CN110627947B - High-crosslinking rosin-based polymer microsphere and preparation method and application thereof - Google Patents
High-crosslinking rosin-based polymer microsphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN110627947B CN110627947B CN201911040979.4A CN201911040979A CN110627947B CN 110627947 B CN110627947 B CN 110627947B CN 201911040979 A CN201911040979 A CN 201911040979A CN 110627947 B CN110627947 B CN 110627947B
- Authority
- CN
- China
- Prior art keywords
- rosin
- highly crosslinked
- based polymer
- crosslinked rosin
- based polymeric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a high-crosslinked rosin-based polymer microsphere, a preparation method and application thereof. The highly crosslinked rosin-based polymer microsphere is a spherical porous material, the particle size distribution of the spherical porous material is 2-10 mu m, the average pore diameter is 12-28nm, and the specific surface area is 32-102m2(iv) g; the chromatographic column packing material has the characteristics of no toxicity, environmental protection, uniform particle size, high mechanical strength, higher pressure resistance, smaller polarity and the like when used as a chromatographic column packing material, and the chromatographic column prepared by packing has a better separation effect on glucoside medicines.
Description
Technical Field
The invention belongs to the field of high performance liquid chromatography, and particularly relates to a high-crosslinking rosin-based polymer microsphere as well as a preparation method and application thereof.
Background
High Performance Liquid Chromatography (HPLC) has become one of the most important and widespread analytical techniques in pharmaceutical analysis, particularly in multi-component analysis and impurity control. Along with the continuous improvement of a theoretical system, the continuous update of a separation method, the continuous improvement of instrument performance and the continuous expansion of the application field, the liquid chromatography analysis technology is bound to be continuously and rapidly developed. In terms of technical development, improvements and improvements in instrumentation performance, data processing, and chromatography column technology have been included. Nowadays, the technology of chromatographic columns is continuously improved and innovated, the types of fillers are increasingly abundant, and the separation mode and the separation method are gradually improved, so that a gorgeous picture is scientifically depicted for separation analysis. Because the chromatographic column is a separate core of liquid chromatography, the development of novel or high-performance high performance liquid chromatography packing (also called filling agent and stationary phase) and the provision of various chromatographic column types are always the most abundant, most active and most creative content in chromatographic research. In order to meet the increasing separation requirements, the development of a chromatographic column with higher selectivity and better performance becomes one of the research hotspots of the liquid chromatography. At present, commercial columns mostly adopt silica gel matrixes as main materials, and silica gel packing has two problems which are difficult to solve in chromatographic application: (1) the usable pH range is narrow: generally, it can only be used under mobile phase conditions with a pH of 2 to 8. The alkalinity is too large, and particularly when quaternary ammonium ions exist, silica gel is easy to crush and dissolve; the acidity is too high and the chemical bond connecting the organic groups is easily broken. (2) The existence of impurities such as residual silicon hydroxyl and metal ions on the surface of the silica gel is easy to generate irreversible adsorption on alkaline substances, particularly nitrogen-containing compounds, so that biological macromolecules, particularly samples such as polypeptide, protein and the like generate denaturation and non-specific adsorption, peak shape deterioration and recovery rate reduction are caused, and the application of the silica gel matrix filler in the separation and analysis of a biological system is limited. The polymer microspheres which are also widely used as chromatographic packing present a good development situation, and compared with silica gel matrixes, the organic polymer column packing has the following advantages in chromatographic performance: (1) the reproducibility of the column is good; (2) the column has long service life; (3) the sample load is high; (4) the pH value range is wide. Therefore, research and development thereof in various fields are actively conducted.
At present, the following documents are found in the report of the preparation method of chromatographic stationary phase:
1. l. Shuquan L V, Shiguo, et al, bonded beta-cyclodextrin agar gel microspheres, and the chromatographic mechanism research thereof [ J ] Chinese herbal medicine, 2016, Vol.47issue (15): 2627) 2634. bonded beta-cyclodextrin agar gel microspheres are prepared by using agar as a raw material and through emulsification, crosslinking and bonding of functional groups beta-cyclodextrin (beta-CD), and the soybean aglycone in the crude product of the soybean isoflavone is efficiently separated and purified.
