CN109115928B - Porous polymer coating capillary chromatographic column and preparation and application methods thereof - Google Patents
Porous polymer coating capillary chromatographic column and preparation and application methods thereof Download PDFInfo
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- CN109115928B CN109115928B CN201811276897.5A CN201811276897A CN109115928B CN 109115928 B CN109115928 B CN 109115928B CN 201811276897 A CN201811276897 A CN 201811276897A CN 109115928 B CN109115928 B CN 109115928B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
- G01N30/6073—Construction of the column body in open tubular form
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
- G01N2030/567—Packing methods or coating methods coating
Abstract
The invention provides a porous polymer coating capillary chromatographic column which comprises a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube, wherein the porous polymer coating is a cross-linked porous polymer microsphere formed by taking kerosene as a pore-forming agent to participate in the polymerization reaction of polymer monomers. The invention also provides a preparation method of the porous polymer coating capillary chromatographic column, which takes pure kerosene as a pore-foaming agent to participate in the polymerization reaction of polymer monomers to generate porous polymer microspheres on the inner wall of the chromatographic column. The invention also provides a porous polymer coating capillary chromatographic column prepared by the preparation method. The capillary chromatographic column in the prior art has the technical problems of high production cost and poor separation effect when being used for separating and analyzing low-carbon hydrocarbons C1-C4, and the inventor finds that the porous polymer generated by using kerosene as a pore-foaming agent can effectively separate the low-carbon hydrocarbons C1-C4, the obtained chromatogram has high separation degree, and the standard front and the tail of the peak shape are small.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a porous polymer coating capillary chromatographic column and a preparation method thereof.
Background
The porous polymer gas chromatography stationary phase is formed into a porous structure macromolecule ball by heat treatment of crosslinked macromolecules obtained by suspension copolymerization of styrene-divinylbenzene, and the modification and application research of the porous polymer gas chromatography stationary phase in China is limited to a gas-phase packed column at present. With the development of chromatographic technology, the stationary phase membrane of the capillary gas chromatographic column is uniform, the column efficiency is high, and the capillary gas chromatographic column is easy to coat and prepare, so that the capillary gas chromatographic column is gradually replacing the use of a packed column, and the production of the packed column is stopped by foreign analytical instrument manufacturers.
The stationary phase of the gas-solid adsorption capillary chromatographic column adopts some adsorption materials with special separation characteristics to replace macromolecular stationary liquid, has good selectivity and higher separation degree, simultaneously has the advantages of rapidness and high efficiency of capillary chromatography, and is an important column type for solving the problem of difficult separation of components. At present, inorganic adsorption materials are mostly adopted for the stationary phase of the gas-solid adsorption capillary chromatographic column, and the research on the stationary phase of the porous polymer capillary chromatographic column is less. Therefore, the porous polymer capillary chromatographic column has limited varieties, has the defects of non-ideal separation of specific components and serious tailing of chromatographic peaks, and cannot well meet the requirements of practical experimental analysis.
The pore structure of the porous polymer has great influence on the chemical and physical properties of the porous polymer and has close relation with the final chromatographic characteristics of the porous polymer. The pore-foaming agent plays an important role in the formation process of the high polymer small spheres, and the key to the successful preparation of the high polymer capillary column lies in the selection of the pore-foaming agent during synthesis. The kerosene is a high-boiling-point hydrocarbon mixture with carbon atoms of C11-C17, the main component is saturated hydrocarbon, and the pure kerosene is colorless transparent liquid, is insoluble in water and is easily soluble in alcohol and other organic solvents. After a plurality of experiments, the kerosene used as the pore-foaming agent can obtain good effect when being used for preparing the porous polymer and being subjected to chromatographic analysis by using the porous polymer, and compared with other pore-foaming agents, the kerosene has low price and relatively low toxicity, and is an excellent mixed pore-foaming agent.
Chinese patent CN104001487A discloses a preparation method of GDX porous polymer series hollow capillary gas chromatography column. The patent uses styrene and divinyl benzene as polymer monomers to prepare suspension, so that the suspension is subjected to in-situ polymerization reaction in a chromatographic column tube, and then a capillary chromatographic column with a high-molecular small ball with a porous structure on the inner wall is produced through heat treatment. The high molecular beads with porous structures in the method are styrene-divinylbenzene polymers with specific molecular weights and pore diameter structures, and can be used for analysis of gas, aldehyde, ether, ester and acid, but the pore structures of the high molecular beads determine that the chromatographic column in the patent is not suitable for analysis of low-carbon hydrocarbons C1-C4, namely the chromatographic column is not suitable for analysis of hydrocarbon substances containing one carbon atom to hydrocarbon substances containing four carbon atoms, the separation effect is poor, and a plurality of isomers are not separated. Because C1-C4 hydrocarbon substance isomer is many, the nature is close, except alumina gas chromatographic column does not have any other chromatographic column to carry on the complete separation to all isomers under C4 at present, the ordinary GDX porous polymer series hollow capillary tube gas chromatographic column water resistance is good to analyzing the performance of the aqueous alcohol substance is excellent, therefore mainly used for the aqueous sample, but this type chromatographic column is poor to the separation effect of the hydrocarbon substance under C4, make porogenic agent raw materials price of the porous polymer higher at the same time, the production cost is big. The invention can make up the defects of the GDX porous polymer series hollow capillary gas chromatographic column in the aspect, well separate low-carbon hydrocarbon substances and reduce the production cost at the same time.
