CN116943287A - Gas chromatographic column and preparation method and application thereof - Google Patents

Gas chromatographic column and preparation method and application thereof Download PDF

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CN116943287A
CN116943287A CN202310961530.1A CN202310961530A CN116943287A CN 116943287 A CN116943287 A CN 116943287A CN 202310961530 A CN202310961530 A CN 202310961530A CN 116943287 A CN116943287 A CN 116943287A
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column
quartz capillary
solution
gas chromatographic
capillary column
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许康
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Beijing Keruimai Technology Co ltd
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    • 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
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • 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
    • 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
    • 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
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography
    • 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

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Abstract

The embodiment of the invention discloses a gas chromatographic column and a preparation method and application thereof. The method comprises the following steps: (1) Carrying out inner wall treatment on the quartz capillary column by acid to hydroxylate the surface; (2) Depositing silicon dioxide on the inner wall of the quartz capillary column to increase the surface roughness; (3) carrying out inert treatment on the inner wall of the quartz capillary column; (4) And coating the stationary phase solution on the inner wall of the quartz capillary column to form a uniform film layer. The gas chromatographic column has higher wettability, stable thermodynamics, stable chemical property, ultrahigh inertia, stable detection signal and high success rate of products, under the scheme, various types of chromatographic columns are developed, various impurities can be jointly detected, the purity analysis of the compounds is improved, and the gas chromatographic column is mainly widely applied to the industries of analysis and detection of fire extinguishing agents in fluorine chemical industry and the like.

Description

Gas chromatographic column and preparation method and application thereof
Technical Field
The embodiment of the invention relates to the technical field of analytical chemistry, in particular to a gas chromatographic column and a preparation method and application thereof.
Background
Chromatographic analysis is a modern separation, analysis method, and any two different substances can be separated, analyzed or measured in a chromatographic process as long as they have differences in physical, chemical or biological properties and differences in partition coefficients among the different phases. Here, the different phases may include a gas phase, a liquid phase, a solid phase, and a supercritical phase. Different chromatographic types can be obtained by matching different phases, for example, a gas chromatography takes gas phase as a mobile phase, the gas chromatography is an important analysis method for analytical chemistry, the current gas chromatography has wide application in fluorine chemical industry, and plays an important role in the analysis of fire extinguishing agents such as perfluoro-hexanone, heptafluoropropane and the like. The accuracy of the analysis results plays a decisive role in the quality and effect of the fire extinguisher, as well as in the harm of the environment, personnel and equipment. Fire protection of buildings in fire extinguishment, most think of fire water sprinkler systems. However, the spraying system can bring secondary damage to the protected object while extinguishing fire, and the sprayed object is difficult to clean; the clean fire extinguishing agent can be quickly released and gasified, inhibits fire in the initial stage, has no harm to human body, is non-conductive, and can be quickly evaporated during spraying, and no residue exists. The residual time of the perfluorinated hexanone in the atmosphere is 3-5 days, the ozone depletion potential value ODP is 0, the ozone layer cannot be damaged, the greenhouse effect value GWP is 1, and the perfluorinated hexanone can be ensured to be used for a long time. The advantages are mainly in the following aspects: 1. the perfluoro-hexanone belongs to an environment-friendly fire extinguishing agent, and can be used for extinguishing fire, so that the environment is not polluted, and the equipment and human body are not damaged; 2. the spraying time of the perfluorinated hexanone fire extinguishing device is not more than 10S, so that a fire source can be quickly and accurately extinguished in the initial stage of a fire, and the loss caused by the fire is reduced; 3. the perfluoro-hexanone has good electrical insulation property, and can be electrified to perform fire extinguishing operation when an unattended fire disaster occurs; 4. the perfluorinated hexanone is used as a fire extinguishing flame retardant, so that the temperature of a fire scene can be rapidly reduced, the fire suppression capability is strong, and the further expansion of the fire is avoided; 5. the perfluorinated hexanone fire extinguishing device has two modes of electric starting and hot starting, and can meet the fire extinguishing starting modes of different conditions. Such fire extinguishing agents are known as cleanest, environmentally friendly fire extinguishing agents.
The development of gas chromatography techniques has been quite mature and the use of methods for the separation and analysis of compounds is widespread. There are many types of gas chromatographs, and the types of detectors are also different, but consist essentially of several units: the gas unit, the sample introduction unit, the separation unit, the detection unit, the data output unit and the like form stable and efficient analysis. Gas chromatography columns are the most important components of gas chromatograph separation, and significantly affect the separation efficiency and analysis speed of gas chromatography. There are several core techniques for gas chromatography columns that need to be mastered, among which the chemical synthesis and coating techniques of the gas chromatography column stationary phase are very important.