2. Application No.: 201510120168.0 title of the invention: a new green synthesis method of macroporous cellulose chromatographic microspheres is provided, wherein a curing agent is adopted to cure cellulose in ionic liquid to form macroporous microspheres; finally, the generated macroporous cellulose microspheres are crosslinked and modified to prepare the cellulose anion exchange material with perfusion and mass transfer effects.
3. Application No.: 201710710292.1 title of the invention: a low-polarity rosin-based polymer microsphere and a preparation method and application thereof are disclosed, wherein methyl methacrylate is used as a monomer, propylene pimaric acid ethylene glycol acrylate is used as a cross-linking agent, and a membrane emulsification-micro suspension polymerization method is adopted to prepare the low-polarity rosin-based polymer microsphere for separating natural products.
However, the chromatographic column stationary phase prepared from the microsphere has poor separation effect on the glycoside drugs, so it is necessary to explore a new polymer microsphere for separating the glycoside drugs.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-crosslinking rosin-based polymer microsphere and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a high-crosslinking rosin-based polymer microsphere is prepared by crosslinking and polymerizing methyl methacrylate and fumaropimaric acid tri (ethylene glycol acrylate),
the structural formula of the fumaropimaric acid tri (ethylene glycol acrylate) ester is as follows:
the structural formula of the highly crosslinked rosin-based polymer microsphere is as follows:
wherein R is:
preferably, the highly crosslinked rosin-based polymeric microspheres have an acid value of less than or equal to 1mgKOH/g resin, are spherical porous materials, have a particle size distribution of 2-10 mu m, an average pore diameter of 12-28nm and a specific surface area of 32-102m2/g。
The preparation method of the highly crosslinked rosin-based polymer microsphere comprises the following steps of using methyl methacrylate as a functional monomer and fumaric pimaric acid tri (ethylene glycol acrylate) as a crosslinking agent, and adopting a membrane emulsification-microsuspension polymerization method to prepare the highly crosslinked rosin-based polymer microsphere, wherein the reaction formula is as follows:
in the formula (I), the compound is shown in the specification,
is the chemical formula of fumaropimaric acid tri (ethylene glycol acrylate),
Preferably, the membrane emulsification-microsuspension polymerization method specifically comprises the following steps: mixing a water phase consisting of deionized water and polyvinyl alcohol with an oil phase consisting of methyl methacrylate, a cross-linking agent of fumaric pimaric acid tri (ethylene glycol acrylate) ester, a solvent of chloroform and an initiator of azobisisobutyronitrile, emulsifying by using a film emulsifying machine to obtain a pre-emulsion, and then heating and polymerizing to obtain the high-crosslinked rosin-based polymer microsphere.
Preferably, the temperature-rising polymerization reaction is a temperature-programmed reaction at 70-80 ℃ for 60-120min, a reaction at 80-85 ℃ for 60-120min, and a reaction at 95-100 ℃ for 60-120 min.
Preferably, the mass ratio of the deionized water to the polyvinyl alcohol in the aqueous phase is 50: 0.1 to 2.
Preferably, the mass ratio of the methyl methacrylate, the fumaropimaric acid tri (ethylene glycol acrylate), the chloroform and the azobisisobutyronitrile in the oil phase is 1-30: 6: 20-100: 0.1 to 5.
The application of the high-crosslinked rosin-based polymer microsphere is that the high-crosslinked rosin-based polymer microsphere is used as a stationary phase filler, and a wet column filling method is adopted to prepare a high-crosslinked rosin-based polymer chromatographic column; the high-crosslinked rosin-based polymer chromatographic column is connected to a liquid chromatograph, and the column loading pressure is 3000-; setting the flow rate of a mobile phase of a liquid chromatograph to be 1.0-2.0mL/min, the detection wavelength to be 203nm and the column temperature to be 35 +/-10 ℃; starting a sample injection valve to enable the mobile phase to bring the panax notoginseng saponins into the rosin-based polymer chromatographic column with high crosslinking degree, thereby realizing the separation of the panax notoginseng saponins.