Disclosure of Invention
In order to solve the technical problems of high production cost and poor separation effect, serious tailing of chromatographic peak, difficult separation of isomers and the like when the method is used for separation and analysis of low-carbon hydrocarbon C1-C4 in the prior art, the inventor finds that a porous polymer generated by using kerosene as a pore-forming agent can effectively separate analysis of the low-carbon hydrocarbon C1-C4, the obtained chromatogram has high separation degree, the standard leading edge and tailing of the peak shape are small, the kerosene pore-forming agent can participate in polymerization reaction of various polymer monomers, and good effects can be achieved when different polymer coatings are used for detection of a mixture sample containing the low-carbon hydrocarbon. In addition, the kerosene is low in price, and the production cost can be reduced by using the kerosene as a pore-foaming agent. Based on the above findings, the present invention has been completed.
Accordingly, the present invention provides a porous polymer coated capillary chromatography column.
The invention also provides a preparation method of the porous polymer coating capillary chromatographic column.
The invention also provides the porous polymer coating capillary chromatographic column prepared by the preparation method.
The porous polymer coating capillary chromatographic column comprises a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube, wherein the chromatographic column tube is a quartz capillary column tube, the porous polymer coating is a crosslinked porous polymer microsphere formed by the polymerization reaction of pure kerosene serving as a pore-foaming agent and polymer monomers, and the content of the pure kerosene serving as the pore-foaming agent is more than 5% of the mass of the total reaction system.
Preferably, the content of the pure kerosene serving as the pore-foaming agent is 10-25% of the mass of the total reaction system.
Further, the pure kerosene comprises jet fuel.
The aviation kerosene is a distillate of kerosene at 150-280 ℃, has high cleanliness, no harmful substances such as mechanical impurities and moisture and the like, has low sulfur content, particularly low thiol sulfur content, and can be directly used as a pore-foaming agent as the existing product.
Furthermore, the polymer monomer is formed by combining divinylbenzene and any one or more of styrene, vinyl pyrrolidone, trichloroethylene and vinyl pyridine. Different monomers are selected to be used for polymer synthesis according to analysis requirements, so that the chromatographic analysis effect of the porous polymer coating is improved.
The invention also provides a preparation method of the porous polymer coating capillary chromatographic column, which comprises the following steps:
(1) pretreating the quartz capillary column tube, leaching the inner wall of the quartz capillary column tube with hydrofluoric acid solution or other reducing acid, leaching the inner wall of the quartz capillary column tube with distilled water or deionized water, introducing dry inert gas into the quartz capillary column tube for purging, placing the quartz capillary column tube in a heating device, adjusting the temperature to 300-350 ℃, and baking for 7-12 hours to obtain the pretreated quartz capillary column tube;
(2) dispersing styrene-divinylbenzene copolymer in dispersant, ultrasonic stirring for more than 50min, and preparing styrene-divinylbenzene initial polymer seed suspension liquid with mass concentration of 3-5%. Then pressing the styrene-divinylbenzene initial polymer seed suspension into the pretreated quartz capillary column tube under the protection of dry inert gas to obtain the quartz capillary column tube with the inner wall coated with the polymer seeds;
(3) distilling kerosene, taking 150-280 ℃ distillate, using the pure kerosene of the distillate as a pore-forming agent, dissolving a polymer monomer in the pure kerosene to prepare a polymerization monomer suspension with the mass concentration of 5-10%, and ultrasonically mixing for 30-50 minutes;
(4) pressing the cross-linking polymerization monomer suspension into a quartz capillary column tube with the inner wall coated with polymer seeds at a constant flow rate under the protection of dry inert gas, and sealing an outlet of the quartz capillary column tube with the inner wall coated with the polymer seeds after the quartz capillary column tube with the inner wall coated with the polymer seeds is filled with the polymerization monomer suspension to obtain the quartz capillary column tube coated with the polymer monomers;
(5) standing the quartz capillary column tube coated with the polymer monomer in a water bath device to perform in-situ polymerization reaction, then taking out the end socket, introducing dry inert gas into the quartz capillary column tube coated with the polymer monomer to blow the wet coating to dry, and generating a white polymer coating on the inner wall of the quartz capillary column tube coated with the polymer monomer after blow-drying to obtain the porous polymer coating capillary chromatographic column to be aged;
(6) and introducing dry inert gas into the porous polymer coating capillary chromatographic column to be aged, meanwhile, placing the quartz capillary column tube in a heating device, adjusting the temperature to 200-350 ℃, and baking for 6-12 hours to obtain the porous polymer coating capillary chromatographic column.
Further, the dispersing agent in the step (2) is a toluene solution of any one of polypropylene and polystyrene with a volume concentration of 2-5%.
The toluene has good solubility for the porous polymer, the boiling point is suitable for the high-order polymerization reaction of the porous polymer and can not boil, and the volatility of the toluene is suitable for the preparation of the invention, so that the toluene is not easy to be dried quickly and can be removed quickly under the premise of full reaction.
Further, in the step (3), the porous polymer monomer is formed by combining divinylbenzene and any one or more of styrene, vinyl pyrrolidone, trichloroethylene and vinyl pyridine.
Different monomers are selected according to analysis requirements for polymer synthesis, so that the chromatographic analysis effect of the porous polymer coating is improved.
Optionally, in the step (3), a polymer monomer is directly dissolved in aviation kerosene serving as a pore-forming agent, wherein the content of the aviation kerosene is 5% -25% of the total reaction system by mass, a polymerization monomer suspension with the mass concentration of 5-10% is prepared, and the polymerization monomer suspension is ultrasonically mixed for 30-50 minutes.
The aviation kerosene is a distillate of kerosene at 150-280 ℃, has high cleanliness, no harmful substances such as mechanical impurities and moisture, and low sulfur content, particularly low thiol sulfur content, can be directly used as a pore-foaming agent as the existing product, and the distillation step in the step (3) is omitted.
