columns (such AS Ionpac AS11 columns and the like), and has the symmetry and peak capacity of chromatographic peaks even exceeding those of the common commercial columns (such AS Ionpac AS11 columns and the like). In addition, the hydrothermal carbon sphere latex with ultra-small particle size is selected to replace the currently common polymer latex to develop the high-efficiency stationary phase, can bypass foreign patent barriers to a certain extent, is expected to realize 'curve overtaking', and is beneficial to realizing domestic replacement in a certain sense.
Drawings
FIG. 1 shows the morphology of the ultra-small particle size hydrothermal carbon spheres prepared in example 1
FIG. 2 is a graph of ultra small particle size hydrothermal carbon spheres prepared in example 2;
FIG. 3 is a graph of ultra small particle size hydrothermal carbon spheres prepared in example 3;
FIG. 4 is a graph of ultra small particle size hydrothermal carbon spheres prepared in example 4;
FIG. 5 is a graph of ultra small particle size hydrothermal carbon spheres prepared in example 5;
FIG. 6 is a schematic representation of the quaternary ammonium functionalized modification based on click reaction and the color change of the product in example 6;
FIG. 7 is the morphology of the product of example 6 based on the click reaction grafting of three layers (a) and six layers (b) of quaternary ammonium functionalization modification;
FIG. 8 is FTIR (a) and nitrogen XPS characterization (b) before and after quaternary ammonium functionalization modification of the click reaction in example 6;
FIG. 9 is a scanning electron micrograph of the chromatographic packing obtained in example 7;
FIG. 10 is a scanning electron micrograph of the chromatographic packing obtained in example 8;
FIG. 11 is a graph of the chromatographic separation of the packing obtained in example 7 against 7 conventional anions;
FIG. 12 is a graph of the chromatographic separation of the packing obtained in example 7 for 3 conventional anions and 4 easily polarizable anions;
FIG. 13 is a graph showing the chromatographic separation of 6 sugars by the filler obtained in example 8.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, but the scope of protection of the invention is not limited to these examples.
The invention provides a preparation method of a novel ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatographic packing, which comprises the following steps:
(1) preparing ultra-small particle size hydrothermal carbon spheres: synthesizing monodisperse ultra-small particle size hydrothermal carbon spheres in batch through a hydrothermal carbonization reaction of fructose;
(2) functional modification of ultra-small particle size hydrothermal carbon spheres: introducing amino based on click reaction, and then reacting with diglycidyl ether compound and methylamine in sequence to obtain quaternized ultra-small particle size hydrothermal carbon spheres with ion exchange capacity;
(3) preparation of latex-agglomerated ion exchange chromatography packing: and then, agglomerating the quaternized hydrothermal carbon spheres with ultra-small particle sizes on the surface of the sulfonated matrix microsphere in an ion bonding manner by using the quaternized hydrothermal carbon spheres as latex to obtain the target ion exchange chromatographic filler.
In the examples of the present invention, after obtaining the target ion exchange chromatography packing, the packing was subjected to column packing by a homogenization method.
In an embodiment of the present invention, the method specifically includes the following steps:
(1) method for preparing ultra-small particle size hydrothermal carbon spheres by fructose hydrothermal carbonization method
Adding fructose and polycation electrolyte into water, fully stirring to obtain a clear and transparent solution, transferring the solution into a hydrothermal kettle with a lining, then putting the hydrothermal kettle into an oven to react at a certain temperature, and treating after the reaction is finished to obtain ultra-small particle size hydrothermal carbon spheres;
(2) functional modification of ultra-small particle size hydrothermal carbon spheres
Dispersing ultra-small particle size hydrothermal carbon spheres in deionized water to form a colloidal solution, adding a water-soluble initiator and a sulfydryl amine compound under the protection of nitrogen and magnetic stirring, carrying out click reaction on double bonds on the surface of the hydrothermal carbon spheres and sulfydryl of the sulfydryl amine compound to obtain aminated carbon spheres, and then reacting with a diglycidyl ether compound and methylamine in sequence to obtain quaternary ammonium functionalized ultra-small particle size hydrothermal carbon spheres;
(3) preparation of latex agglomeration type chromatographic packing
Sulfonating the base spheres to enable the surfaces of the base spheres to have negative charges, and agglomerating the quaternized ultra-small particle size hydrothermal carbon spheres with the positive charges on the surfaces of the base spheres as latex through ionic bonds under reaction conditions to obtain the target ion exchange chromatographic packing.