The principle of the invention is as follows:
the highly crosslinked rosin-based polymer microsphere is prepared by crosslinking and polymerizing methyl methacrylate and fumaropimaric acid tri (ethylene glycol acrylate), and a model diagram of the highly crosslinked rosin-based polymer microsphere is shown in fig. 7. On one hand, the tris (ethylene glycol acrylate) fumarate contains a steroid ring structure similar to notoginsenoside, and chiral C atoms on the tris (ethylene glycol acrylate) fumarate enable the synthesized rosin-based polymer chromatographic column to have better stereoselectivity for similar separation results, and on the other hand, the tris (ethylene glycol acrylate) fumarate has three ester groups, has higher crosslinking degree, can form a more compact network structure, and is beneficial to improving the pressure resistance of the chromatographic column; the pore structure on the surface of the microsphere can be adjusted according to the size of the substance to be separated, which is beneficial to the adsorption and analysis in the separation process.
Compared with the prior art, the invention has the beneficial effects that:
(1) the highly crosslinked rosin-based polymer microsphere takes the derivative of rosin, i.e. fumaropimaric acid tri (ethylene glycol acrylate) as a raw material, is renewable, high in mechanical strength, safe and nontoxic, and can be used for food-grade separation.
(2) The highly crosslinked rosin-based polymer microsphere is low in polarity, has a lower acid value compared with the existing rosin-based polymer microsphere, belongs to a completely neutral microsphere, and has the characteristics of better alkali resistance, small swelling degree and the like.
(3) The high-crosslinked rosin-based polymer microsphere used as a chromatographic stationary phase filler has small swelling degree, uniform particle size and large specific surface area, and has a good separation effect on glucoside medicines; compared with rosin-based polymer microspheres prepared by adopting two propylene groups in the prior application 201710710292.1 of the applicant, the mechanical strength is high, the pressure resistance of the chromatographic column packing is higher, the polarity is smaller, the network structure of the microspheres cannot be damaged due to expansion, and the pressure resistance is improved from 8MPa to 20 MPa.
Drawings
FIG. 1 is a scanning electron microscope image of the highly crosslinked rosin-based polymeric microspheres prepared in example 1;
FIG. 2 is a nitrogen adsorption-desorption graph of the highly crosslinked rosin-based polymeric microspheres prepared in example 2;
FIG. 3 is a distribution diagram of the particle size of the highly crosslinked rosin-based polymeric microspheres prepared in example 3;
FIG. 4 is a thermogram of a highly crosslinked rosin-based polymeric microsphere prepared in example 4;
FIG. 5 is a graph of the flow through performance of a highly crosslinked rosin-based polymer chromatography column prepared in example 5;
fig. 6 is a separation diagram of the highly crosslinked rosin-based polymeric chromatographic column of example 6 of the present invention from the mixed solution of panax notoginseng saponins.
FIG. 7is a schematic diagram of a highly crosslinked rosin-based polymeric microsphere of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the scope of the present invention.
Preparation of highly crosslinked rosin-based polymer microspheres
Preparation of example 1
500g of deionized water and 1g of polyvinyl alcohol (the mass ratio of the ionized water to the polyvinyl alcohol is 50: 0.1) are mixed, and the mixture is heated to 100 ℃ to completely dissolve the polyvinyl alcohol, so that a water phase is obtained. Dissolving 6.0g of fumaric pimaric acid tri (ethylene glycol acrylate) ester in 20.0g of chloroform, promoting dissolution by using ultrasonic waves, after the fumaric pimaric acid tri (ethylene glycol acrylate) ester is completely dissolved, sequentially adding 1.0g of methyl methacrylate and 0.1g of azodiisobutyronitrile (the mass ratio of the functional monomer, the cross-linking agent, the solvent and the initiator is 1: 6: 20: 0.1), and oscillating for 10-15 min by ultrasonic waves to completely dissolve to obtain an oil phase. Adding the oil phase into the water phase, emulsifying with a membrane emulsifying machine to obtain emulsion, heating the emulsion at a stirring speed of 200rad/min for polymerization, maintaining the temperature at 70 deg.C for 120min, maintaining the temperature at 80 deg.C for 120min, and maintaining the temperature at 95 deg.C for 120 min. After the reaction is finished, sequentially extracting the product with ethyl acetate and ethanol, and finally removing the ethyl acetate and the ethanol in the microspheres by a steam distillation method to obtain the high-crosslinked rosin-based polymer microspheres.