The chemical reaction mechanism of the gas chromatographic column stationary phase is not known in domestic enterprises and research institutions, all the gas chromatographic column stationary phase is purchased from abroad, the abroad is completely monopoly, and meanwhile, the coating technology of the gas chromatographic column has the advantages of good selectivity to compounds, high column efficiency, uniform liquid film and inert surface, and the gas chromatographic column can separate samples to be analyzed, and can be stable for a long time, and does not adsorb and react to the samples. The silica bridge is characterized in that a proper quartz tube raw material is selected, the silica tube is drawn by a special process, the silanol groups on the inner wall can adsorb a compound with high electron density although the inner wall is smooth, the ionic characteristics of the silica bridge are taken as proton acceptors to form hydrogen bonds so as to adsorb a compound which is easy to give protons, and metal ions on the surface of glass cause more serious adsorption and catalysis, so that a fixing solution at high temperature is decomposed and lost. The inner surface must therefore be treated prior to coating with the fixative solution to alter the chemical and physical properties to improve the wettability of the surface with the fixative solution. Wettability refers to the ability of a liquid to wet a solid surface, as measured by contact angle. The contact angle refers to the angle between the tangent of the interface of a droplet and the solid surface. When the contact angle is zero, the liquid completely wets the solid surface, and is easy to coat into a uniform film. Conversely, when the contact angle increases, the ability of the liquid to cover the solid surface decreases, and whether the liquid can infiltrate the solid surface depends on the cohesion of the liquid and the energy of the solid surface. The cohesion of a liquid is characterized by its surface tension, while the surface energy of a solid is expressed by the surface free energy. When the surface tension of the liquid is greater than the critical surface tension of a solid surface, the liquid has a contact angle value on the solid surface greater than zero. Critical surface tension of smooth clean glass is less than 3 x 10 -5 N/cm, while the surface tension of most fixatives is 5X 10 -5 N/cm, which indicates that most fixatives do not wet the glass surface. To produce an effective capillary column, the inner wall surfaces of glass and quartz tubes must be roughened or roughenedThe chemical and physical modification increases the surface energy and critical surface tension of the materials.
Disclosure of Invention
Therefore, the embodiment of the invention provides a gas chromatographic column, and a preparation method and application thereof.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
according to a first aspect of embodiments of the present invention, the present invention provides a method for preparing a gas chromatographic column, the method comprising the steps of:
(1) Carrying out inner wall treatment on the quartz capillary column by acid to hydroxylate the surface;
(2) Depositing silicon dioxide on the inner wall of the quartz capillary column to increase the surface roughness;
(3) Inert treatment is carried out on the inner wall of the quartz capillary column;
(4) And coating the stationary phase solution on the inner wall of the quartz capillary column to form a uniform film layer.
Further, in the step (1), HCl solution with the concentration of 12-18% is pressed into a quartz capillary column, the quartz capillary column is heated at 120-180 ℃, and then is washed by pure water and dried at 280-320 ℃ so as to thoroughly remove water vapor and acid gas in the column.
Further, in the step (2), CHCl is used 3 And dioxane as solvent to prepare silica into SiO with concentration of 10-15 mg/mL 2 The mixed solution is treated by ultrasonic treatment to obtain SiO 2 Suspension, siO is added to the suspension 2 The suspension was pressed into a quartz capillary column and the SiO was allowed to flow with nitrogen 2 The suspension was passed through the column and the solvent was then removed with a low flow of nitrogen.
Further, in the step (3), dicyanopropyl hexamethyl cyclotetrasiloxane is prepared into a solution of 0.4-0.6g/mL by using methylene dichloride, the solution is pressed into a quartz capillary column by using a dynamic method, the solvent is blown off by using nitrogen, two ends of the column are sealed after vacuum pumping, the temperature is raised to 420 ℃ at 4-6 ℃ per minute and kept for 12 hours, the temperature is slowly cooled to room temperature, and the column is washed by using methylene dichloride under a nitrogen flow.
Further, in the step (4), the fixed phase is prepared into a solution by using methylene dichloride, the solution is pressed into a quartz capillary column, the tail end is sealed, vacuum is pumped, and then aging is carried out under the protection of nitrogen at the temperature of 28-32psi and 250-280 ℃.