In the embodiment of the invention, the concentration of fructose in the solution in the step (1) is 0.08-0.5 g/mL
In the embodiment of the invention, the polycationic electrolyte in the step (1) is any one or a combination of more than one of poly (diallyldimethylammonium chloride), poly (quaternary ammonium salt-11), poly (quaternary ammonium salt-7), poly (quaternary ammonium salt-28), poly (methacrylamidopropyltrimethylammonium chloride) and the like, and more preferably poly (diallyldimethylammonium chloride).
In the embodiment of the invention, the mass ratio of the feeding mass of the polycation electrolyte to the fructose in the step (1) is 1: 50-1: 400, more preferably 1: 200-1: 300.
in the embodiment of the invention, the oven reaction temperature in the step (1) is 120-150 ℃, and the reaction time is 4-24 hours.
In the embodiment of the invention, the ratio of the volume of the hydrothermal solution to the volume of the hydrothermal kettle in the step (1) is 1: 1.1-1: 2.5, more in the examples of the invention 1: 1.3-1: 1.8; the hydrothermal solution is obtained by adding fructose and polycation electrolyte into water.
In the embodiment of the invention, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the deionized water in the step (2) is 1: 10-1: 100, more in the examples of the present invention 1: 40-1: 70.
in the embodiment of the invention, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the water-soluble initiator in the step (2) is 10: 1-100: 1, more preferably 30: 1-60: 1.
in the embodiment of the present invention, the water-soluble initiator in step (2) includes, but is not limited to, any one or combination of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride, azodicyan valeric acid, azodiisopropyl imidazoline, etc.
In the embodiment of the invention, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the mercaptoamine compound in the step (2) is 1: 1-5: 1, more preferably 2: 1-3.5: 1.
in the embodiment of the present invention, the mercaptoamines in step (2) include, but are not limited to, mercaptoethylamine, mercaptopropylamine, cysteamine, cysteine, and any one or a combination of several thereof.
In the embodiment of the invention, the click reaction temperature in the step (2) is 60-90 ℃, the reaction time is 6-24 h, and the nitrogen atmosphere is protected (the nitrogen flow rate is 10-30 mL/min).
In the embodiment of the invention, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the methylamine in the step (2) is 0.5: 1-5: 1, more preferably 1: 1-2: 1.
in the embodiment of the present invention, the diglycidyl ether compound in step (2) includes, but is not limited to, any one or a combination of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, resorcinol diglycidyl ether, bisphenol a diglycidyl ether, and the like.
In the embodiment of the present invention, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the diglycidyl ether compound in step (2) is 0.5: 1-5: 1, more preferably 1: 1-2: 1.
in the embodiment of the invention, in the step (2), the reaction temperature of the aminated carbon spheres with the diglycidyl ether compound and methylamine is 60-70 ℃, and the reaction time is 1-3 h; more preferably, the reaction temperature is 65 ℃ and the reaction time is 1.5 h.
In the embodiment of the invention, the reaction conditions in the step (3) are that the reaction temperature is 25-50 ℃ and the reaction time is 2-5 hours.
In the embodiment of the invention, the reaction in the step (3) is carried out in water, and the ultra-small particle size hydrothermal carbon spheres and the base spheres are fully fused by stirring.
In an embodiment of the present invention, the base sphere in the step (3) is polystyrene-divinylbenzene.
In the embodiment of the invention, the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the base spheres in the step (3) is 1: 3-1: 20, more preferably 1: 5.5-1: 10.
in an embodiment of the present invention, the excessive hydrothermal carbon sphere latex with ultra-small particle size in step (3) may be removed by a sedimentation method: standing the solution after the reaction for 0.5-3 hours, then pouring out the upper layer latex solution, adding deionized water for dilution, and performing ultrasonic dispersion for 5-30 minutes; repeating the above operation for 3-10 times to remove the free latex which is not combined with the base ball, prevent column blockage, reduce column pressure, and improve the stability of chromatographic column.