Through detection and analysis, the acid value of the highly crosslinked rosin-based polymeric microspheres obtained in the example is 0.52mgKOH/g resin, the particle size distribution is 2-5 μm, the average pore diameter is 18nm, and the specific surface area is 32m2/g。
Preparation of example 2
400g of deionized water and 8g of polyvinyl alcohol (the mass ratio of the ionized water to the polyvinyl alcohol is 50: 1) are mixed, and the mixture is heated to 100 ℃ to completely dissolve the polyvinyl alcohol, so that a water phase is obtained. Dissolving 6.0g of fumaric pimaric acid tri (ethylene glycol acrylate) ester in 70.0g of chloroform, promoting dissolution by using ultrasonic waves, after the fumaric pimaric acid tri (ethylene glycol acrylate) ester is completely dissolved, sequentially adding 10.0g of methyl methacrylate and 4g of azodiisobutyronitrile (the mass ratio of the functional monomer, the cross-linking agent, the solvent and the initiator is 10: 6: 70: 4), and carrying out ultrasonic oscillation for 2-10 min to obtain an oil phase after complete dissolution. Adding the oil phase into the water phase, emulsifying with a membrane emulsifying machine to obtain emulsion, heating the emulsion at a stirring speed of 160rad/min for polymerization, keeping the temperature at 70 deg.C for 90min, keeping the temperature at 83 deg.C for 90min, and keeping the temperature at 98 deg.C for 90 min. After the reaction is finished, sequentially extracting the product with ethyl acetate and ethanol, and finally removing the ethyl acetate and the ethanol in the microspheres by a steam distillation method to obtain the high-crosslinked rosin-based polymer microspheres.
Through detection and analysis, the acid value of the highly crosslinked rosin-based polymeric microspheres obtained in the example is 0.40mgKOH/g resin, the particle size distribution is 2-5 μm, the average pore diameter is 12nm, and the specific surface area is 49m2/g。
Preparation of example 3
500g of deionized water and 20g of polyvinyl alcohol (the mass ratio of the ionized water to the polyvinyl alcohol is 50: 2) are mixed, and the mixture is heated to 100 ℃ to completely dissolve the polyvinyl alcohol, so that a water phase is obtained. Dissolving 6.0g of fumaropimaric acid tri (ethylene glycol acrylate) ester in 30.0g of chloroform, promoting dissolution by using ultrasonic waves, after the fumaropimaric acid tri (ethylene glycol acrylate) ester is completely dissolved, sequentially adding 20.0g of methyl methacrylate and 5g of azodiisobutyronitrile (the mass ratio of the functional monomer, the cross-linking agent, the solvent and the initiator is 20: 6: 30: 5), and oscillating for 2-10 min by ultrasonic waves to completely dissolve to obtain an oil phase. Adding the oil phase into the water phase, emulsifying with a membrane emulsifying machine to obtain emulsion, heating the emulsion at a stirring speed of 200rad/min for polymerization, keeping the temperature at 80 deg.C for 60min, keeping the temperature at 85 deg.C for 60min, and keeping the temperature at 100 deg.C for 60 min. After the reaction is finished, sequentially extracting the product with ethyl acetate and ethanol, and finally removing the ethyl acetate and the ethanol in the microspheres by a steam distillation method to obtain the high-crosslinked rosin-based polymer microspheres.
Through detection and analysis, the acid value of the highly crosslinked rosin-based polymeric microspheres obtained in the example is 0.43mgKOH/gLipid with particle size distribution of 5-8 μm, average pore diameter of 25nm, and specific surface area of 76m2/g。
Preparation of example 4
500g of deionized water and 6g of polyvinyl alcohol (the mass ratio of the ionized water to the polyvinyl alcohol is 50: 0.6) are mixed, and the mixture is heated to 100 ℃ to completely dissolve the polyvinyl alcohol, so that a water phase is obtained. Dissolving 6.0g of fumaropimaric acid tri (ethylene glycol acrylate) ester in 100.0g of chloroform, promoting dissolution by using ultrasonic waves, after the fumaropimaric acid tri (ethylene glycol acrylate) ester is completely dissolved, sequentially adding 30.0g of methyl methacrylate and 3g of azodiisobutyronitrile (the mass ratio of the functional monomer, the cross-linking agent, the solvent and the initiator is 30: 6: 100: 3), and oscillating for 2-10 min by ultrasonic waves to completely dissolve to obtain an oil phase. Adding the oil phase into the water phase, emulsifying with a membrane emulsifying machine to obtain emulsion, heating the emulsion at a stirring speed of 200rad/min for polymerization, keeping the temperature at 75 deg.C for 60min, keeping the temperature at 80 deg.C for 60min, and keeping the temperature at 95 deg.C for 60 min. After the reaction is finished, sequentially extracting the product with ethyl acetate and ethanol, and finally removing the ethyl acetate and the ethanol in the microspheres by a steam distillation method to obtain the high-crosslinked rosin-based polymer microspheres.
