CN115651143B - Phenolic resin microsphere, porous carbon material microsphere, preparation method and application thereof - Google Patents
Phenolic resin microsphere, porous carbon material microsphere, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses phenolic resin microspheres, porous carbon material microspheres, and preparation methods and applications thereof. The phenolic resin microspheres are obtained by mixing and reacting a phenolic compound, water, an aldehyde compound, an alkaline catalyst and a dispersion medium; wherein the dispersion medium is selected from alkanes and/or cycloalkanes; the dispersing medium is not added with a small molecular surfactant. The phenolic resin microspheres in the invention have good control on particle size, uniform distribution of the particle size and high yield; meanwhile, the preparation method of the phenolic resin microspheres has the advantages of fewer steps, low cost, no need of using a curing agent, a pore-foaming agent and the like, and reduction of process treatment difficulty and risks in the production process; furthermore, the porous carbon material microspheres prepared by the phenolic resin microspheres have controllable particle sizes, and have the advantages of high loading rate and low loss rate when being used for loading drugs or nuclides.
Description
Technical Field
The invention relates to the field of medical treatment, in particular to phenolic resin microspheres, porous carbon material microspheres and preparation methods and applications thereof.
Background
Malignant tumors are a group of diseases seriously threatening human health, and currently, there are various treatment means including chemotherapy, radiotherapy, interventional therapy, biological immunotherapy, and the like. As one of the therapies, it has been greatly developed to provide radioactive materials for positioning cancer patients, the radioactive materials are incorporated into small particles that can be directly implanted into cancer solid tumors, and α or β rays released by radioactive elements are used to achieve local cell killing, reduce the influence on normal cells around tumor cells, and improve the safety as much as possible while ensuring the therapeutic effect.
In recent years, the carbon material microspheres show potential application prospects in the aspects of adsorption, catalysis, drug delivery, energy storage and the like. The carbon material is generally divided into three types, namely solid carbon material microspheres, hollow carbon material microspheres and porous carbon material microspheres. The porous carbon material microsphere has excellent properties such as high specific surface area, high chemical stability, high adsorbability and the like, and is widely applied to the fields of batteries, adsorption and the like. The carbon material microspheres as adsorption carriers for loading drugs and even radioactive elements have been studied, but the disclosures are few, and further research is needed.
The carbon aerogel material is generally obtained by preparing organic hydrogel, drying the organic hydrogel (the drying mode has important influence on the parameters such as the particle size, the pore diameter and the like of the microspheres, for example, supercritical drying and the like can be adopted) to obtain the organic aerogel, and carbonizing the organic aerogel. The carbon aerogel material reserves the skeleton structure of the organic aerogel, has very high porosity (generally 80-99.8%), very small density, very loose skeleton structure and basically interconnected pore channels, and is generally used as a lithium ion secondary battery cathode material or an electrode material of a super capacitor and the like. However, carbon aerogel materials have low strength, are easy to collapse and break, and are not suitable for loading drugs or nuclides.
As one of important precursors for preparing the porous carbon material microspheres, the phenolic resin microspheres have the characteristics of stable raw materials, low price and high char yield, but the raw materials of the phenolic resin microspheres, which are sold in the market or reported in literature, are basically in a nanometer grade or have the particle size of more than 100 micrometers. At present, linear phenolic resin and a curing agent are often mixed when phenolic resin microspheres are prepared, and then the phenolic resin microspheres are prepared through crushing, dispersing and high-temperature curing, so that the process is complicated, and the diameter of the microspheres is too high, often more than 100 mu m. The conventional hydrothermal preparation reaction also requires high temperature and high pressure, the reaction time is as long as more than 12 hours, the limitation of solid content (generally 5% or less) is difficult to break through, and the industrial production cost is too high.