The technical solutions of the present invention can be proved by experiments, and only some specific examples are listed below, so it should be understood that the described examples are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and the scope of the present invention is not limited thereto, and other variations and modifications may be made without departing from the technical solutions described in the claims.
Example 1
Adding 11 g of fructose into 45 mL of deionized water, adding 80 mg of poly (diallyldimethylammonium chloride), carrying out magnetic stirring to fully dissolve the fructose to form a transparent solution, transferring the solution to a hydrothermal kettle, and placing the hydrothermal kettle into an oven with a set temperature of 130 ℃ for reaction, wherein the reaction time is 15 h. And (3) taking the kettle out of the oven after the reaction is finished, naturally cooling to room temperature, centrifugally separating the product, respectively washing with deionized water and ethanol for 4 times, and drying at 70 ℃ for 10 hours to obtain 2.1 g of hydrothermal carbon spheres with the average particle size of 62 nm. The scanning electron micrograph of the surface topography is shown in FIG. 1.
Example 2
The preparation method is the same as that of the embodiment 1, except that the hydrothermal reaction temperature is 135 ℃, 2.5 g of monodisperse hydrothermal carbon spheres with the average particle size of 79 nm are prepared, and the micro-morphology of the monodisperse hydrothermal carbon spheres is shown in the attached figure 2.
Example 3
The preparation method was the same as in example 1, except that the amount of fructose added was 20 g, and 4.8 g of monodisperse hydrothermal carbon spheres having an average particle size of 97 nm were prepared, and the microscopic morphology thereof is shown in FIG. 3.
Example 4:
adding 110 g of fructose into 450 mL of deionized water, adding 0.8 g of poly (diallyldimethylammonium chloride), carrying out magnetic stirring to fully dissolve the fructose to form a transparent solution, transferring the solution to a 1000 mL hydrothermal kettle, and placing the hydrothermal kettle into an oven with a set temperature of 130 ℃ for reaction for 15 h. And (3) after the reaction is finished, taking the kettle out of the oven, naturally cooling to room temperature, centrifugally separating the product, washing with deionized water and ethanol for 4 times respectively, and drying at 65 ℃ for 10 hours to obtain 19.26 g of monodisperse hydrothermal carbon spheres with the average particle size of 60 nm, wherein the graph is shown in figure 4.
Example 5:
the preparation method was the same as that of example 4, except that the hydrothermal reaction temperature was 135 deg.C, and 21.64 g of monodisperse hydrothermal carbon spheres having an average particle size of 78 nm were obtained, and their microscopic morphology is shown in FIG. 5.
Example 6:
based on the click reaction of the surface alkylene of ultra-small particle diameter hydrothermal carbon spheres (UCSs) and mercaptoamines, quaternization modification is carried out, which generally comprises the following steps: 0.4 g of ultra-small particle size hydrothermal carbon spheres are ultrasonically dispersed in 40 mL of deionized water to form a colloidal solution, nitrogen is introduced at the flow rate of 5 mL/min to keep the solution in a nitrogen atmosphere, 10 mL of an aqueous solution containing 0.1 g of 2,2' -azobisisobutyramidine dihydrochloride and 0.3 g of cysteamine is added into the colloidal solution, the mixture is heated and stirred at 70 ℃ for 20 hours, and then the obtained solid is washed by deionized water and ethanol for 2 times respectively to obtain cysteamine modified carbon spheres (Cyst-UCSs). Ultrasonically dispersing the product in 50 mL of 1, 4-butanediol diglycidyl ether aqueous solution (2 wt%), heating and stirring at 65 ℃ for 1.5 hours, and washing the obtained solid with deionized water and ethanol for 2 times respectively; the obtained solid was further dispersed in 50 mL of an aqueous methylamine solution (1.2 wt%) by ultrasonic dispersion, heated and stirred at 65 ℃ for 1.5 hours, and the obtained solid was washed with deionized water and ethanol 2 times each. The two-step hyperbranched reaction is repeated for 2 times and 5 times to respectively obtain the ultra-small particle size hydrothermal carbon sphere latex modified by grafted 3 and 6 layers of hyperbranched quaternary ammonium polymers (HAP), and then the ultra-small particle size hydrothermal carbon sphere latex is dried at 70 ℃. The schematic diagram of the modification reaction of the ultra-small particle size hydrothermal carbon spheres and the color change of the product are shown in FIG. 6.