Through detection and analysis, the acid value of the highly crosslinked rosin-based polymeric microspheres obtained in the example is 0.41mgKOH/g resin, the particle size distribution is 5-7 μm, the average pore diameter is 22nm, and the specific surface area is 93m2/g。
Preparation of example 5
500g of deionized water and 15g of polyvinyl alcohol (the mass ratio of the ionized water to the polyvinyl alcohol is 50: 1.5) are mixed, and the mixture is heated to 100 ℃ to completely dissolve the polyvinyl alcohol, so that a water phase is obtained. Dissolving 6.0g of fumaropimaric acid tri (ethylene glycol acrylate) ester in 45.0g of chloroform, promoting dissolution by using ultrasonic waves, after the fumaropimaric acid tri (ethylene glycol acrylate) ester is completely dissolved, sequentially adding 15.0g of methyl methacrylate and 2g of azodiisobutyronitrile (the mass ratio of the functional monomer, the cross-linking agent, the solvent and the initiator is 15: 6: 45: 2), and oscillating for 2-10 min by ultrasonic waves to completely dissolve to obtain an oil phase. Adding the oil phase into the water phase, emulsifying with a membrane emulsifying machine to obtain emulsion, heating the emulsion at a stirring speed of 200rad/min for polymerization, keeping the temperature at 70 deg.C for 70min, keeping the temperature at 80 deg.C for 70min, and keeping the temperature at 100 deg.C for 70 min. After the reaction is finished, sequentially extracting the product with ethyl acetate and ethanol, and finally removing the ethyl acetate and the ethanol in the microspheres by a steam distillation method to obtain the high-crosslinked rosin-based polymer microspheres.
Through detection and analysis, the acid value of the highly crosslinked rosin-based polymeric microspheres obtained in the example is 0.49mgKOH/g resin, the particle size distribution is 5-10 μm, the average pore diameter is 28nm, and the specific surface area is 102m2/g。
Material characterization of the highly crosslinked rosin-based polymeric microspheres:
characterization analysis method
Scanning Electron Microscopy (SEM) is an important method for characterizing the morphology of nanomaterials. The study used a Field Emission Scanning Electron Microscope (FESEM) to perform microscopic morphology analysis of the highly crosslinked rosin-based polymeric microspheres.
The nitrogen adsorption-desorption curve is an important method for characterizing porous materials. The specific surface area, pore volume and pore diameter of the highly crosslinked rosin-based polymeric microspheres were characterized in this study using a Micromeritics ASAP 2020M physical adsorption apparatus.
The laser particle sizer is an instrument that analyzes particle size by the spatial distribution of diffracted or scattered light (scattering spectrum) of the particles, and this study uses a Malvern laser particle sizer (Mastersizer 3000, Malvern, UK) to characterize the particle size of the highly crosslinked rosin-based polymeric microspheres.
Thermo gravimetric Analysis (TG), the thermal stability of the highly crosslinked rosin-based polymer microspheres is researched by adopting a Japanese Shimadzu DTA-60/60H type thermo gravimetric analyzer through the change of the weight loss rate along with the temperature programming.
The flow performance index of the chromatographic column is a curve for explaining the relation between the flow rate of the chromatographic column and the column pressure, and the chromatographic column does not deform in a set operation range, so that the packing has high mechanical strength and high pressure resistance.
(II) characterization of the results of the analysis
1. The scanning electron micrograph of the highly crosslinked rosin-based polymeric microspheres prepared in example 1 is shown in FIG. 1. As can be seen from figure 1, the highly crosslinked rosin-based polymeric microspheres prepared by the invention have the advantages of uniform size, rich surface pores, good sphericity and no adhesion phenomenon.
2. The nitrogen adsorption-desorption curve of the highly crosslinked rosin-based polymeric microspheres prepared in example 2 is shown in fig. 2. As can be seen from figure 2, the highly crosslinked rosin-based polymeric microspheres prepared by the method of the invention present a relatively obvious IV curve, and a hysteresis loop exists between the relative pressure of 0.4 and 0.9, which indicates that mesopores exist in the material.