Further, the reaction temperature of the water bath device subjected to in-situ polymerization in the step (5) is 68-72 ℃, and the reaction time is 6-8 hours; the specific operation steps of blowing dry nitrogen to blow dry the wet coating are firstly blowing for 30-60 minutes under 0.5-1.5 Mpa, and then blowing for 2-4 hours under the pressure of 0.08-0.15 Mpa.
The invention also provides a porous polymer coating capillary chromatographic column which is prepared by the preparation method provided by the invention.
Compared with the prior art, the invention has the following advantages:
1. the porous polymer coating capillary chromatographic column provided by the invention has the advantages that the coating is a cross-linked porous polymer microsphere formed by taking kerosene as a pore-forming agent to participate in the polymerization reaction of porous polymer monomers. Because C1-C4 hydrocarbon substance has more isomers and close properties, no other chromatographic column except an alumina gas chromatographic column can withdraw all isomers below C4 for complete separation at present, kerosene is used as a mixed pore-forming agent, and the hydrocarbon substance of C1-C4 can be effectively separated by using a porous polymer formed by the participation of the kerosene in polymerization reaction, so that the defects of analysis and detection of the capillary gas chromatographic column on the aspect are overcome.
2. The pore-foaming agent used in the prior art is mostly a multi-carbon organic solvent, the price is high, the use cost is high, and the kerosene is used as the pore-foaming agent, so that the production cost can be effectively reduced.
3. The coating of the porous polymer coating capillary chromatographic column provided by the invention is a cross-linked high molecular compound, has good thermal stability, no column loss in a high temperature range and high corrosion resistance, and improves the reproducibility of a separation method and the service life of the chromatographic column.
Additional features and corresponding advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described as follows:
FIG. 1 is a chromatogram obtained by chromatography of a lower hydrocarbon using the column provided in example 1;
FIG. 2 is a chromatogram obtained from the chromatographic analysis of a lower hydrocarbon using the column provided in example 2;
FIG. 3 is a chromatogram obtained from the chromatographic analysis of a lower hydrocarbon using the column provided in example 3;
FIG. 4 is a chromatogram obtained from the chromatographic analysis of a lower hydrocarbon using the column provided in example 4;
FIG. 5 is a chromatogram obtained from the chromatographic analysis of a lower hydrocarbon using the column provided in example 5;
fig. 6 is a chromatogram obtained by performing a chromatographic analysis of a lower hydrocarbon using the column provided in comparative example 1.
Detailed Description
The present invention is described in further detail with reference to the following embodiments, which are not intended to limit the invention, and those skilled in the art can make various modifications and improvements based on the basic idea of the invention, but within the scope of the invention, unless departing from the basic idea of the invention.
In the description of the present invention, unless otherwise specified, terms in the present specification have the same meaning as those generally understood by those skilled in the art, but if different, the definitions in the present specification shall control; unless otherwise specified, the test methods are all conventional methods; unless otherwise specified, the raw materials and test materials used in the present specification are all available commercially in a conventional manner; unless otherwise specified, the percentages (%) in this specification are mass percentages (% by mass).
Example 1:
a quartz capillary column tube having a length of 30m and an inner diameter of 0.32mm was prepared, and the dry inert gas used in this example was dry nitrogen gas. And (2) leaching the inner wall of the quartz capillary column tube with hydrofluoric acid solution, then leaching the inner wall of the quartz capillary column tube with deionized water, then introducing dry nitrogen into the quartz capillary column tube for purging, meanwhile, placing the quartz capillary column tube in a heating device, adjusting the temperature to 350 ℃, and baking for 7 hours to obtain the pretreated quartz capillary column tube.
Dispersing a styrene-divinylbenzene copolymer in a dispersing agent, and ultrasonically stirring for 1 hour to prepare a styrene-divinylbenzene initial polymer seed suspension with the mass concentration of 5%, wherein the dispersing agent is a toluene solution of polystyrene with the volume concentration of 3.5%. Then, the styrene-divinylbenzene initial polymer seed suspension was pressed into the pretreated quartz capillary column tube with dry nitrogen gas under a pressure of 0.5Mpa using a high-pressure coating apparatus to obtain a quartz capillary column tube having an inner wall coated with polymer seeds. It is to be understood that the high-pressure coating apparatus is an apparatus in which a coating liquid container is provided in a closed container, one end of a column is inserted into the closed container and is introduced with the coating liquid, and then the coating liquid is pressed into the column by pressurizing the closed container.
Distilling kerosene, taking 150-280 ℃ distillate, using the pure kerosene of the distillate as a pore-forming agent, dissolving a polymer monomer in the pure kerosene as the pore-forming agent, wherein the content of the pore-forming agent is 5% of the mass of the total reaction system, preparing a polymerization monomer suspension with the mass concentration of 10%, and placing the polymerization monomer suspension into an ultrasonic dispersion instrument for ultrasonic mixing and dispersion for 50min, wherein the polymer monomer is divinylbenzene and styrene with the mass ratio of 1:1 in the embodiment.
And then pressing the cross-linking polymerization reaction monomer suspension into the pretreated quartz capillary column tube by using dry nitrogen in a closed environment, controlling the pressure of the dry nitrogen to be constant at 0.5Mpa, so that a liquid plug formed by the cross-linking polymerization reaction monomer suspension in the pretreated quartz capillary column tube keeps constant and uniform coating speed in the pretreated quartz capillary column tube and flows until the liquid plug is completely pressed out, and sealing the outlet end after the liquid plug is pressed out from the outlet end to obtain the quartz capillary column tube coated with the polymer monomer.
Standing the quartz capillary column tube coated with the polymer monomer in a water bath device to perform in-situ polymerization reaction at 72 ℃ for 6 hours, introducing dry nitrogen into the quartz capillary column tube coated with the polymer monomer, blowing the dry nitrogen at 1.5MPa for 30 minutes, then regulating the pressure to 0.15MPa for blowing for 2 hours, finally blowing the wet coating to dry, and generating a white polymer coating on the inner wall of the quartz capillary column tube coated with the polymer monomer after drying, thereby obtaining the porous polymer coating capillary chromatographic column to be aged.