The Fourier infrared spectrogram before and after modification of the ultra-small particle size hydrothermal carbon spheres is shown in figure 8a, and the nitrogen element X-ray photoelectron spectroscopy analysis is shown in figure 8 b. The surface morphology is shown in fig. 7a and 7b, which shows that the modified ultra-small particle size hydrothermal carbon spheres still have better monodispersity, and the average particle sizes of the 3-layer hyperbranched polymer functionalized ultra-small particle size carbon spheres (3 HAP-UCSs) and the 6-layer hyperbranched polymer functionalized ultra-small particle size carbon spheres (6 HAP-UCSs) are 99 nm and 148 nm respectively.
Example 7:
a three-layer quaternary ammonium polymer modified ultra-small particle size hydrothermal carbon sphere latex agglomerated polystyrene-divinylbenzene-based sphere chromatographic packing is prepared by the general steps of: polystyrene-divinylbenzene microspheres (degree of crosslinking 45%) having a particle size of 5 μm were obtained by a classical suspension polymerization method (J. chromatography. A, 2012, 1251, 154-159), washed with hot water and dried. 3 g of the dry-weight substrate microspheres were put in 10 mL of acetic acid and stirred at 100 rpm/min for 30 minutes to fully swell the microspheres, and 70 mL of concentrated sulfuric acid (98%) was added thereto and stirred at 40 ℃ for 10 minutes with heating (200 rpm/min). After heating is stopped, the solution is transferred to an ice water bath, 30 mL of dilute sulfuric acid with the concentration of 4 moL/L is added into the solution for 3 times in 3 minutes, 50 mL of dilute sulfuric acid with the concentration of 1 moL/L is added into the solution for 3 times in 3 minutes, 60 mL of deionized water is added into the solution for 6 times in 6 minutes, the sulfonation reaction is quenched under the condition that the temperature of the solution is not obviously increased, and then the obtained solid is filtered and washed by the deionized water until the pH value of the supernatant is neutral. 0.25 g of the three-layer quaternary ammonium polymer functionalized ultra-small particle size hydrothermal carbon sphere latex (3 HPA-UCS) prepared in example 6 was ultrasonically dispersed in 25 mL of water, and then added into 25 mL of sulfonated polystyrene-divinylbenzene matrix microsphere suspension aqueous solution, stirred at 40 ℃ for 2 hours, and then left to stand for 1 hour, the supernatant was removed, and the supernatant was removed by washing with deionized water and standing several times, to obtain a latex agglomeration type chromatographic packing, the surface morphology of which is shown in FIG. 9. The resulting filler was homogenized and packed into a column (4.6X 100 mm) under a pressure of 30 MPa to obtain a 3HPA-UCS column.
Example 8:
a chromatographic packing of polystyrene-divinylbenzene agglomerated by six layers of quaternary ammonium polymer modified ultra small particle size hydrothermal carbon sphere latex was prepared as in example 7, except that the agglomerated latex was six layers of quaternary ammonium polymer modified ultra small particle size hydrothermal carbon spheres packed in a chromatographic column (4.6X 150 mm) to give a 6HPA-UCS column. The microscopic morphology of the resulting filler is shown in FIG. 10.
Example 9:
the column packed in example 7 (3 HPA-UCS column) was flushed with deionized water for 1 hour with a pumpThe rate was set at 1 mL/min, followed by a 2-hour wash with 10 mM KOH, using a Saimer flight ICS 2000 ion chromatograph equipped with a suppressed conductance detector. Using 7.8 mM KOH as mobile phase, sample F-、Cl-、NO2 -、Br-、NO3 -、SO4 2-、PO4 3-And mixing the seven kinds of anion mixed standard solutions, testing the separation performance, and obtaining a chromatogram as shown in FIG. 11. Chromatographic performance indicators of the column, such as resolution, Asymmetry factor (A)s) Column efficiency (Effectieneces, E)ff.) See table 1, for example. The column can realize baseline separation of the 7 anions within 6 minutes, and the column efficiency and chromatographic peak symmetry of the column are better than those of a common Ionpac AS11 HC ion chromatographic column.