3. The distribution diagram of the particle size of the highly crosslinked rosin-based polymeric microspheres prepared in example 3 is shown in fig. 3. As can be seen from FIG. 3, the particle size distribution of the highly crosslinked rosin-based polymeric microspheres prepared by the invention is concentrated at 2-10 μm, the distribution range is narrow, and the requirements of the high performance liquid chromatography stationary phase can be met.
4. The thermal weight loss curve of the highly crosslinked rosin-based polymeric microspheres prepared in example 4 is shown in fig. 4. As can be seen from FIG. 4, the high-crosslinked rosin-based polymeric microspheres prepared by the invention have good thermal stability, start to decompose at about 350 ℃ and completely decompose at about 500 ℃, and have weight loss rate of more than 95%.
5. The flow-through performance evaluation of the highly crosslinked rosin-based polymeric microspheres prepared in example 5 is shown in fig. 5. As can be seen from FIG. 5, the highly crosslinked rosin-based polymeric microspheres prepared by the invention, as a chromatographic stationary phase, show a good linear relationship with the column pressure within the flow rate range of 0-2 mL/min.
Comparative application example 1 separation of notoginsenoside in Panax notoginseng saponins by C18 chromatographic column
C18 chromatography column, commercially available.
Acetonitrile water is used as a mobile phase, the detection wavelength is set to be 203nm, the column temperature is set to be 25 ℃, and the flow rate is set to be 1.5 mL/min. Starting a sample injection valve to introduce the sample into the C18 chromatographic column by using acetonitrile water, wherein the sample injection amount is 20 mu L, and the notoginsenoside in the notoginsenoside is separated, and the separation degree is 0.56.
Comparative application example 2 separation of notoginsenoside in Panax notoginsenosides by using a weakly polar rosin-based polymeric chromatography column
The low-polarity rosin-based polymer chromatographic column is prepared according to the method disclosed by the invention patent application with the application number of 201710710292.1.
Acetonitrile water is used as a mobile phase, the detection wavelength is set to be 203nm, the column temperature is 25 ℃, and the flow rate is 1.5 mL/min. Starting a sample injection valve to introduce the sample into the rosin-based polymer chromatographic column by using acetonitrile water, wherein the sample injection amount is 20 mu L, and separating the notoginsenoside in the panax notoginseng saponins, wherein the separation degree is 2.18.
Application example 1 separation of Panax notoginsenosides in Panax notoginsenosides by use of highly crosslinked rosin-based polymeric chromatography column
Taking the highly crosslinked rosin-based polymer microspheres obtained in the preparation example 1 as stationary phase filler, and preparing a highly crosslinked rosin-based polymer chromatographic column by adopting wet column packing; the high-crosslinked rosin-based polymer chromatographic column is connected to a liquid chromatograph, and the column loading pressure is 3000-; using acetonitrile water as a mobile phase, setting the detection wavelength to be 203nm, the column temperature to be 35 +/-10 ℃, and the flow rate of the mobile phase to be 1.0-2.0 mL/min; starting a sample injection valve to lead the acetonitrile water to bring the panax notoginseng saponins into the rosin-based polymer chromatographic column with high crosslinking degree, thus realizing the separation of the panax notoginseng saponins. The obtained results are shown in FIG. 6, wherein the sanchinoside Rg1 appeared at retention time of 15.56min, and the sanchinoside Re peak appeared at retention time of 18.71min, with a separation degree of 3.36.
Therefore, the separation effect of the highly crosslinked rosin-based polymer chromatographic column on notoginsenoside in the panax notoginseng saponins is far better than that of a C18 chromatographic column under the same chromatographic condition, and is also better than that of a weakly polar rosin-based polymer chromatographic column under the same chromatographic condition.