And introducing dry nitrogen into the porous polymer coating capillary chromatographic column to be aged, simultaneously placing the quartz capillary column tube into a heating device, adjusting the temperature to 350 ℃, and baking for 6 hours to obtain the porous polymer coating capillary chromatographic column.
The chromatographic column manufactured by the method is the porous polymer coating capillary chromatographic column provided by the invention. The porous polymer coating capillary chromatographic column provided by the embodiment comprises a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube. The chromatographic column tube is a quartz capillary column tube with the length of 15m and the inner diameter of 0.25mm, the porous polymer coating is an organic macromolecular porous polymer formed by the polymerization reaction of pure kerosene serving as a pore-forming agent and polymer monomers, the polymer monomers are divinylbenzene and styrene with the mass ratio of 1:1, and the content of the pore-forming agent is 5% of the mass of the total reaction system.
The porous polymer coating capillary chromatographic column in the embodiment is used for detecting samples such as methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne, the separation effect is evaluated, the chromatogram is shown in figure 1, the chromatographic conditions are shown in table 1, the evaluation data are shown in table 2, and the results are as follows:
TABLE 1
TABLE 2
As can be seen from fig. 1 and table 2: in the hydrocarbon substance containing two carbon atoms, ethylene is completely separated from ethylene, acetylene and ethane, and the acetylene and the ethane are not separated into a mixture chromatographic peak C2; in hydrocarbon substances containing three carbon atoms, propyne is successfully separated from propane, propylene, cyclopropane and propyne, and a chromatographic peak C3 of a mixture formed by the propane, the propylene and the cyclopropane is successfully separated from the propyne peak, and the propane, the propylene and the cyclopropane are not separated due to similar properties.
It is to be understood that the degree of separation is used to determine the separation of the substance to be separated in the chromatographic column, and is commonly used as an index of the overall separation performance of the column. The separation degree is equal to the ratio of the difference of retention time of adjacent chromatographic peaks to the width average value of the two chromatographic peaks, and represents the separation degree of the two adjacent peaks. The larger the separation degree is, the better the separation effect of two adjacent components is.
Example 2:
example 1 was repeated except that the porogen content was 10% by mass of the total reaction system.
The porous polymer coating capillary chromatographic column in the embodiment is used for detecting samples such as methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne, the separation effect is evaluated, the chromatogram is shown in figure 2, the chromatographic conditions are shown in table 3, the evaluation data are shown in table 4, and the results are as follows:
TABLE 3
TABLE 4
| Peak name | Retention time | Degree of separation |
| Methane | 4.52 | 12.74 |
| Ethylene | 5.69 | 3.28 |
| C2 (ethane and acetylene) | 6.13 | 20.85 |
| Propylene (PA) | 10.83 | 2.17 |
| C3' (propane, propylene and cyclopropane) | 11.35 | 6.91 |
| Propyne | 12.42 | 0 |
As can be seen from fig. 2 and table 4: in the hydrocarbon substance containing two carbon atoms, ethylene is completely separated from ethylene, acetylene and ethane, and the acetylene and the ethane are not separated into a mixture chromatographic peak C2; in the hydrocarbon substance containing three carbon atoms, the propyne was kept separated, propylene was successfully separated from propane, cyclopropane and propylene glycol, which had not been separated yet, to form a mixed chromatographic peak C31, in comparison with the evaluation results in example 1.
Example 3:
example 1 was repeated except that the porogen content was 15% by mass of the total reaction system.
The porous polymer coating capillary chromatographic column in the embodiment is used for detecting samples such as methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne, the separation effect is evaluated, the chromatogram is shown in figure 3, the chromatographic conditions are shown in table 5, the evaluation data are shown in table 6, and the results are as follows:
TABLE 5
TABLE 6
| Peak name | Retention time | Degree of separation |
| Methane | 4.52 | 12.74 |
| Ethylene | 5.69 | 3.28 |
| C2 (ethane and acetylene) | 6.13 | 20.85 |
| Propylene (PA) | 10.83 | 2.61 |
| Propane | 11.52 | 1.79 |
| Propylene glycol | 11.78 | 0.72 |
| Cyclopropane | 11.93 | 4.21 |
| Propyne | 12.54 | 0 |
As can be seen from fig. 3 and table 6: in the hydrocarbon substance containing two carbon atoms, ethylene is completely separated from ethylene, acetylene and ethane, and the acetylene and the ethane are not separated into a mixture chromatographic peak C2; in hydrocarbon substances containing three carbon atoms, propylene, propane, propylene diene, cyclopropane and propyne are all separated, but the separation degree of the propylene diene and the cyclopropane is poor, and a certain tail exists between two chromatographic peaks of the propane and the propylene diene.
Example 4:
example 1 was repeated except that the porogen content was 25% by mass of the total reaction system.
The porous polymer coating capillary chromatographic column in the embodiment is used for detecting samples such as methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne, the separation effect is evaluated, the chromatogram is shown in figure 4, the chromatographic conditions are shown in table 7, the evaluation data are shown in table 8, and the results are as follows:
TABLE 7
TABLE 8
| Peak name | Retention time | Degree of separation |
| Methane | 4.50 | 7.26 |
| Ethylene | 5.68 | 2.75 |
| Acetylene | 6.04 | 0.43 |
| Ethane (III) | 6.16 | 30.66 |
| Propylene (PA) | 10.93 | 3.21 |
| Propane | 11.52 | 2.65 |
| Propylene glycol | 12.07 | 1.49 |
| Cyclopropane | 12.39 | 5.62 |
| Propyne | 12.97 | 0 |
As can be seen from fig. 4 and table 8, the samples to be tested were all effectively separated from methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne.