Therefore, in order to solve the problems that the preparation process of the phenolic resin microspheres is complex, the energy consumption is too high, the particle distribution range of the prepared phenolic resin microspheres is too large, the particle size and the strength do not meet the requirements, the phenolic resin microspheres cannot be used as precursors of porous carbon material microspheres, and the like, the phenolic resin microspheres and the preparation method thereof are urgently needed to provide high-performance resin microsphere raw materials for preparing the porous carbon material microspheres.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art to a certain extent, and provides phenolic resin microspheres, porous carbon material microspheres and preparation methods and applications thereof. The phenolic resin microspheres in the invention have uniform sphere diameter distribution and high yield; meanwhile, the preparation method of the phenolic resin microspheres has the advantages of good control of the particle size (the average particle size is 20-40 mu m), few steps, low cost, no need of using a curing agent, a pore-forming agent and the like, and reduction of the process treatment difficulty and the risk in the production process; furthermore, the porous carbon material microspheres prepared from the phenolic resin microspheres have controllable particle size (the average particle size is 20-40 μm), are suitable for the pharmaceutical field (such as loading metal elements), and have the remarkable advantages of high loading rate, low loss rate and high safety.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes provided by the invention is as follows: a preparation method of phenolic resin microspheres. The preparation method of the phenolic resin microspheres comprises the following steps: mixing a phenolic compound, water, an aldehyde compound, an alkaline catalyst and a dispersion medium, and reacting to obtain the phenolic resin microspheres;
wherein the dispersion medium is selected from alkanes and/or cycloalkanes; and the dispersion medium is not added with a micromolecular surfactant.
In the present invention, the mixing may be conventional in the art, for example, the phenolic compound is mixed with deionized water, and then the deionized water solution of the basic catalyst, formaldehyde and the dispersion medium are added.
In the present invention, the mixing can be generally performed uniformly under stirring.
Wherein the stirring may be conventional in the art, such as magnetic stirring.
The stirring speed is preferably 50 to 300rpm/min, and more preferably 100 to 200rpm/min.
The stirring time is preferably 20 to 60min, and more preferably 30 to 40min.
In the present invention, the reaction temperature may be 50 to 100 ℃, preferably 60 to 85 ℃.
The reaction time may be 24 to 72h, for example 48h.
In the present invention, after the reaction is completed, the preparation method of the phenolic resin microspheres may further include steps of solid-liquid separation, cleaning and drying, according to the convention in the art.
Wherein, the solid-liquid separation can be conventional in the field, and filtration or rotary evaporation is preferred.
Wherein, the cleaning can be conventional in the field, and preferably absolute ethyl alcohol and deionized water are used for washing.
Wherein, the drying can be conventional in the field, and vacuum drying or forced air drying oven drying is preferred.
In the present invention, the alkane may be known in the art, and is preferably one or more of n-pentane, n-hexane, n-heptane, and n-octane, and more preferably n-heptane.
In the present invention, the cycloalkane may be known in the art, and cyclohexane is preferred.
In the present invention, the small molecule surfactant may be known in the art, and generally refers to a surfactant with a molecular weight of less than 1000, such as one or more of Span-type surfactant (such as Span-80), tween-type surfactant, sulfopropyl betaine-type surfactant (such as hexadecylsulfopropyl betaine), sorbitan monooleate surfactant, sodium cocoyl propionate, bromohexadecyl trimethylamine (CTAB), dodecyl polyoxyethylene ether-9, and polyethylene glycol octyl phenyl ether.
In the present invention, the kind of the basic catalyst may be known in the art, and inorganic bases are preferred. The inorganic base may be one or more of ammonia, metal hydroxides, carbonates and bicarbonates.
Wherein the metal hydroxide may be known in the art, preferably NaOH, KOH or Ca (OH) 2 。
Wherein the carbonate may be known in the art, preferably Na 2 CO 3 、K 2 CO 3 Or Cs 2 CO 3 。
Wherein the bicarbonate can be as known in the art, preferably NaHCO 3 Or KHCO 3 。
The alkaline catalyst is preferably NaOH, KOH, ca (OH) 2 、Na 2 CO 3 And K 2 CO 3 More preferably Na 2 CO 3 Or Ca (OH) 2 。
In the present invention, the basic catalyst is generally provided in the form of an aqueous solution thereof.
In the present invention, the molar ratio of the phenolic compound to the basic catalyst may be (0.001 to 0.1) 100, preferably (0.005 to 0.05), more preferably (100).
In the present invention, the phenolic compound may be known in the art, and generally refers to a phenolic compound having an electron donating substituent on a benzene ring or not, preferably one or more of resorcinol, phenol, cresol, nonylphenol, aralkylphenol, cardanol, octylphenol, bisphenol a, and xylenol; more preferably resorcinol or phenol.
In the present invention, the aldehyde compound may be known in the art, and is preferably one or more selected from the group consisting of formaldehyde, acetaldehyde and furfural, and more preferably formaldehyde.