Claims (7)
1. A high-crosslinking rosin-based polymer microsphere is characterized in that the high-crosslinking rosin-based polymer microsphere is formed by crosslinking and polymerizing methyl methacrylate and fumaropimaric acid tri (ethylene glycol acrylate),
the structural formula of the fumaropimaric acid tri (ethylene glycol acrylate) ester is as follows:
the structural formula of the highly crosslinked rosin-based polymer microsphere is as follows:
wherein R is:
；
the highly crosslinked rosin-based polymer microsphere has an acid value of less than or equal to 1mgKOH/g resin, is a spherical porous material, has a particle size distribution of 2-10 mu m, an average pore diameter of 12-28nm and a specific surface area of 32-102m2/g。
2. The method for preparing the highly crosslinked rosin-based polymeric microspheres according to claim 1, wherein the highly crosslinked rosin-based polymeric microspheres are prepared by a membrane emulsification-microsuspension polymerization method with methyl methacrylate as a functional monomer and tris (ethylene glycol acrylate) fumarate as a crosslinking agent, and the reaction formula is as follows:
3. the method for preparing the highly crosslinked rosin-based polymeric microspheres according to claim 2, wherein the film emulsification-microsuspension polymerization method specifically comprises: mixing a water phase consisting of deionized water and polyvinyl alcohol with an oil phase consisting of methyl methacrylate, a cross-linking agent of fumaric pimaric acid tri (ethylene glycol acrylate) ester, a solvent of chloroform and an initiator of azobisisobutyronitrile, emulsifying by using a film emulsifying machine to obtain a pre-emulsion, and then heating and polymerizing to obtain the high-crosslinked rosin-based polymer microsphere.
4. The method for preparing a highly crosslinked rosin-based polymeric microsphere according to claim 3, wherein the temperature-rising polymerization reaction is a temperature-programmed reaction at 70-80 ℃ for 60-120min, a reaction at 80-85 ℃ for 60-120min, and a reaction at 95-100 ℃ for 60-120 min.
5. The method for preparing the highly crosslinked rosin-based polymeric microspheres according to claim 3, wherein the mass ratio of the deionized water to the polyvinyl alcohol in the aqueous phase is 50: 0.1 to 2.
6. The preparation method of the highly crosslinked rosin-based polymeric microspheres according to claim 5, wherein the mass ratio of methyl methacrylate, fumaropimaric acid tri (ethylene glycol acrylate), chloroform, and azobisisobutyronitrile in the oil phase is 1-30: 6: 20-100: 0.1 to 5.
7. The use of the highly crosslinked rosin-based polymeric microspheres according to claim 1 or the highly crosslinked rosin-based polymeric microspheres prepared by the method according to any one of claims 2 to 6, wherein the highly crosslinked rosin-based polymeric microspheres are used as a stationary phase filler, and are subjected to wet column packing to prepare a highly crosslinked rosin-based polymeric chromatographic column; the high-crosslinked rosin-based polymer chromatographic column is connected to a liquid chromatograph, and the column loading pressure is 3000-; setting the flow rate of a mobile phase of a liquid chromatograph to be 1.0-2.0mL/min, the detection wavelength to be 203nm and the column temperature to be 35 +/-10 ℃; starting a sample injection valve to enable the mobile phase to bring the panax notoginseng saponins into the rosin-based polymer chromatographic column with high crosslinking degree, thereby realizing the separation of the panax notoginseng saponins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911040979.4A CN110627947B (en) | 2019-10-30 | 2019-10-30 | High-crosslinking rosin-based polymer microsphere and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911040979.4A CN110627947B (en) | 2019-10-30 | 2019-10-30 | High-crosslinking rosin-based polymer microsphere and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110627947A CN110627947A (en) | 2019-12-31 |
| CN110627947B true CN110627947B (en) | 2022-05-20 |
Family
ID=68978499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911040979.4A Active CN110627947B (en) | 2019-10-30 | 2019-10-30 | High-crosslinking rosin-based polymer microsphere and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110627947B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057958B (en) * | 2022-01-10 | 2023-03-24 | 广西民族大学 | Hydrogenated rosin-based macroporous adsorption resin and preparation method and application thereof |
| CN114835836A (en) * | 2022-04-12 | 2022-08-02 | 广西民族大学 | Core-shell SiO 2 @ rosin-based polymer anion exchange resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565732A (en) * | 2016-12-08 | 2017-04-19 | 广西民族大学 | Method for separating camptothecin and 10-hydroxycamptothecin by adoption of rosin-based macromolecules |