Example 5:
example 1 was repeated except that the porogen content was 35% by mass of the total reaction system.
The porous polymer coating capillary chromatographic column in the embodiment is used for detecting samples such as methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne, the separation effect is evaluated, the chromatogram is shown in figure 5, the chromatographic conditions are shown in table 9, the evaluation data are shown in table 10, and the results are as follows:
TABLE 9
As can be seen from fig. 5 and table 10, the samples to be tested were all effectively separated from methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne. In this example, compared with the chromatogram obtained by detecting the sample by the porous polymer coating capillary chromatographic column provided in example 4, the difference of retention time is slightly increased, the peak width is increased, the difference of the resolution is not large, but the consumption of the pore-forming agent is large, so that the effect of using kerosene as the pore-forming agent is the best when the content is 25% of the total reaction system quality.
Comparative example 1:
the porous polymer capillary gas chromatographic column is prepared according to the method described in the prior art and is connected to a chromatograph for evaluation. For example, a quartz capillary column having an inner diameter of 0.32mm and a length of 35m was prepared, the inner wall of the column tube was passivated with hydrofluoric acid, and then a styrene-divinylbenzene copolymer seed suspension having a mass concentration of 5% was coated in the column. And then, taking an n-heptane solution as a pore-foaming agent, dissolving styrene and divinylbenzene with the mass ratio of 1:1 in the pore-foaming agent, fully mixing, adding ethylene glycol acrylate, and then loading the mixed solution into a chromatographic column. Finally, the chromatographic column is put into a water bath device at 60 ℃ for reaction for 24 hours and then aged.
The porous polymer coating capillary chromatographic column in the comparative example is used for detecting samples such as methane, ethylene, acetylene, ethane, propylene, propane, propylene, cyclopropane and propyne, the separation effect is evaluated, the chromatogram is shown in figure 6, the chromatographic conditions are shown in table 11, the evaluation data are shown in table 12, and the results are as follows:
TABLE 11
TABLE 12
As can be seen from fig. 6 and table 12, in the case where kerosene is not used as a pore-forming agent, the compounds having the same carbon number are difficult to separate, and the hydrocarbon substances containing two carbon atoms, ethylene, ethane and acetylene, in the sample to be measured are not separated, so as to form a mixed peak C2'; the hydrocarbon substances containing three carbon atoms, propane, propylene diene, cyclopropane and propyne are not separated, and a mixed peak C3' is formed.
Evaluation and analysis:
in comparative example 1, the compounds having the same carbon number were difficult to separate, and hydrocarbons having two carbon atoms and hydrocarbons having three carbon atoms were not separated in the sample to be measured. In example 1, when the pure kerosene content was 5% by mass of the total reaction system, ethylene was completely separated from ethylene, acetylene and ethane in a hydrocarbon substance containing two carbon atoms; in hydrocarbon materials containing three carbon atoms, propyne is effectively separated from propane, propylene glycol, cyclopropane and propyne. In example 2, when the pure kerosene content was 10% by mass of the total reaction system, ethylene was completely separated from ethylene, acetylene and ethane in a hydrocarbon substance containing two carbon atoms; in the hydrocarbon substance containing three carbon atoms, propyne was kept separated and propylene was successfully separated from propane, cyclopropane and propylene glycol, as compared with the evaluation results in example 1. In example 3, when the pure kerosene content was 15% by mass of the total reaction system, ethylene was completely separated from ethylene, acetylene and ethane in a hydrocarbon substance containing two carbon atoms; in the hydrocarbon material containing three carbon atoms, propylene, propane, propylene diene, cyclopropane and propyne are separated from each other completely. In example 4, when the pure kerosene content was 25% by mass of the total reaction system, the two-carbon hydrocarbon substances ethylene, acetylene and ethane were effectively separated from each other, and the three-carbon hydrocarbon substances propylene, propane, propylene, cyclopropane and propyne were effectively separated from each other. In example 5, when the pure kerosene content was 35% by mass of the total reaction system, the two-carbon hydrocarbon substances ethylene, acetylene and ethane were effectively separated from each other, and the three-carbon hydrocarbon substances propylene, propane, propylene, cyclopropane and propyne were effectively separated from each other.
Compared with the comparative example 1, the porous polymer coating capillary chromatographic column in any one of the embodiments 1 to 5 provided by the invention has a greatly improved separation effect on the hydrocarbon substances with the same carbon number, so that the porous polymer coating capillary chromatographic column can effectively have a better separation effect on the low carbon hydrocarbon substances by taking pure kerosene as a pore-forming agent, and the defect of the capillary gas chromatographic column in analyzing and detecting the low carbon hydrocarbon substances is overcome.
Example 6:
example 1 was repeated with the following differences: the polymer monomers in this example are divinylbenzene, styrene, and vinyl pyrrolidone.
A quartz capillary column tube having a length of 15m and an inner diameter of 0.25mm was prepared, and the dry inert gas used in this example was dry helium. And (2) leaching the inner wall of the quartz capillary column tube with hydrofluoric acid solution, then leaching the inner wall of the quartz capillary column tube with deionized water, then introducing dry helium into the quartz capillary column tube for purging, meanwhile, placing the quartz capillary column tube in a heating device, adjusting the temperature to 325 ℃, and baking for 10 hours to obtain the pretreated quartz capillary column tube.