In the present invention, the aldehyde compound is generally provided in the form of an aqueous solution thereof, for example, a 37% aqueous formaldehyde solution.
In the invention, the molar weight ratio of the phenolic compound to the aldehyde compound can be 1 (1~5), preferably 1 (2~4), more preferably 1:3.
In the invention, the weight-to-volume ratio (w/v) of the phenolic compound to the water can be 1 (3~8) g/mL, preferably 1 (4.7 to 7) g/mL, and more preferably 1 (5 to 6.25) g/mL.
In the present invention, the volume ratio of the water to the dispersion medium may be 1 (0.75 to 6), preferably 1 (1~5), more preferably 1 (2~4), and still more preferably 1 (2.4 to 3).
In the present invention, the water may be deionized water which is conventional in the art. The "water" in the "weight-to-volume ratio of the phenolic compound to the water" and "volume ratio of the water to the dispersion medium" includes, unless otherwise specified, the total volume of "water" used when the aqueous solution of the phenolic compound and the aqueous solution of the basic catalyst are prepared (when the basic catalyst is provided in the form of an aqueous solution thereof).
In the preparation method of the phenolic resin microspheres, a curing agent and/or a pore-forming agent are not generally added. Among them, the curing agent may be known in the art, such as hexamethylenetetramine, melamine, and the like. The porogen may be known in the art, for example, toluene, DOP, octadecanol, and the like.
In the invention, the preparation method of the phenolic resin microspheres can comprise the following steps:
(1) Mixing a phenolic compound, water, a basic catalyst, an aldehyde compound and a dispersion medium under stirring to obtain a mixed solution;
preferably, the molar ratio of the phenolic compound to the basic catalyst is 100 (0.001 to 0.1); the volume ratio of the water to the dispersion medium is 1 (0.75-6); the stirring speed is 50 to 300rpm/min;
(2) Placing the mixed liquid obtained in the step (1) in a reaction kettle for reaction;
preferably, the reaction temperature is 50 to 100 ℃;
(3) And (3) after the reaction in the step (2) is finished, carrying out solid-liquid separation, cleaning and drying treatment to obtain the phenolic resin microspheres.
The second technical scheme provided by the invention is as follows: phenolic resin microspheres. The phenolic resin microspheres are prepared by the preparation method of the phenolic resin microspheres.
In the invention, the average particle size of the phenolic resin microspheres is preferably 20-40 μm.
The third technical scheme provided by the invention is as follows: a preparation method of porous carbon material microspheres. The preparation method of the porous carbon material microsphere comprises the following steps: the phenolic resin microspheres as described above are carbonized.
In the present invention, the carbonization may be conventional in the art, and generally, may be performed in a tube furnace.
Wherein the atmosphere of the carbonization may be conventional in the art, such as an inert atmosphere. The inert atmosphere may be an argon atmosphere.
Wherein the carbonization temperature is preferably 400 to 1000 ℃, and more preferably 700 to 800 ℃.
The carbonization time is preferably 1 to 10h, and more preferably 2 to 4h.
In the present invention, the preparation method of the porous carbon material microspheres after the carbonization may further include the steps of washing, drying and sieving, according to the conventional practice in the art.
Wherein the washing may be conventional in the art, preferably washing with dilute nitric acid (e.g., 0.3mol/L dilute nitric acid) and deionized water sequentially.
Wherein, the drying can be conventional in the field, and vacuum drying or drying in a forced air drying oven is preferred.
Wherein the sieving can be conventional in the art, and preferably is performed using a sieving machine.
In the present invention, the method for preparing the porous carbon material microspheres preferably includes the steps of:
placing the phenolic resin microspheres in a tubular furnace, and carbonizing in an inert atmosphere; and after carbonization, cleaning, drying and screening to obtain the porous carbon material microspheres.
The fourth technical scheme provided by the invention is as follows: porous carbon material microspheres. The porous carbon material microsphere is prepared by the preparation method of the porous carbon material microsphere.
