JPS59141064A - Column for chromatography - Google Patents

Abstract

PURPOSE:To obtain a column which stably holds a solid phase and has excellent separation capacity, by forming an organopolysiloxane type crosslinked high- molecular membrane to the inner surface of the column for chromatography while applying a fixing phase liquid to the surface of said membrane. CONSTITUTION:A volatile solvent solution prepared by adding a radical generating agent such as benzoyl proxide to organopolysiloxane having one or more of vinyl groups such as methylphenylvinylsilicone to the inner surface of the tube 1 for chromatography comprising soda lime glass, borosilicate glass or stainless steel and dried and heated for a time sufficient to form a crosslinked membrane 2. In the next step, a solution of non-polar or polar methylphenylsilicone is applied to said membrane 2 and a solvent is removed to form a uniform fixing phase liquid coating 3. As mentioned above, surface roughening treatment such as chemical etching of an internal surface becomes unnecessary and excellent separation capacity in which the feature of the inert surface possessed by quartz glass is usefully adapted can be provided, especially, to the capillary tube made of quartz glass.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a column for chromatography. More specifically, it relates to chromatography columns used in chromatography such as gas chromatography and liquid chromatography, particularly columns using a liquid as a stationary phase.

←) Prior Art Columns for chromatography that use a liquid as the inner stationary phase have been known for some time.

Various polar types are known as this stationary phase liquid,
Various choices have been made in combination with target components to be separated.

However, there are various problems when coating the inner surface of a column tube with such a stationary phase liquid.

For example, in the case of gas chromatography columns and capillary columns, it is difficult to coat polar stationary phase liquids in the form of droplets (particularly when the polarity is medium to strong, coating is often difficult), and it is usually difficult to coat the polar stationary phase liquid in the form of droplets. It was necessary to roughen the inner surface of the column by chemically etching it or forming a layer of inorganic, poorly soluble salt. moreover,
Such pretreatment can be applied when a capillary tube whose inner surface is not sufficiently inert, such as a soda-lime glass tube or a borosilicate glass tube, is used as a capillary tube. It cannot be said that this is an appropriate treatment when using a preferred tube. In other words, unlike soda-lime glass and borosilicate glass, quartz glass tubes contain almost no impurities (metal oxides, silanol groups, etc.), so they are chemically inert and have very little effect on separated components. Although quartz glass is suitable for high-precision measurements, it has the disadvantage that the inertness of its inner surface is impaired when the above-mentioned pretreatment is carried out, and the advantages of quartz glass cannot be utilized. However, chemical etching itself was difficult.

That is, it has been difficult to coat the inner surface of a quartz glass capillary tube with a polar stationary phase liquid without impairing the inertness of the high-grade inner surface. Furthermore, ordinary chromatography columns do not require special pretreatment like capillary columns, but
Improving the affinity of polar stationary phase liquids for internal surfaces has been one of the more desirable issues in terms of stationary phase stability.

(c) Purpose of the Invention The present invention has been made to solve the above-mentioned conventional problems. That is, one object of the present invention is to provide a capillary tube whose inner surface is sufficiently inert and whose inner surface is stably coated with a polar stationary phase liquid.

Another object of the present invention is to provide a capillary column whose inner surface is stably coated with a stationary phase liquid without performing surface porosity treatment such as etching treatment.

Another object of the present invention is to provide a chromatography column whose inner surface is more stably coated with a stationary phase liquid.

B) Structure of the Invention Thus, the present invention provides a chromatography method in which an organopolysiloxane crosslinked polymer thin film is formed on the inner surface of a column tube, and a stationary phase liquid is coated on the surface of the crosslinked polymer thin film. The purpose of this paper is to summarize the columns used in this paper.

Examples of the column tube include various known tubes used for gas chromatography and liquid chromatography, and the material thereof may be stainless steel, soda lime glass, borosilicate glass, quartz glass, etc. .

In particular, it is most effective when a quartz glass capillary tube is used. Note that the outer surface of such a column tube may be coated with a protective material such as synthetic resin.

After forming an organopolysiloxane crosslinked polymer thin film, which is the most characteristic feature of the present invention, on the inner surface of the column tube, the inner surface is coated with a stationary phase liquid to obtain the chromatography column of the present invention.