Dispersing a styrene-divinylbenzene copolymer in a dispersing agent, and ultrasonically stirring for 1 hour to prepare a styrene-divinylbenzene initial polymer seed suspension with the mass concentration of 4%, wherein the dispersing agent is a toluene solution of polystyrene with the volume concentration of 2%. Then, the styrene-divinylbenzene initial state polymer seed suspension was pressed into the pretreated quartz capillary column tube with dry helium gas under a pressure of 0.5Mpa using a high-pressure coating apparatus to obtain a quartz capillary column tube coated with polymer seeds on the inner wall. It is to be understood that the high-pressure coating apparatus is an apparatus in which a coating liquid container is provided in a closed container, one end of a column is inserted into the closed container and is introduced with the coating liquid, and then the coating liquid is pressed into the column by pressurizing the closed container.
Distilling kerosene, taking 150-280 ℃ distillate, using the pure kerosene of the distillate as a pore-forming agent, dissolving a porous polymer monomer in the pure kerosene as the pore-forming agent, wherein the content of the pore-forming agent is 5% of the mass of the total reaction system, preparing a polymerization monomer suspension with the mass concentration of 8%, and placing the polymerization monomer suspension into an ultrasonic dispersion instrument for ultrasonic mixing and dispersion for 40min, wherein the porous polymer monomer is divinylbenzene, styrene and vinyl pyrrolidone, and the mass ratio of the porous polymer monomer to the substance is 1:1:1 in the embodiment.
And then pressing the cross-linking polymerization reaction monomer suspension into the pretreated quartz capillary column tube by using dry helium in a closed environment, controlling the pressure of the dry helium to be constant at 0.5Mpa, so that a liquid plug formed by the cross-linking polymerization reaction monomer suspension in the pretreated quartz capillary column tube keeps constant and uniform coating speed in the pretreated quartz capillary column tube and flows until the liquid plug is completely pressed out, and sealing the outlet end after the liquid plug is pressed out from the outlet end to obtain the quartz capillary column tube coated with the polymer monomer.
Standing the quartz capillary column tube coated with the polymer monomer in a water bath device to perform in-situ polymerization reaction at the reaction temperature of 70 ℃ for 7 hours, introducing dry helium into the quartz capillary column tube coated with the polymer monomer, blowing the dry helium for 45 minutes at 1MPa, then reducing the pressure to 0.1MPa, blowing the dry helium for 3 hours, finally drying the wet coating, and generating a white polymer coating on the inner wall of the quartz capillary column tube coated with the polymer monomer after drying, thereby obtaining the porous polymer coating capillary chromatographic column to be aged.
And introducing dry helium into the porous polymer coating capillary chromatographic column to be aged, simultaneously placing the quartz capillary column tube into a heating device, adjusting the temperature to 270 ℃, and baking for 9 hours to obtain the porous polymer coating capillary chromatographic column.
The chromatographic column manufactured by the method is the porous polymer coating capillary chromatographic column provided by the invention. The porous polymer coating capillary chromatographic column provided by the embodiment comprises a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube. The chromatographic column tube is a quartz capillary column tube with the length of 30m and the inner diameter of 0.32mm, the porous polymer coating is an organic macromolecular porous polymer formed by the polymerization reaction of pure kerosene serving as a pore-forming agent and polymer monomers, and the polymer monomers are divinylbenzene, styrene and vinyl pyrrolidone with the mass ratio of 1:1: 1.
The porous polymer coating capillary chromatographic column provided by the embodiment has a greatly improved separation effect on hydrocarbon substances with the same carbon atom number, so that the porous polymer coating capillary chromatographic column can effectively have a good separation effect on the low carbon hydrocarbon substances by taking pure kerosene as a pore-forming agent, and the defect of analysis and detection on the low carbon hydrocarbon substances by the capillary gas chromatographic column is overcome. Meanwhile, the porous polymer coating formed by adding the vinyl pyrrolidone into the polymerization reaction monomer is beneficial to the separation of the oxygen-containing compound.
Example 7:
a quartz capillary column tube having a length of 50m and an inner diameter of 0.53mm was prepared, and the dry inert gas used in this example was dry helium. And (2) leaching the inner wall of the quartz capillary column tube with hydrofluoric acid solution, then leaching the inner wall of the quartz capillary column tube with deionized water, then introducing dry helium into the quartz capillary column tube for purging, meanwhile, placing the quartz capillary column tube in a heating device, adjusting the temperature to 300 ℃, and baking for 12 hours to obtain the pretreated quartz capillary column tube.
Dispersing a styrene-divinylbenzene copolymer in a dispersing agent, and ultrasonically stirring for 1 hour to prepare a styrene-divinylbenzene initial polymer seed suspension with the mass concentration of 3%, wherein the dispersing agent is a toluene solution of polypropylene with the volume concentration of 5%. Then, the styrene-divinylbenzene initial state polymer seed suspension was pressed into the pretreated quartz capillary column tube with dry helium gas under a pressure of 0.5Mpa using a high-pressure coating apparatus to obtain a quartz capillary column tube coated with polymer seeds on the inner wall. It is to be understood that the high-pressure coating apparatus is an apparatus in which a coating liquid container is provided in a closed container, one end of a column is inserted into the closed container and is introduced with the coating liquid, and then the coating liquid is pressed into the column by pressurizing the closed container.
Distilling pure kerosene, taking 150-280 ℃ distillate, using the pure kerosene of the distillate as a pore-forming agent, dissolving a porous polymer monomer in the pure kerosene as the pore-forming agent, wherein the content of the pore-forming agent is 5% of the mass of the total reaction system, preparing a polymerization monomer suspension with the mass concentration of 5%, and placing the polymerization monomer suspension into an ultrasonic dispersion instrument for ultrasonic mixing and dispersion for 30min, wherein the porous polymer monomer in the embodiment is divinylbenzene, styrene and trichloroethylene with the mass ratio of 1:1: 0.25.