In the invention, the BET multipoint specific surface area of the porous carbon material microsphere can be 10 to 30m 2 The BET multipoint specific surface area of the porous carbon material microspheres can be any value from 10 to 30, such as 10.01m 2 /g、12m 2 /g、14m 2 /g、16m 2 /g、18m 2 /g、20m 2 /g、22.32m 2 /g、24m 2 /g、26m 2 G or 28m 2 /g。
The average pore diameter of the mesopores of the porous carbon material microspheres can be 5 to 10nm, and the porous carbon material microspheres have the advantages of higher strength and suitability for preparing radiopharmaceuticals in the range of 5 to 10nm, and it can be understood that the pore diameter can be any value between 5 and 10nm, such as 5nm, 6nm, 6.75nm, 7nm, 8nm, 9nm, 9.32nm, 10nm and the like, or other values not listed in the range of 5 to 10nm.
The average particle size of the porous carbon material microspheres can be 20-40 μm.
The fifth technical scheme provided by the invention is as follows: use of porous carbon material microspheres as hereinbefore described in the preparation of a radiopharmaceutical.
In the present invention, the radiopharmaceutical is generally understood to be a drug for the treatment of tumors.
In the present invention, the radiopharmaceutical preferably includes the porous carbon material microspheres, and a metal element supported on the porous carbon material microspheres.
Wherein the metal element can be a therapeutic or imaging radionuclide, generally selected from, but not limited to 90 Y， 32 P， 192 Ir， 103 Pd， 89 Sr， 226 Ra， 131 I， 125 I， 188 Re， 186 Re， 153 Sm， 166 Ho， 111 In， 99m Tc， 192 Ir， 226 Ra， 177 Lu， 225 Ac， 212 Bi， 213 Bi and 223 one or more of Ra.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) The preparation method of the phenolic resin microspheres comprises the steps of stirring and mixing a reaction monomer, a catalyst and a dispersion medium, and then reacting to prepare the phenolic resin microspheres (solid microspheres). Compared with the prior art in which the reaction monomer is pre-polymerized under the action of the catalyst, and then the prepolymer is added into the dispersion medium to carry out the balling process, the preparation process of the invention has the advantages of simple steps and post-treatment, good particle size control (especially, the particle size distribution is better between 20 mu m and 40 mu m, and the particle size distribution is suitable for interventional therapy of hepatic artery radiotherapeutic embolization), uniform sphere diameter distribution, and high yield of more than 70%.
(2) According to the preparation method of the phenolic resin microspheres, a curing agent, a pore-forming agent and the like are not needed, unnecessary materials are reduced, and the process treatment difficulty is reduced, for example, hexamethylenetetramine is an easily explosive dangerous chemical, and the risk in the production process can be reduced if the hexamethylenetetramine is not used.
(3) The phenolic resin microspheres prepared by the method are beneficial to preparing porous carbon material microspheres (with good distribution between 20 and 40 micrometers, and suitable for interventional therapy of hepatic artery radiotherapeutic embolization), which are controllable in particle size, uniform in sphere diameter distribution and high in strength, more suitable for loading nuclides, high in loading rate and low in loss rate, and can ensure medication safety.
Drawings
FIG. 1 is a graph showing the particle size distribution of the phenolic resin microspheres obtained in examples 1 to 4.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the porous carbon material microspheres prepared in example 2.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the porous carbon material microspheres prepared in example 3.
Detailed Description
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following examples and comparative examples, formaldehyde was a 37% aqueous formaldehyde solution.
Examples 1-1 to 1-15 and comparative examples 1~3 preparation of phenolic resin microspheres
Mixing a phenolic compound and deionized water, uniformly stirring by magnetic force, adding a deionized water solution of a basic catalyst, formaldehyde and a dispersion medium, and stirring by magnetic force for 30 minutes to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, reacting for 48 hours at a certain temperature, washing with absolute ethyl alcohol and deionized water, drying in vacuum at 60 ℃, and sieving to obtain the phenolic resin microspheres.
The specific process parameters and reaction results are shown in tables 1-1 and 1-2 below:
TABLE 1-1
Remarking: the volume of deionized water in the above table includes the total volume of deionized water in "mixing phenolic compound with deionized water" and "deionized water solution of basic catalyst".
Tables 1 to 2
Remarking: the volume of deionized water in the above table includes the total volume of deionized water in "mixing phenolic compound with deionized water" and "deionized water solution of basic catalyst".