Further, the stationary phase preparation method comprises the following steps:
under the protection of nitrogen, carrying out a first reaction on 3-pentafluorophenyl propylene and phenyl dichlorosilane in the presence of Pt solution to obtain phenyl pentafluorophenyl propyl dichlorosilane;
the phenyl pentafluorophenyl propyl dichlorosilane and dimethyl dichlorosilane are subjected to a second reaction in the presence of an NaOH aqueous solution to obtain a transparent viscous compound.
Further, the mass ratio of the 3-pentafluorophenyl propene to the phenyl dichlorosilane is 105-110:70-80, preferably 109.2:76.4;
the temperature of the first reaction is 80-90 ℃ and the time is 6-10h;
the mass ratio of the phenyl pentafluorophenyl propyl dichlorosilane to the dimethyl dichlorosilane is 35-40:10-15, preferably 38.5:12.9;
the concentration of the NaOH aqueous solution is 1.8-2.2M;
the temperature of the second reaction is 80-90 ℃ and the time is 4-6h.
According to a second aspect of embodiments of the present invention, there is provided a gas chromatography column made by the method as described in any one of the preceding claims.
According to a third aspect of embodiments of the present invention, the present invention provides the use of a gas chromatography column as described above in fluorochemical and fire extinguishing agent detection.
The embodiment of the invention has the following advantages:
the gas chromatographic column has higher wettability, stable thermodynamics, stable chemical property, ultrahigh inertia, stable detection signal and high success rate of products, under the scheme, various types of chromatographic columns are developed, various impurities can be jointly detected, the purity analysis of the compounds is improved, and the gas chromatographic column is mainly widely applied to the industries of analysis and detection of fire extinguishing agents in fluorine chemical industry and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
FIG. 1 shows the dehydration and conversion process of quartz materials provided by the invention at different temperatures;
FIG. 2 is a diagram of the structure of the inner wall of a quartz capillary column provided by the invention;
FIG. 3 is a diagram showing the structure of the inner wall of a quartz capillary column after being treated by HCl solution and silica suspension;
FIG. 4 is a diagram of the inner wall of an inertly treated quartz capillary column according to the present invention;
FIG. 5 is a GC diagram of an actual sample according to the present invention;
FIG. 6 is a GC spectrum of another practical sample provided by the present invention.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a gas chromatographic column, which comprises the following steps:
(1) The chemical nature of the glass surface affects the performance of the chromatographic column. Various metal oxides form acid action points on the surface of the glass, and can absorb compounds with high local electron density such as alcohols, ketones, ammonia, pi-bond-containing molecules (such as aromatic compounds and olefins) and the like. The quartz material has no or little acidification points on the surface due to the extremely small metal impurity content, and has natural intelligence compared with glass. Glass and quartz surface hydroxyl groups are the main factors constituting ammonia-bond adsorption. When the distance of oxygen atoms between the surface hydroxyl groups is more than 0.45nm, hydrogen bonds cannot be formed between two hydroxyl groups. The hydroxyl group has the greatest activity and can absorb some compounds with high electron cloud density, such as amine, ketone, alcohol and pi-bond compounds. Is also a main point of action for carrying out the surface silanization treatment. Hydrogen and oxygen readily form hydrogen bonds at a distance of 0.24 to 0.28nm, with approximately 60% of the surface hydroxyl groups interacting with each other to form hydrogen bonds. The water adsorbed on the surface hydroxyl groups can also adsorb the compound with high electron cloud density, and the activity of the water is similar to that of the free surface hydroxyl groups. The physically adsorbed water may be removed when heated, leaving free hydroxyl groups for further heating to dehydrate the silica surface with adjacent hydroxyl groups to form oxygen bridges. Heating to 170 ℃ drives away the physically adsorbed water, and about 400 ℃ dehydrates the hydroxyl groups to form oxygen bridges. At this point, if the silica is cooled and exposed to water vapor, it can be restored to silanol groups. The amount of moisture-absorbing hydroxyl groups recovered by cooling again at 400 ℃ is reduced, e.g., the loss of hydroxyl groups on the silica surface is irreversible upon heating to 800 ℃ (see figure 1).