The organopolysiloxane-based crosslinked polymer thin film is normally formed by coating the inner surface of the column with organopolysiloxane and then subjecting it to crosslinking treatment. Suitable organopolysiloxanes include those having crosslinkable functional groups, such as those containing at least one vinyl group, such as alkyl and/or vinyl groups such as 1-1', methylphenyl vinyl silicone, methyl vinyl silicone, and phenyl vinyl silicone. Alternatively, it is preferable to use aryl vinyl silicone. Such organopolysiloxanes include benzoyl peroxide, dicumyl peroxide,
After adding a radical generator such as ter-butyl peroxide (or other crosslinking accelerator in some cases), crosslinking can be easily carried out by subjecting the mixture to crosslinking conditions such as heating. Therefore, usually, a crosslinking accelerator such as a radical generator is added to a solution of organopolysiloxane in a volatile organic solvent, and this solution is applied to the inner surface of the column and then heated to remove the organic solvent and cause crosslinking. It is suitable to form The amount of the radical generator to be added is preferably about several weights based on the organopolysiloxane. Further, the thickness of the crosslinked polymer thin film to be formed is suitably about 0.1 to 0.5 μm, and these can be adjusted by the conditions of the coating treatment.

As the stationary phase liquid of this invention, various liquids known in the art can be used, and specific examples include polyethylene glycol and its derivatives, phthalate esters, organopolysiloxanes (non-crosslinked), etc. Liquids with zero or very little polarity, such as branched alkanes, can also be used. Among these, the effects of the present invention are most exhibited when a stationary phase liquid having medium to strong polarity is used.

In the above structure, since the organopolysiloxane crosslinked layer is formed on the inner surface of the column tube, the stationary phase liquid is more easily wetted and more stably retained than an untreated liquid, which leads to the effects of the present invention. It is thought that the

(e) Example: Methylphenyl vinyl silicone (Silicone BK-54; manufactured by General Electric Co., Ltd.) was attached to a capillary tube made of fused silica glass with a diameter of 0.2 m and whose outer periphery was coated with a heat-resistant resin layer (polyimide resin) as a protective layer. ) to lW/v% n-pentane solution o-tW/v% (5
The inner surface was coated using a solution containing benzoyl peroxide (for M-54). Note that the inner surface coating was performed by a dynamic coating method.

The tube coated with methylphenylvinyl silicone was then set in a column tank of a gas chromatograph and held at 100°C for 8 hours, then raised to 800°C and held for 15 hours. This operation allows the residual solvent (n
- Pentane) is removed and the methylphenylvinyl silicone is crosslinked, and - a capillary tube having a crosslinked polymer thin film (about 0.1 μm thick) of the methylphenylvinyl silicone formed on the inner surface is obtained.

Then, polar methylphenyl silicone (Silicone OV-17 Applied Sci,
A 5 w/v % n-hexane solution (manufactured by Labs, Inc.) was passed through the capillary tube using a dynamic method and the solvent was removed, thereby immobilizing the tube to a thickness of approximately 0.5 μm on the inner surface of the crosslinked polymer thin film. A polar flexible quartz capillary column, which is an embodiment of the present invention, as shown in FIG. 1, is obtained which is uniformly coated with a phase liquid. In Fig. 1, (1) is a fused silica capillary tube, (2) is a crosslinked polymer thin film,
(3) shows the coated stationary phase liquid, and (4) shows the heat-resistant resin layer.

Note that it is difficult to directly coat silicone 0-17 on a quartz capillary tube on which the crosslinked polymer thin film (2) is not formed.

Similarly, a chromatography column can be obtained by stably coating various stationary phase liquids on the circular surface of a soda-lime glass or borosilicate glass capillary tube or a normal chromatography tube.

(F) Effects of the Invention As described above, the present invention provides a chromatography column in which a quartz glass capillary tube is stably and uniformly coated with various polar stationary phase liquids, which have conventionally been difficult to coat on the inside. . Furthermore, the crosslinked polymer thin layer of organopolysiloxane that makes it possible to coat the inner surface does not impair the properties of quartz glass. Therefore, it is possible to obtain a chromatography column that takes advantage of the characteristics of a silica glass capillary tube without being limited by the polarity or strength of the stationary phase liquid, and the field of application is expanded.

Furthermore, even for capillary tubes made of materials other than quartz glass, a chromatography column whose inner surface is uniformly coated with a stationary phase liquid can be obtained without performing the conventional surface roughening treatment.

Furthermore, even in ordinary chromatography columns, the retention of the stationary phase liquid is more stable, and a preferable column can be obtained.

Therefore, the chromatography column of the present invention is extremely useful in this field.

[Brief explanation of the drawing]

FIG. 1 is a partial sectional view showing an embodiment of a chromatography column of the present invention. (1)--Fused silica capillary tube, (2)-
...Crosslinked polymer thin film, (3) ...Stationary phase liquid, (4)
・−・Heat-resistant resin layer.

Claims (1)

[Claims] 1. A column for chromatography, in which an organopolysiloxane crosslinked polymer thin film is formed on the inner surface of a column tube, and a stationary phase liquid is coated on the surface of the crosslinked polymer thin film. . 2. The column according to claim 1, wherein the column tube is a capillary tube.