Example 2 preparation of porous carbon Material microspheres
Calcining the phenolic resin microspheres (the particle size distribution diagram is shown in figure 1) prepared in the examples 1-4 for 4 hours at 700 ℃ in Ar atmosphere to prepare porous carbon material microspheres (the heating rate is 3 ℃/min); sequentially cleaning porous carbon material microspheres with 0.3mol/L dilute nitric acid and deionized water for 2 times, drying and screening to obtain porous carbon material microspheres (a scanning electron microscope picture of which is shown in figure 2); the BET multipoint specific surface area of the porous carbon material microspheres in example 2 was 10.01m 2 (g), the average pore diameter of the mesopores is 9.32nm.
Example 3 preparation of porous carbon Material microspheres
Calcining the phenolic resin microspheres prepared in the examples 1 to 15 at 800 ℃ for 4h in Ar atmosphere to prepare porous carbon material microspheres (the heating rate is 3 ℃/min), sequentially cleaning the porous carbon material microspheres for 2 times by using 0.3mol/L dilute nitric acid and deionized water, drying and screening to obtain the porous carbon material microspheres (the scanning electron microscope picture of which is shown in figure 3); the BET multipoint specific surface area of the porous carbon material microspheres in example 3 was 22.32m 2 The average pore diameter of mesopores is 6.75nm.
Example 4 preparation of phenolic resin microspheres and porous carbon Material microspheres (Scale-Up production)
Mixing 640g of resorcinol and 3L of deionized water uniformly, adding a sodium carbonate aqueous solution (62 g of sodium carbonate/0.5L of deionized water), 1.1L of formaldehyde and 10L of n-heptane, and magnetically stirring at 200rpm/min for 30 minutes to obtain a mixed solution; the mixture was transferred to a reaction vessel and reacted at 60 ℃ for 72 hours. And after the reaction is finished, performing solid-liquid separation to obtain phenolic resin microspheres, cleaning with n-heptane and ethanol, drying by a rotary evaporator, and drying by an air blast drying oven to obtain the phenolic resin microspheres (the particle size is intensively distributed in a range from 20 micrometers to 40 micrometers).
Placing the prepared phenolic resin microspheres in a tubular furnace, carbonizing for 4 hours at 800 ℃ under the protection of argon atmosphere to obtain porous carbon material microspheres, sequentially cleaning with dilute nitric acid and purified water, placing in a blast drying oven for drying, and screening with a screening instrument to obtain the porous carbon material microspheres; the particle size of the product is distributed in a concentrated manner from 20 μm to 40 μm, and the yield is 76.2%.
Comparative example 4 preparation of phenolic resin microspheres and porous carbon Material microspheres
And (2) mixing heat conduction oil and silicone oil according to a mass ratio of 4:1, mixing, preheating at 115 ℃ and stirring for 1h. Weighing thermosetting phenolic resin and ethanol (the mass ratio is 1:4), uniformly mixing and stirring, slowly pouring the mixed solution into preheated mixed oil, stirring (500 r/min) for 2h at 115 ℃, filtering, separating, washing and drying to obtain phenolic resin microspheres, wherein the particle size distribution of the phenolic resin microspheres is concentrated in 10-20 microns.
Carbonizing the obtained phenolic resin microspheres for 1h at 800 ℃ in Ar atmosphere to obtain porous carbon material microspheres, wherein the particle size distribution of the porous carbon material microspheres is concentrated in 10-20 mu m, and the BET multipoint specific surface area is 540m 2 The average pore diameter of the mesopores is 0.89nm.
Comparative example 5 preparation of phenolic resin microspheres and porous carbon material microspheres
Adding phloroglucinol (1 eq), resorcinol (1 eq) and formaldehyde (1 eq) into deionized water, stirring for dissolving, stirring at a high rotating speed of 800r/min for 5min, and stirring at a low rotating speed of 100r/min for 5min to prepare a precursor solution; adding the precursor solution into industrial white oil containing span-80 with the volume fraction of 1% (the volume ratio of the precursor solution to the industrial white oil is 1:8), stirring and mixing uniformly, and carrying out oil bath reaction at 25 ℃ for 12h to obtain turbid solution; and (3) carrying out suction filtration and separation on the turbid solution, and cleaning the turbid solution for multiple times by using dichloromethane to obtain powdery solid (namely phenolic resin microspheres) with particle size distribution concentrated in about 1-10 mu m. Mixing the powderCarbonizing the solid at 850 ℃ for 5h to prepare the porous carbon material microspheres, wherein the particle size distribution of the porous carbon material microspheres is concentrated at about 1-10 mu m, and the BET multipoint specific surface area is 930m 2 The average pore diameter of the mesopores is 18.56nm.