(2) The elastic quartz capillary column of the gas chromatographic column is made of a smooth inner wall of fused quartz glass (figure 2), the quartz glass is an informal solid, the surface of the quartz glass is smoother than the surface of a common solid and lacks a contact angle, so that liquid is difficult to stay, the surface roughness of the glass surface on the inner wall of a capillary column tube is increased by treating with HCl solution and silica suspension, the contact angle between molecules of a fixing liquid and the glass surface can be increased, the adhesion of the molecules of the fixing liquid can be enhanced, and a silicate surface is formed (figure 3), therefore, the inner wall of the capillary column tube needs to be subjected to inerting treatment, and polysiloxane is bonded with silanol groups on the surface through a high-temperature thermal decomposition product to form a macromolecular siloxane coalescing structure (figure 4), so that the wetting degree and the ultrahigh inertness of the fixing liquid are increased, and the detection limit of compounds in analysis is improved.
(3) Static coating: pressing the mixed fixed liquid solution into a capillary column under a certain pressure, sealing the tail end, extracting the tail end from the other end for a certain time by using vacuum suction, heating the gas capillary chromatographic column coated with the stationary phase to 250 ℃ under the state of introducing inert gas, and keeping the temperature for 22 hours.
In some embodiments, the inner wall treatment of the gas chromatography column is hydrothermized:
the inner wall treatment process of the gas chromatographic column comprises the following steps: the method comprises the steps of leaching, dehydrating, modifying and deactivating, wherein the glass and quartz surfaces of a gas chromatographic column are provided with a compound with high silanol groups to adsorb electron density, the ionic characteristics of a silica bridge are taken as proton acceptors to form hydrogen bonds to adsorb a compound which is easy to give protons, metal ions existing on the glass surface cause more serious adsorption and catalysis, fixing liquid at high temperature is decomposed, and the roughening treatment is needed in the second step, wherein a uniform film layer is formed in the wall of the chromatographic column by adopting a silica precipitation method, and the inner part of the chromatographic column is further subjected to chemical treatment before the fixing liquid is coated. The chemical method adopts polysiloxane to bond with silanol groups on the surface through high-temperature thermal decomposition products to form a high-analysis siloxane coalescence structure so as to increase the wetting degree and the ultrahigh inertia of the fixing liquid.
The physical method treatment comprises the following two steps:
the first step: the gas chromatographic column is washed by removing ions from the inner surface with acid to form a large number of silanol groups on the glass surface, suitably hydrochloric acid at a concentration of 15%. Acid leaching the glass surface replaces metal ions with hydrogen ions, i.e., metal ions that are slightly deeper in and above the glass surface migrate out.
And a second step of: the roughening treatment of the inner wall is to precipitate a layer of uniform granular material with a certain thickness from the solution, and the method adopts a silicon dioxide deposition method to deposit SiO 2 The powder, dichloromethane and dioxane are mixed into proper solution, and the proper solution is poured into a chromatographic column hollow tube, and then a stable film layer is formed by deposition.
Chemical method treatment:
the surface roughness and the cleaning degree in the tube are higher, but the wettability and the inertness are poorer, so that the chemical method needs to perform inerting treatment on the inner wall of the capillary tube, and polysiloxane is bonded with silanol groups on the surface through a high-temperature heated decomposition product to form a high-analysis siloxane coalescing structure so as to increase the wetting degree and the ultrahigh inertness of a fixing liquid.
In some embodiments, the stationary phase used in the present invention is prepared by reacting 3-pentafluorophenyl propene (compound a) and phenyl dichlorosilane (compound B) as raw materials under specific conditions, i.e., synthesizing phenyl pentafluorophenyl propyl dichlorosilane (compound C) by reaction equation one, and synthesizing phenyl pentafluorophenyl propyl dichlorosilane (compound C) and dimethyl dichlorosilane (compound D) by reaction equation two.
A brand new compound is used as a chromatographic column stationary phase, a unique chromatographic column is produced, and a separation solution is provided for a sample. Wherein the structures of 3-pentafluorophenyl propene (compound a) and phenyl dichlorosilane (compound B) are as follows:
(1) Reaction equation one:
(2) Reaction equation two:
in some embodiments, the specific process of equation one is: 109.2 g of Compound A and 76.4 g of Compound B are added into a four-necked flask, placed on a water bath reactor, inert gas is introduced to ensure the nitrogen protection state, a stirrer is uniformly stirred, and the temperature is set: and (3) continuously adding Pt solution at 85 ℃ to react for 8 hours to obtain the compound C.
Pt is a noble metal, platinum is used as a catalyst for the reaction, mainly because the d-orbital electrons of the component are not filled, the d-orbital is relatively stable in half-filled and full-filled states, and the d-orbital electrons of platinum are treated in the unfilled state. Meanwhile, d-rail electrons have the phenomenon of energy level staggering. Therefore, the component is adopted as an active ingredient to have better activity, stability and selectivity. First, platinum is treated to a catalytically active platinum black.