And then pressing the cross-linking polymerization reaction monomer suspension into the pretreated quartz capillary column tube by using dry helium in a closed environment, controlling the pressure of the dry helium to be constant at 0.5Mpa, so that a liquid plug formed by the cross-linking polymerization reaction monomer suspension in the pretreated quartz capillary column tube keeps constant and uniform coating speed in the pretreated quartz capillary column tube and flows until the liquid plug is completely pressed out, and sealing the outlet end after the liquid plug is pressed out from the outlet end to obtain the quartz capillary column tube coated with the polymer monomer.
Standing the quartz capillary column tube coated with the polymer monomer in a water bath device to perform in-situ polymerization reaction at the reaction temperature of 68 ℃ for 8 hours, introducing dry helium into the quartz capillary column tube coated with the polymer monomer, blowing the dry helium for 60 minutes at 0.5MPa, then reducing the pressure to 0.08MPa, blowing the dry helium for 4 hours, finally blowing the wet coating to dry, and generating a white polymer coating on the inner wall of the quartz capillary column tube coated with the polymer monomer after drying, thereby obtaining the porous polymer coating capillary chromatographic column to be aged.
And introducing dry helium into the porous polymer coating capillary chromatographic column to be aged, simultaneously placing the quartz capillary column tube into a heating device, adjusting the temperature to 200 ℃, and baking for 12 hours to obtain the porous polymer coating capillary chromatographic column.
The chromatographic column manufactured by the method is the porous polymer coating capillary chromatographic column provided by the invention. The porous polymer coating capillary chromatographic column provided by the embodiment comprises a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube. The chromatographic column tube is a quartz capillary column tube with the length of 50m and the inner diameter of 0.53mm, the porous polymer coating is an organic macromolecular porous polymer formed by the polymerization reaction of pure kerosene serving as a pore-forming agent and polymer monomers, and the polymer monomers are divinylbenzene, styrene and trichloroethylene with the mass ratio of 1:1: 0.25.
The porous polymer coating capillary chromatographic column provided by the embodiment has a greatly improved separation effect on hydrocarbon substances with the same carbon atom number, so that the porous polymer coating capillary chromatographic column can effectively have a good separation effect on the low carbon hydrocarbon substances by taking pure kerosene as a pore-forming agent, and the defect of analysis and detection on the low carbon hydrocarbon substances by the capillary gas chromatographic column is overcome. The porous polymer coating formed by adding the trichloroethylene into the polymerization reaction monomer is beneficial to the separation of the chlorine-containing compound.
Example 8:
a quartz capillary column tube having a length of 15m and an inner diameter of 0.25mm was prepared, and the dry inert gas used in this example was dry argon gas. And (2) leaching the inner wall of the quartz capillary column tube with hydrofluoric acid solution, then leaching the inner wall of the quartz capillary column tube with deionized water, then introducing dry argon into the quartz capillary column tube for purging, meanwhile, placing the quartz capillary column tube in a heating device, adjusting the temperature to 350 ℃, and baking for 7 hours to obtain the pretreated quartz capillary column tube.
Dispersing a styrene-divinylbenzene copolymer in a dispersing agent, and ultrasonically stirring for 1 hour to prepare a styrene-divinylbenzene initial polymer seed suspension with the mass concentration of 5%, wherein the dispersing agent is a toluene solution of polystyrene with the volume concentration of 3.5%. Then, the styrene-divinylbenzene initial polymer seed suspension was pressed into the pretreated quartz capillary column tube with dry argon gas under a pressure of 0.5Mpa using a high-pressure coating apparatus to obtain a quartz capillary column tube having an inner wall coated with polymer seeds. It is to be understood that the high-pressure coating apparatus is an apparatus in which a coating liquid container is provided in a closed container, one end of a column is inserted into the closed container and is introduced with the coating liquid, and then the coating liquid is pressed into the column by pressurizing the closed container.
Aviation kerosene is used as a pore-foaming agent, a polymer monomer is dissolved in pure kerosene used as the pore-foaming agent to prepare a polymerization reaction monomer suspension with the mass concentration of 10%, the content of the pore-foaming agent is 5% of the mass of the total reaction system, the polymerization reaction monomer suspension is placed into an ultrasonic disperser for ultrasonic mixing and dispersing for 50min, and the polymer monomer in the embodiment is 1:1:1 divinylbenzene, styrene and vinylpyridine. The aviation kerosene is a distillate of kerosene at 150-280 ℃, has high cleanliness, no harmful substances such as mechanical impurities and moisture and the like, has low sulfur content, particularly low thiol sulfur content, can be directly used as a pore-foaming agent as the existing product, and saves a distillation step.
And then pressing the cross-linking polymerization reaction monomer suspension into the pretreated quartz capillary column tube by using dry argon in a closed environment, controlling the pressure of the dry argon to be constant at 0.5Mpa, so that a liquid plug formed by the cross-linking polymerization reaction monomer suspension in the pretreated quartz capillary column tube keeps constant and uniform coating speed in the pretreated quartz capillary column tube and flows until the liquid plug is completely extruded out, and sealing the outlet end after the liquid plug is extruded from the outlet end to obtain the quartz capillary column tube coated with the polymer monomer.
Standing the quartz capillary column tube coated with the polymer monomer in a water bath device to perform in-situ polymerization reaction at 72 ℃ for 6 hours, introducing dry argon into the quartz capillary column tube coated with the polymer monomer, blowing the dry argon at 1.5MPa for 30 minutes, then regulating the pressure to 0.15MPa for blowing for 2 hours, finally blowing the wet coating to dry, and generating a white polymer coating on the inner wall of the quartz capillary column tube coated with the polymer monomer after drying, thereby obtaining the porous polymer coating capillary chromatographic column to be aged.