Effect example 1 porous carbon material microspheres supporting metal nuclide
Respectively uniformly mixing 0.15g of porous carbon material microspheres prepared in examples 2-3 and comparative examples 4-5 with 0.025g/mL of tartaric acid solution, standing for 12h, and then adding YCl into the mixed solution 3 The solution (0.0125 g/mL) was shaken in a constant temperature shaker at 25 ℃ for 1h, so that the Y-containing complex was sufficiently loaded on the porous carbon material microspheres (the total volume of the solution was 3 mL).
And (3) carrying out suction filtration on the solution loaded with the porous carbon material microspheres containing the Y complex for 3 times through deionized water, and measuring the loading rate.
And (3) soaking the collected porous carbon material microspheres loaded with the Y-containing complex in normal saline for 6 days, measuring the content of Y ions in the solution, and calculating the loss rate.
The specific results are shown in table 2 below:
TABLE 2
Therefore, the porous carbon material microspheres prepared in the embodiment have the advantages of good sphericity maintenance, high loading rate and low loss rate in the element loading process, and are more suitable for element loading.
When the mesoporous size of the porous carbon material microsphere is smaller (comparative example 4), the mesoporous space is relatively limited, the reactant enters and exits the mesopores to be limited, and the capability of adsorbing complex precipitates generated outside the mesopores is insufficient, so that the overall loading rate is low. When the size of the mesopores of the porous carbon material microspheres is larger (comparative example 5), the specific surface area and the mesopore space of the porous carbon material microspheres are larger, the complex precipitation amount generated outside the mesopores which can be adsorbed into the mesopores is more sufficient, the loading rate is better, but the embedding and fixing effects on the complex precipitation in the mesopores are relatively limited, the loss rate is obviously increased, and the requirement on safety cannot be met.
As can be seen from the foregoing, the inventors of the present application found that porous carbon material microspheres for supporting metal elements should satisfy certain particle size requirements. Specifically, the method of carbonizing organic material microspheres at high temperature to obtain carbon microspheres is one of the common methods for preparing carbon materials, but if a porous carbon material microsphere which supports a drug or a nuclide is desired to be obtained, certain requirements are imposed on the particle size of the organic material microspheres as a precursor. By adopting the preparation method, the phenolic resin microspheres with the particle size meeting the requirements can be obtained, and the preparation method has the advantages of good sphericity and high yield; furthermore, the phenolic resin microspheres are used as precursors, the particle size of the prepared porous carbon microspheres is almost unchanged, the appearance is well maintained after metal elements are loaded, and the strength is high.
Claims (14)
1. The preparation method of the phenolic resin microspheres is characterized by comprising the following steps: mixing a phenolic compound, water, an aldehyde compound, an alkaline catalyst and a dispersion medium, and reacting to obtain the phenolic resin microspheres;
wherein the dispersion medium is selected from alkanes and/or cycloalkanes; and no small molecule surfactant is added into the dispersion medium;
the alkane is one or more of n-pentane, n-hexane, n-heptane and n-octane, and the cycloalkane is cyclohexane; and
the alkaline catalyst is NaOH, KOH, ca (OH) 2 、Na 2 CO 3 And K 2 CO 3 One or more of (a).
2. The method for preparing phenolic resin microspheres according to claim 1, wherein the method for preparing phenolic resin microspheres satisfies the following conditions:
(1) the mixing comprises the steps of mixing the phenolic compound with deionized water, and then adding a deionized water solution of a basic catalyst, formaldehyde and a dispersion medium;
(2) the mixing is uniformly mixing under the stirring condition; the stirring speed is 50 to 300rpm/min;
(3) the temperature of the reaction is 50 to 100 ℃.
3. The method for preparing phenolic resin microspheres according to claim 2, wherein the method for preparing phenolic resin microspheres satisfies the following conditions:
(4) the stirring speed is 100 to 200rpm/min;
(5) the stirring time is 20 to 60min;
(6) the temperature of the reaction is 60 to 85 ℃.