TABLE 1 separation Performance of ultra-small particle size hydrothermal carbon sphere agglomeration type anion chromatographic packing for conventional anions
| Anion | Resolution | As | Eff. (plates/m), | As a | Eff (plates/m)a |
| Fluoride | 5.45 | 1.09 | 58700 | 2.1 | 19600 |
| Chloride | 3.33 | 1.01 | 71100 | 1.4 | 29100 |
| Nitrite | 4.01 | 1.03 | 66900 | 1.4 | 27700 |
| Bromide | 1.99 | 1.05 | 59600 | 1.3 | 34700 |
| Nitrate | 3.12 | 1.06 | 54500 | 1.2 | 32500 |
| Sulfate | 5.04 | 1.08 | 51000 | 1.2 | 26300 |
| Phosphate | n.a. | 1.05 | 44800 | 1.2 | 23600 |
aIonpac AS11 HC column separation effectiveness data from:
https://assets.thermofisher.cn/TFS-Assets/CMD/manuals/man-031333-ionpac-as11-hc-columns- man031333-en.pdf
example 10:
the procedure was as in example 9, except that 18.3 mM KOH was used as the mobile phase and the ions to be injected were three conventional anions (F)-、Cl-、SO4 2-) And four readily polarizable anions (S)2O3 2-、I-、SCN-、ClO4 -) The typical chromatogram obtained by mixing the standard solutions is shown in FIG. 12. Measuring the intra-day precision RSD (RSD) value of the method by continuously injecting samples for 8 timesIntra) Measuring the inter-day precision RSD value (RSD) by continuous 3-day sample injectionInter.). The column efficiency, chromatographic peak asymmetry factor and process precision of the four easily polarizable anions are shown in table 2. The column can efficiently and stably realize baseline separation of the four easily polarizable anions within 6 minutes, and the column efficiency and chromatographic peak symmetry of the column are not weaker than those of a common Ionpac AS16 ion chromatographic column.
TABLE 2 separation of polarizable anions by ultra-small particle size hydrothermal carbon sphere agglomeration type anion chromatographic packing
aIonpac AS16 column from: https:// assetts. thermofisher. cn/TFS-Assets/CMD/manuals/Man-031475-IonPac-AS16-Man031475-EN.pdf
Example 10:
the column packed in example 8 (6 HPA-UCS column) was flushed with deionized water using a pump for 1.5 hours with a flow rate set at 0.9 mL/min, then flushed with 25 mM NaOH for 3 hours, and then a mixed standard solution of six sugars such as fucose, sucrose, galactose, xylose, fructose, raffinose, etc. was injected using a seemeofei ICS 3000 ion chromatograph equipped with an electrochemical detector with 1.1 mM KOH as a mobile phase to test separation performance, and the chromatogram was as shown in fig. 13, and the chromatographic parameters are shown in table 3. The column can realize baseline separation of the 6 kinds of small molecular sugars within 7 minutes, and the column efficiency and chromatographic peak symmetry of the column are not weak compared with the common CarboPac-SA10 commercial column.