And introducing dry argon into the porous polymer coating capillary chromatographic column to be aged, simultaneously placing the quartz capillary column tube into a heating device, adjusting the temperature to 350 ℃, and baking for 6 hours to obtain the porous polymer coating capillary chromatographic column.
The chromatographic column manufactured by the method is the porous polymer coating capillary chromatographic column provided by the invention. The porous polymer coating capillary chromatographic column provided by the embodiment comprises a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube. The chromatographic column tube is a quartz capillary column tube with the length of 15m and the inner diameter of 0.25mm, the porous polymer coating is an organic macromolecular porous polymer formed by the polymerization reaction of aviation kerosene serving as a pore-foaming agent participating in polymer monomers, and the weight ratio of the polymer monomers is 1:1:1 divinylbenzene, styrene and vinylpyridine.
The porous polymer coating capillary chromatographic column provided by the embodiment has a greatly improved separation effect on hydrocarbon substances with the same carbon atom number, so that the aviation kerosene serving as a pore-forming agent can effectively enable the porous polymer coating capillary chromatographic column to have a better separation effect on the low-carbon hydrocarbon substances, and the defect of analysis and detection of the capillary gas chromatographic column on the low-carbon hydrocarbon substances is overcome. Meanwhile, the porous polymer coating formed by adding the vinylpyridine into the polymerization reaction monomer is beneficial to improving the surface activity of the polymer, can enable the porous polymer balls to be adhered and compacted, and is beneficial to the detection of heterocyclic compounds.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. The porous polymer coating capillary chromatographic column is characterized by comprising a chromatographic column tube and a porous polymer coating coated on the inner wall of the chromatographic column tube, wherein the chromatographic column tube is a quartz capillary column tube, the porous polymer coating is a crosslinked porous polymer microsphere formed by taking pure kerosene as a pore-foaming agent to participate in polymerization reaction of polymer monomers, and the content of the pure kerosene as the pore-foaming agent is 25-35% of the mass of a total reaction system.
2. The porous polymer coated capillary chromatography column according to claim 1, wherein said pure kerosene comprises jet fuel.
3. A porous polymer coated capillary chromatography column according to any of claims 1-2, wherein said polymer monomers comprise divinylbenzene and styrene, and further comprise any of vinylpyrrolidone, trichloroethylene and vinylpyridine.
4. A preparation method of a porous polymer coating capillary chromatographic column is characterized by comprising the following steps:
(1) leaching the inner wall of a pretreated quartz capillary column tube with reducing acid liquor, leaching the inner wall of the quartz capillary column tube with distilled water or deionized water, introducing dry inert gas into the quartz capillary column tube for purging, placing the quartz capillary column tube in a heating device, adjusting the temperature to 300-350 ℃, and baking for 7-12 hours to obtain the pretreated quartz capillary column tube;
(2) dispersing a styrene-divinylbenzene copolymer in a dispersing agent, ultrasonically stirring, preparing a styrene-divinylbenzene initial polymer seed suspension liquid with the mass concentration of 3-5%, and then pressing the styrene-divinylbenzene initial polymer seed suspension liquid into a pretreated quartz capillary column tube under the protection of inert gas to obtain the quartz capillary column tube with the inner wall coated with polymer seeds;
(3) distilling kerosene, taking fractions at 150-280 ℃ to obtain pure kerosene, dissolving a polymer monomer in the pure kerosene serving as a pore-forming agent, wherein the content of the pure kerosene accounts for 25-35% of the mass of a total reaction system, preparing a polymerization reaction monomer suspension with the mass concentration of 5-10%, and ultrasonically mixing for 30-50 minutes;
(4) pressing the polymerization reaction monomer suspension into the quartz capillary column tube with the inner wall coated with the polymer seeds at a constant flow rate under the protection of inert gas, and sealing an outlet of the quartz capillary column tube with the inner wall coated with the polymer seeds after the quartz capillary column tube with the inner wall coated with the polymer seeds is filled with the polymerization reaction monomer suspension to obtain the quartz capillary column tube coated with the polymer monomers;
(5) standing the quartz capillary column tube coated with the polymer monomer in a water bath device to perform in-situ polymerization reaction, then taking out the end enclosure, introducing dry inert gas into the quartz capillary column tube coated with the polymer monomer to blow the wet coating to dry, and generating a white polymer coating on the inner wall of the quartz capillary column tube coated with the polymer monomer after drying to obtain a porous polymer coating capillary chromatographic column to be aged;
(6) and introducing dry inert gas into the porous polymer coating capillary chromatographic column to be aged, meanwhile, placing the quartz capillary column tube in a heating device, adjusting the temperature to 200-350 ℃, and baking for 6-12 hours to obtain the porous polymer coating capillary chromatographic column.
5. The method for preparing the porous polymer coating capillary chromatographic column according to the claim 4, characterized in that the dispersant in the step (2) is a toluene solution of any one of polypropylene or polystyrene with a volume concentration of 2-5%.
6. The method of claim 4, wherein in step (3), the polymer monomers comprise divinylbenzene and styrene, and further comprise any one of vinylpyrrolidone, trichloroethylene and vinylpyridine.
7. The method for preparing a porous polymer coated capillary chromatography column according to claim 4, wherein in step (3), the pure kerosene is jet fuel.
8. The method for preparing the porous polymer coating capillary chromatographic column as claimed in any one of claims 4 to 7, wherein the reaction temperature of the in-situ polymerization of the water bath device in the step (5) is 68-72 ℃, and the reaction time is 6-8 hours; the specific operation steps of blowing dry inert gas to blow the wet coating to dry are firstly blowing for 30-60 minutes under 0.5-1.5 Mpa, and then reducing the pressure to 0.08-0.15 Mpa for blowing for 2-4 hours.
9. A porous polymer-coated capillary chromatography column, characterized in that it is produced by the production method according to any one of claims 4 to 8.
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