4. The method for preparing phenolic resin microspheres according to claim 1, wherein the method for preparing phenolic resin microspheres satisfies the following conditions:
a. the basic catalyst is provided in the form of an aqueous solution thereof;
b. the molar ratio of the phenolic compound to the basic catalyst is 100 (0.001 to 0.1);
c. the phenolic compound is one or more of resorcinol, phenol, cresol, nonyl phenol, aralkyl phenol, cardanol, octyl phenol, bisphenol A and xylenol;
d. the aldehyde compound is selected from one or more of formaldehyde, acetaldehyde and furfural;
e. the aldehyde compound is provided in the form of an aqueous solution thereof;
f. the molar weight ratio of the phenolic compound to the aldehyde compound is 1 (1~5);
g. the weight-to-volume ratio of the phenolic compound to the water is 1 (3~8) g/mL;
h. the volume ratio of the water to the dispersion medium is 1 (0.75-6);
i. the preparation method of the phenolic resin microspheres does not add a curing agent and/or a pore-foaming agent.
5. The method for preparing the phenolic resin microspheres according to claim 4, wherein the method for preparing the phenolic resin microspheres meets the following conditions:
I. the molar ratio of the phenolic compound to the basic catalyst is 100 (0.005 to 0.05);
II. The molar weight ratio of the phenolic compound to the aldehyde compound is 1 (2~4);
III, the weight volume ratio of the phenolic compound to the water is 1 (4.7 to 7) g/mL;
IV, the volume ratio of the water to the dispersion medium is 1 (1~5).
6. The method for preparing phenolic resin microspheres according to claim 5, wherein the method for preparing phenolic resin microspheres satisfies the following conditions:
v, the weight volume ratio of the phenolic compound to the water is 1 (5 to 6.25) g/mL;
VI, the volume ratio of the water to the dispersion medium is 1 (2~4).
7. The method for preparing phenolic resin microspheres according to claim 1, wherein the method for preparing phenolic resin microspheres comprises the following steps:
(1) Mixing a phenolic compound, water, a basic catalyst, an aldehyde compound and a dispersion medium under stirring to obtain a mixed solution;
(2) Placing the mixed liquid obtained in the step (1) in a reaction kettle for reaction; and
(3) And (3) after the reaction in the step (2) is finished, carrying out solid-liquid separation, cleaning and drying treatment to obtain the phenolic resin microspheres.
8. Phenolic resin microspheres, characterized in that they are produced by the method of any one of claims 1~7.
9. A preparation method of porous carbon material microspheres is characterized by comprising the following steps: carbonizing the phenolic resin microspheres of claim 8.
10. The method for preparing porous carbon material microspheres according to claim 9, wherein the atmosphere for carbonization is an inert atmosphere;
the carbonization temperature is 400 to 1000 ℃;
the carbonization time is 1 to 10 hours.
11. The method for preparing porous carbon material microspheres according to claim 10, wherein the inert atmosphere is an argon atmosphere;
the temperature of carbonization is 700 to 800 ℃;
the carbonization time is 2 to 4 hours.
12. The method for preparing porous carbon material microspheres according to any one of claims 9 to 11, wherein the method for preparing porous carbon material microspheres comprises the following steps:
placing the phenolic resin microspheres in a tubular furnace, and carbonizing in an inert atmosphere; and after carbonization, cleaning, drying and screening to obtain the porous carbon material microspheres.
13. A porous carbon material microsphere is characterized by being prepared by the preparation method of the porous carbon material microsphere according to any one of claims 9 to 12.
14. Use of porous carbon material microspheres according to claim 13 for the preparation of a radiopharmaceutical.
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| CN107032324A (en) * | 2017-03-23 | 2017-08-11 | 太原理工大学 | A kind of preparation method of the order mesoporous Nano carbon balls of magnetic for target administration |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
| CN113816373A (en) * | 2021-09-16 | 2021-12-21 | 常州大学 | Preparation method of biomass modified phenolic resin carbon spheres with controllable particle size |
| CN115449042A (en) * | 2021-06-09 | 2022-12-09 | 济南精智方正新材料有限公司 | Micro-spherical phenolic resin and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032324A (en) * | 2017-03-23 | 2017-08-11 | 太原理工大学 | A kind of preparation method of the order mesoporous Nano carbon balls of magnetic for target administration |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
| CN115449042A (en) * | 2021-06-09 | 2022-12-09 | 济南精智方正新材料有限公司 | Micro-spherical phenolic resin and preparation method and application thereof |
| CN113816373A (en) * | 2021-09-16 | 2021-12-21 | 常州大学 | Preparation method of biomass modified phenolic resin carbon spheres with controllable particle size |
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