In some embodiments, the specific process of equation one is:
38.5 g of compound C and 12.9 g of dimethyldichlorosilane are added into a four-necked flask, the flask is placed on a water bath reactor, inert gas is introduced, the nitrogen protection state is ensured, a stirrer is uniformly stirred, and the temperature is set: and continuously adding 800ml of 2M (mol/L) sodium hydroxide aqueous solution at the temperature of 85 ℃ to react for 5 hours to obtain a transparent viscous compound E, thus obtaining the required stationary phase.
The elemental analysis of product E was analyzed for theoretical and actual values, and the results are shown in Table 1.
TABLE 1
At different molar ratios of C and D, equation two yields product E, resulting in the corresponding ratios of M and N for product E. The element theory value is calculated by using element analysis (shown in the above diagram), the actual value under different proportions is actually measured, and the element characteristic of the product E is met by analyzing the data result.
Example 1
The embodiment provides a preparation method of a gas chromatographic column, which comprises the following steps:
(1) Pressing 15% HCl solution into capillary column (column length of 120 m, tube diameter of 0.25 mm) by high pressure method, slowly heating the capillary column to overflow part of the HCl solution, cooling to room temperature, sealing the capillary column under vacuum condition, and continuously heating. Moderate leaching is achieved at 130 ℃, and if deep leaching is desired, the leaching can be heated to 175 ℃. The leached capillary column should be immediately washed, typically with pure water, to remove concentrated hydrochloric acid solution and leached metal ions. The washed capillary column is filled with dry nitrogen and is placed at the temperature of about 350 ℃ for 15-20 hours, so that water vapor and acid gas in the column are thoroughly removed.
(2) Preparing a silicon dioxide polymer microsphere seed suspension: heating at 300℃for 3 hours, followed by CHCl 3 And dioxane as solvent to prepare 10-15 mg/mLSiO 2 And (3) mixing the liquid. Ultrasound for 35h to make SiO 2 Dispersed into a uniform suspension. The suspension was diluted with CHCl 3 The wet capillary column is 1/10 of the column length, the liquid plug is made to pass through the column by nitrogen flow, and the solvent is removed by nitrogen with low flow rate to complete SiO 2 And (3) coating. The post thus treated is deposited with a layer of SiO 2 The dual purposes of covering the surface active groups and roughening are achieved.
(3) The dicyanopropyl hexamethyl cyclotetrasiloxane reagent is used, a dichloromethane solution with the concentration of 0.5g/mL is used, the mixed solution is pressed into a chromatographic column through a high-pressure device by a dynamic method, after the solvent is blown away by nitrogen, the two ends of the column are sealed under vacuum pumping, the temperature is raised to 420 ℃ at 5 ℃/min, and the temperature is kept for 12 hours. Finally, the temperature was cooled down slowly to room temperature, one end of the column was put into methylene chloride and then opened, so that a part of methylene chloride was introduced into the column and the column was washed with the solvent under a nitrogen stream.
(4) Preparing a stationary phase solution: the compound C of the invention is selected as a stationary phase, 0.5g is weighed by a precision balance, 20ml of dichloromethane solution is weighed by a dosage cylinder, and the dichloromethane solution is fully dissolved by ultrasonic.
(5) And (3) pressing the solution with the stationary phase into a corresponding quartz capillary column under the high pressure of 0.6MPa by using a special high-pressure device, flowing out the tail end, namely sealing the tail end, and connecting the other end to a vacuum pump. The pumping is completed for 24 hours or more.
(6) And (3) the capillary chromatographic column is connected into a special baking oven for aging, the pressure is set to be 30psi, the temperature is set to be 260 ℃ and the setting time is set to be 20 hours under the protection of high-purity nitrogen, and the aging treatment is carried out, so that the chromatographic column with better column effect and better inertia can be obtained.
Example 2
Sample: perfluoro-hexanone fire extinguishing agent
Chromatographic column: unnamed column, 60 x 0.25 x 1.40
Chromatographic conditions:
sample inlet: 200 ℃; a detector: FID,200 ℃; split ratio: 35:1
Column temperature: the initial temperature was 35℃for 56min, and the temperature was raised to 100℃at a rate of 15℃per min for 15min.
The detection results are shown in Table 2. The actual sample pattern is shown in FIG. 5.
TABLE 2
Sequence number Peak time Component name
1 48.468 Perfluoro hexanone
2 49.531 Trans-perfluoro-4-methyl-2-pentylene
3 50.016 Epoxy-2-pentylene
4 52.365 Cis-perfluoro-4-methyl-2-pentylene
5 53.048 Perfluoro-2-methyl-2-pentylene
Example 3
Chromatographic column: unnamed column, 60 x 0.32 x 1.8
Chromatographic conditions:
sample inlet: 240 ℃; a detector: 250 ℃; split ratio: 40:1; sample injection amount: 1 μl
Control mode: constant pressure; column pressure: 11psi
Column temperature: the column temperature is kept at 85 ℃ for 5min;5 ℃/min to 110 ℃; and maintaining at 20 deg.c/min to 230 deg.c for 20min.
The detection results are shown in Table 3. The actual sample pattern is shown in FIG. 6.
TABLE 3 Table 3
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (9)

1. A method for preparing a gas chromatographic column, comprising the steps of:
(1) Carrying out inner wall treatment on the quartz capillary column by acid to hydroxylate the surface;
(2) Depositing silicon dioxide on the inner wall of the quartz capillary column to increase the surface roughness;
(3) Inert treatment is carried out on the inner wall of the quartz capillary column;
(4) And coating the stationary phase solution on the inner wall of the quartz capillary column to form a uniform film layer.
2. The method for preparing a gas chromatographic column according to claim 1, wherein in step (1), 12-18% HCl solution is pressed into a quartz capillary column, the quartz capillary column is heated at 120-180 ℃, and then washed with pure water and dried at 280-320 ℃ to thoroughly remove water vapor and acid gas in the column.
3. The method for producing a gas chromatography column according to claim 1, wherein CHCl is used in step (2) 3 And dioxane as solvent to prepare silica into SiO with concentration of 10-15 mg/mL 2 The mixed solution is treated by ultrasonic treatment to obtain SiO 2 Suspension, siO is added to the suspension 2 The suspension was pressed into a quartz capillary column and the SiO was allowed to flow with nitrogen 2 The suspension was passed through the column and the solvent was then removed with a low flow of nitrogen.
4. The method for preparing a gas chromatographic column according to claim 1, wherein in the step (3), dicyanopropyl hexamethyl cyclotetrasiloxane is prepared into a solution of 0.4-0.6g/mL by using methylene chloride, the solution is pressed into a quartz capillary column by using a dynamic method, the solvent is blown off by using nitrogen, both ends of the column are sealed after vacuum pumping, the temperature is raised to 420 ℃ at 4-6 ℃/min and maintained for 12 hours, the temperature is slowly cooled to room temperature, and the column is washed by using methylene chloride under the nitrogen flow.
5. The method of preparing a gas chromatographic column according to claim 1, wherein in step (4), the fixed phase is prepared into a solution with methylene chloride, the solution is pressed into a quartz capillary column, the tail end is sealed, vacuum is applied, and then aging is performed under the protection of nitrogen at 28-32psi and 250-280 ℃.
6. The method for preparing a gas chromatographic column according to claim 5, wherein the method for preparing the stationary phase comprises the following steps:
under the protection of nitrogen, carrying out a first reaction on 3-pentafluorophenyl propylene and phenyl dichlorosilane in the presence of Pt solution to obtain phenyl pentafluorophenyl propyl dichlorosilane;
the phenyl pentafluorophenyl propyl dichlorosilane and dimethyl dichlorosilane are subjected to a second reaction in the presence of an NaOH aqueous solution to obtain a transparent viscous compound.
7. The method for preparing a gas chromatographic column according to claim 6, wherein,
the mass of the 3-pentafluorophenyl propene and the phenyl dichlorosilane is 105-110:70-80, preferably 109.2:76.4;
the temperature of the first reaction is 80-90 ℃ and the time is 6-10h;
the mass ratio of the phenyl pentafluorophenyl propyl dichlorosilane to the dimethyl dichlorosilane is 35-40:10-15, preferably 38.5:12.9;
the concentration of the NaOH aqueous solution is 1.8-2.2M;
the temperature of the second reaction is 80-90 ℃ and the time is 4-6h.
8. A gas chromatography column, characterized in that it is made by the method of any one of claims 1-7.
9. The use of the gas chromatographic column of claim 8 in the detection of fluorochemical and fire extinguishing agents.
CN202310961530.1A 2023-08-01 2023-08-01 Gas chromatographic column and preparation method and application thereof Pending CN116943287A (en)

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