TABLE 3 separation of small molecule saccharides by ultra small particle size hydrothermal carbon sphere agglomeration type anion chromatographic packing
| Sugar | Resolution | As | Eff. (plates/m) | As a | Eff. Plates/ma |
| Fucose | 3.03 | 1.05 | 27300 | 1.2 | 20600 |
| Sucrose | 1.95 | 1.08 | 24600 | 1.2 | 13800 |
| Galactose | 1.89 | 1.11 | 23500 | 1.3 | 20700 |
| Xylose | 1.56 | 1.02 | 22600 | n.a. | 21300 |
| Fructose | 2.18 | 1.01 | 22000 | n.a. | 15900 |
| Melitose | n.a. | 1.05 | 20400 | n.a. | n.a. |
aCarboPac-SA10 column separation effect data from:
https://assets.thermofisher.cn/TFS-Assets/CMD/manuals/Man-065384-CarboPac-SA10-Columns-Man065384-EN.pdf 。
Claims (10)
1. a preparation method of an ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatographic packing is characterized by comprising the following steps:
(1) preparing ultra-small particle size hydrothermal carbon spheres: synthesizing ultra-small particle size hydrothermal carbon spheres through a hydrothermal carbonization reaction of fructose;
(2) functional modification of ultra-small particle size hydrothermal carbon spheres: introducing amino based on click reaction, and then reacting with diglycidyl ether compound and methylamine in sequence to obtain quaternized ultra-small particle size hydrothermal carbon spheres with ion exchange capacity;
(3) preparation of ion exchange chromatography packing: and agglomerating the quaternized hydrothermal carbon spheres with ultra-small particle sizes on the surface of the sulfonated base spheres in an ion bonding manner to obtain the target ion exchange chromatographic filler.
2. The method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatographic packing as claimed in claim 1, wherein the method specifically comprises the following steps:
(1) preparing ultra-small particle size hydrothermal carbon spheres by a fructose hydrothermal carbonization method:
adding fructose and polycation electrolyte into water, stirring to obtain a solution, transferring the solution into a hydrothermal kettle, reacting at a certain temperature, and treating after the reaction is finished to obtain ultra-small particle size hydrothermal carbon spheres;
(2) functional modification of ultra-small particle size hydrothermal carbon spheres:
carrying out click reaction on surface double bonds of the ultra-small particle size hydrothermal carbon spheres, a mercaptoamine compound and a water-soluble initiator to obtain aminated carbon spheres, and then reacting with a diglycidyl ether compound and methylamine in sequence to obtain quaternized ultra-small particle size hydrothermal carbon spheres;
(3) preparation of ion exchange chromatography packing:
sulfonating the base spheres, and agglomerating the quaternized hydrothermal carbon spheres with ultra-small particle size on the surface of the base spheres as latex through reaction to obtain the target ion exchange chromatographic filler.
3. The method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatographic packing as claimed in claim 2, wherein the polycationic electrolyte in the step (1) is any one or a combination of poly (diallyldimethylammonium chloride), poly (quaternary ammonium salt-11), poly (quaternary ammonium salt-7), poly (quaternary ammonium salt-28) and poly (methacrylamidopropyltrimethylammonium chloride); the mass ratio of the feeding mass of the polycation electrolyte to the fructose is 1: 50-1: 400.
4. the method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatography packing as claimed in claim 2, wherein the reaction temperature in the step (1) is 120-150 ℃, and the reaction time is 4-24 hours.
5. The method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatography packing material as claimed in claim 2, wherein the water-soluble initiator in the step (2) is any one or a combination of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride, azodicyano valeric acid and azodiisopropyl imidazoline; the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the water-soluble initiator is 10: 1-100: 1.
6. the method for preparing the ultra-small particle size hydrothermal carbon sphere latex-agglomerated ion exchange chromatography filler according to claim 2, wherein the mercaptoamine compound in the step (2) is any one or a combination of mercaptoethylamine, mercaptopropylamine, cysteamine and cysteine; the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the mercaptoamine compound is 1: 1-5: 1.
7. the method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatography packing material as claimed in claim 2, wherein the click reaction temperature in the step (2) is 60-90 ℃, and the reaction time is 6-24 h.
8. The method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatographic packing as claimed in claim 2, wherein the diglycidyl ether compound in the step (2) is any one or a combination of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, resorcinol diglycidyl ether and bisphenol A diglycidyl ether; the mass ratio of the ultra-small particle diameter hydrothermal carbon spheres to the diglycidyl ether compound is 0.5: 1-5: 1.
9. the method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomerated ion exchange chromatography packing material of claim 2, wherein the mass ratio of the ultra-small particle size hydrothermal carbon spheres to the methylamine in the step (2) is 0.5: 1-5: 1.
10. the method for preparing the ultra-small particle size hydrothermal carbon sphere latex agglomeration type ion exchange chromatography packing material as claimed in claim 2, wherein the reaction temperature in the step (3) is 25-50 ℃, and the reaction time is 2-5 hours.
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