| CN107529536A (en) * | 2017-08-18 | 2018-01-02 | 广西民族大学 | A kind of low pole rosinyl polymer microsphere and its preparation method and application |
| CN109651387A (en) * | 2018-12-13 | 2019-04-19 | 广西民族大学 | A kind of hud typed SiO of application2The method that@rosin based high molecular chromatographic column efficiently separates camptothecine and 10-hydroxycamptothecine |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59170165A (en) * | 1983-03-17 | 1984-09-26 | Nippon Shokubai Kagaku Kogyo Co Ltd | Ultraviolet curing composition |
| JP2980009B2 (en) * | 1995-08-22 | 1999-11-22 | 荒川化学工業株式会社 | Rosin derivative and method for producing the same |
| JP4505661B1 (en) * | 2008-12-19 | 2010-07-21 | 日東化成株式会社 | Antifouling paint composition, antifouling coating film formed using the composition, coated product having the coating film on the surface, and antifouling treatment method for forming the coating film |
| US9896537B2 (en) * | 2013-07-08 | 2018-02-20 | Hui Yu | Norbornanyl rosin resin and process for preparing same |
-
2019
- 2019-10-30 CN CN201911040979.4A patent/CN110627947B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565732A (en) * | 2016-12-08 | 2017-04-19 | 广西民族大学 | Method for separating camptothecin and 10-hydroxycamptothecin by adoption of rosin-based macromolecules |
| CN107529536A (en) * | 2017-08-18 | 2018-01-02 | 广西民族大学 | A kind of low pole rosinyl polymer microsphere and its preparation method and application |
| CN109651387A (en) * | 2018-12-13 | 2019-04-19 | 广西民族大学 | A kind of hud typed SiO of application2The method that@rosin based high molecular chromatographic column efficiently separates camptothecine and 10-hydroxycamptothecine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110627947A (en) | 2019-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | Application of deep eutectic solvents in chromatography: A review | |
| CN107529536B (en) | Weak-polarity rosin-based polymer microsphere and preparation method and application thereof | |
| CN110627947B (en) | High-crosslinking rosin-based polymer microsphere and preparation method and application thereof | |
| Liu et al. | A review of the design of packing materials for ion chromatography | |
| CN104785225A (en) | Method for preparing antiphase weak anion exchange mixed mode chromatographic stationary phase by using organic polymer as substrate | |
| Du et al. | Enrichment and purification of total flavonoid C-glycosides from Abrus mollis extracts with macroporous resins | |
| Cong et al. | Preparation of porous sulfonated poly (styrene-divinylbenzene) microspheres and its application in hydrophilic and chiral separation | |
| WO2008064525A1 (en) | A super macroporous polymeric microsphere and preparation process thereof | |
| CN105616709A (en) | Novel technology for extracting tea polyphenol in tea leaves | |
| CN105669782A (en) | Method for solid-phase extraction of flavonoid compounds in radix puerariae | |
| CN102936355B (en) | Preparation method of crosslinked polymethyl methacrylate resin microspheres with narrow particle size distribution | |
| Dong et al. | Boronate affinity monolith via two-step atom transfer radical polymerization for specific capture of cis-diol-containing compounds | |
| CN106046254B (en) | It is enriched with the hydrophilic molecular engram polymer and preparation method and application of geniposide | |
| Luo et al. | Preparation and application of molecularly imprinted polymers for the selective extraction of naringin and genistein from herbal medicines | |
| CN106046256A (en) | Method for preparing geniposide molecularly imprinted polymer magnetic microspheres | |
| CN1045610C (en) | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs | |
| Yu et al. | Diazoresin modified monodisperse porous poly (glycidylmethacrylate-co-divinylbenzene) microspheres as the stationary phase for high performance liquid chromatography | |
| CN107163170A (en) | Core-shell polymers chromatographic media of single dispersing porous surface and preparation method thereof | |
| Wang et al. | Extraction of geniposidic acid and aucubin employing aqueous two-phase systems comprising ionic liquids and salts | |
| CN105664886A (en) | Preparation method of weak acid cation exchange stationary phase | |
| CN101260138B (en) | Highly effective separation purification method for polygalic acid and tenuigenin | |
| CN104788609A (en) | Highly cross-linked monodisperse epoxy-group-containing polymeric microsphere and preparation method thereof | |
| CN102936306B (en) | The preparation method of the cross-linked polystyrene resin microballoon of narrow size distribution | |
| CN104558446A (en) | Porous silica gel microsphere surface tripterygium wilfordii extract molecularly imprinted polymer and preparation and application thereof | |
| CN107096509A (en) | The sephadex and preparation method of a kind of succinic acid of amido containing α function base |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |