TWI498157B - Stationary phase material for chromatography and a chromatographic column - Google Patents

Description

Chromatographic stationary phase material and chromatography column

The present invention relates to a chromatographic material and a chromatography column, and more particularly to a chromatographic stationary phase material for column chromatography, and a chromatography column having the chromatographic stationary phase material.

Chromatography is to use the difference in chemical or physical properties of the analyte to distribute the components in the analyte to different degrees in two phases. The two phases, one fixed on a support, called the stationary phase or the stationary phase, and the other, are mobile, called the mobile phase or the mobile phase. The stationary phase can be a solid or a liquid, and the mobile phase can be a liquid or a gas. Because of its advantages of trace amount, rapidity, simplicity, and high efficiency, chromatography is widely used in various fields such as analytical chemistry, organic chemistry, and biochemistry.

However, no matter what field the chromatographic method is applied, the chromatographic analysis/separation results are highly correlated with the properties of the static phase layer material itself. In the case of gas chromatography, since gas chromatography needs to be carried out under high temperature conditions, there are more stringent requirements for the thermal stability of the material of the static phase layer, which is currently commercially available. The static phase layer material used for the gas chromatographic chromatography column is mostly composed of a polydecane oxygen compound, and is used to reduce the loss of the static phase layer material from the chromatography column at a high temperature, and to enhance The thermal stability of the static phase layer material usually bonds the static phase layer material to the support surface of the chromatography column or cross-linked the static phase layer material to form a mesh. Covalently priced to increase its thermal stability.

In order to improve the thermal stability of the static phase layer material, it has better high temperature durability and better resolution when separating different mixtures, so different static phase layer materials have also been proposed; Ionic liquids can be used to separate mixtures of different polar compositions because of their simultaneous presence of diionic (anion/cation) in their molecular structure and the ability to change the affinity and hydrophobicity of ionic liquids by adjusting their anions. Therefore, the development of ionic liquids in stationary phase layer materials has received increasing attention. The inventor also disclosed in the invention patent No. I385382 of the Republic of China that a main chain type polyimidazolium salt ionic liquid is used as a static phase layer material, and the static phase layer material has good separation effect and temperature resistance up to 410 ° C or higher.

However, when the molecular weight of the static phase layer material of the chromatography column is insufficient, after the chromatography column is left to stand for a long time, the static phase layer may be displaced due to gravity due to insufficient stability of the film, thereby affecting the Reproducibility of chromatographic column analysis; for example, a chromatography column using the above-mentioned main chain type polyimidazolium salt-based ionic liquid as a static phase layer material, although having superior separation effect and temperature resistance, is The membrane type polyimidazolium salt ionic liquid has insufficient membrane stability, and therefore, the chromatography column is allowed to stand for a period of time, and the static phase is The layer is displaced by the influence of gravity, resulting in deterioration of the film uniformity of the static phase layer. Therefore, when the sample column is reused for sample analysis, the analysis result is shifted.

Accordingly, it is an object of the present invention to provide a chromatographic stationary phase material having both film stability and thermal stability.

Thus, the chromatographic stationary phase material of the present invention comprises a main chain type imidazolium salt type polyionic liquid having a repeating unit represented by the following formula (I), and a polycondensation having a repeating unit represented by the following formula (II) a dialkyl diallyl ammonium ionic liquid, wherein R ₁ is hydrogen or an alkyl group, and R ₂ and R ₃ are each independently hydrogen, an alkyl group, or a benzene ring-substituted group, Y is selected From C ₁ to C ₂₀ alkyl, R ₄ and R ₅ are C ₁ -C ₁₀ alkyl, Z ^- , and X ^- are respectively selected from N(SO ₂ CF ₃ ) ₂ ^- , N(SO ₂ CF ₂ CF ₃ ) ₂ ^- , CF ₃ SO ₃ ^- , or a combination thereof, the molecular weight of the polydialkyl diallyl ammonium ionic liquid is not less than 500,000, and the polydialkyl diallyl ammonium ionic liquid and the The weight ratio of the main chain type imidazolium salt polyionic liquid is between 1:1 and 1:10.

Preferably, the chromatographic stationary phase material, wherein the polydialkyl diallyl ammonium ionic liquid has a molecular weight of between 5,000 and 2,000,000 between.

Preferably, the chromatography static phase material, wherein the polydialkyl diallyl ammonium ionic liquid has a molecular weight of not less than 900,000.

Preferably, the chromatography static phase material, wherein the weight ratio of the polydialkyl diallyl ammonium ionic liquid to the main chain type imidazolium salt polyionic liquid is between 1:2 and 1:5. between.

Preferably, the chromatographic stationary phase material, wherein the main chain type imidazolium salt polyionic liquid has a molecular weight of not less than 20,000, and R ₁ , R ₂ , and R ₃ are each selected from hydrogen, or C ₁ to C ₁₀ An alkyl group, and Y is a single bond alkyl group selected from C ₃ to C ₂₀ .

Preferably, the chromatographic stationary phase material, wherein the main chain type imidazolium salt polyionic liquid has a molecular weight of not less than 20,000, R _{1 is} selected from hydrogen, or a C ₁ -C ₁₀ alkyl group, R ₂ and R ₃ constituting a monophenyl ring-substituted group to form a benzimidazole structure represented by the following formula (III), and Y is a single bond alkyl group selected from C ₃ to C ₂₀ , and the R ₆ to R ₉ are individual It is selected from hydrogen, or a C ₁ -C ₁₀ alkyl group.

Preferably, the chromatographic stationary phase material, wherein Z ^{- is} selected from the group consisting of N(SO ₂ CF ₃ ) ₂ ^- .

Preferably, the chromatographic stationary phase material, wherein X ^{- is} selected from the group consisting of N(SO ₂ CF ₃ ) ₂ ^- .

Further, another object of the present invention is to provide a chromatography column which has both film stability and thermal stability.

Thus, the chromatographic stationary phase material of the present invention comprises a hollow tubular body and a static phase layer formed on the inner wall surface of the body, wherein the static phase layer is composed of a layer as described above. Analyze the static phase material.

The effect of the invention is that the static phase chromatography material obtained by blending the polydialkyl diallyl ammonium ionic liquid with the main chain type imidazolium salt polyionic liquid can not only have superior separation effect, but also It can also have both thermal stability and film stability.

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a TGA diagram illustrating P[ImC ₆ ][NTf ₂ ] and P[DADMA][NTf ₂ ] And the TGA measurement results of P[ImC ₆ ][NTf ₂ ] and P[DADMA][NTf ₂ ] in different blending ratios; FIG. 2 is a gas chromatographic separation diagram illustrating the specific examples 3, 4 and comparison The chromatographic column prepared in Examples 1 and 2 was subjected to gas chromatography separation of Sample 1, and FIG. 3 is a gas chromatographic separation diagram showing the layers obtained in Specific Examples 3 and 4 and Comparative Examples 1 and 2. The column was subjected to gas chromatography separation of the sample 2; FIG. 4 is a gas chromatographic separation diagram illustrating the chromatographic column prepared in the specific examples 3 and 4 and the comparative examples 1, 2, and the sample 3 Gas chromatographic separation results; FIG. 5 is a gas chromatographic separation diagram illustrating the gas chromatography separation results of the sample 4 in the chromatographic column prepared in the specific examples 3 and 4 and the comparative examples 1 and 2; 6 is a gas chromatographic separation diagram, illustrating the gas chromatographic separation result of the sample 1 prepared by the specific example 3 after standing for 60 days; FIG. 7 is a gas chromatographic separation diagram, illustrating The layer prepared in the specific example 4 After 60 days of standing on the column, the gas chromatographic separation result of the sample 1; FIG. 8 is a gas chromatographic separation diagram, indicating that the chromatography column prepared in the comparative example 1 was allowed to stand for 60 days, The gas chromatographic separation result of the sample 1; FIG. 9 is a gas chromatographic separation diagram, illustrating the gas chromatography separation result of the sample 2 after the chromatography column prepared in the specific example 3 is allowed to stand for 60 days; Figure 10 is a gas chromatographic separation diagram illustrating the gas chromatographic separation of the sample 2 after 60 days of standing on the chromatography column prepared in the specific example 4; Figure 11 is a gas chromatographic separation diagram, The gas chromatographic separation result of the sample 2 obtained by the comparative example 1 after standing for 60 days is shown; FIG. 12 is a gas chromatographic separation diagram illustrating the chromatogram obtained in the specific example 3. After gas column chromatography for 60 days, the gas chromatographic separation result of the sample 3; FIG. 13 is a gas chromatographic separation diagram, indicating that the chromatography column prepared in the specific example 4 is allowed to stand for 60 days, The gas chromatographic separation result of the sample 3; FIG. 14 is a gas chromatographic separation diagram, illustrating the gas chromatography of the sample 3 after the 60-day column of the comparative example 1 was allowed to stand for 60 days. Fig. 15 is a gas chromatographic separation diagram illustrating the gas chromatographic separation of the sample 4 after 60 days of standing in the specific example 3; FIG. 16 is a gas chromatography separation. FIG. 17 is a gas chromatographic separation diagram of the sample tube prepared in the specific example 4 after standing for 60 days; FIG. 17 is a gas chromatographic separation diagram, and the comparative example 1 was prepared. After the chromatography column was allowed to stand for 60 days, the result of gas chromatography separation of the sample 4 was carried out.

The chromatographic static phase material of the present invention is a static phase layer as a chromatography column, and the chromatography column can be applied to the technical field of analysis such as gas chromatography, liquid chromatography, capillary electrophoresis, etc., in this embodiment, The method is applied to gas chromatography (hereinafter referred to as GC) as an example, but the application of the invention is not limited thereto.

A preferred embodiment of the chromatographic stationary phase material of the present invention comprises a main chain type imidazolium salt type polyionic liquid, and a polydialkyl diallyl ammonium ion ionic liquid, and the polydialkyl diallyl group The weight ratio of the ammonium ionic liquid to the main chain type imidazolium salt polyionic liquid is between 1:1 and 1:10.

The main chain type imidazolium salt-type polyionic liquid has a repeating unit represented by the following formula (I), wherein R ₁ is hydrogen or an alkyl group, and R ₂ and R ₃ are each independently hydrogen, an alkyl group, or a common A benzene ring-substituted group is formed, Y is an alkyl group selected from C ₁ to C ₂₀ , and Z ^{- is} selected from N(SO ₂ CF ₃ ) ₂ ^- , N(SO ₂ CF ₂ CF ₃ ) ₂ ^- , CF ₃ SO ₃ ^- , or a combination of the foregoing. It is to be noted that when the substituents R ₂ and R ₃ in the formula (I) form a benzene ring substituent group together, the repeating unit represented by the formula (I) will have the formula (III). The benzimidazole structure is shown, and the substituents R ₆ to R ₉ on the benzene ring in the benzimidazole structure are each independently hydrogen or an alkyl group.

Specifically, the main chain type imidazolium salt polyionic liquid is prepared by first alkylating an imidazole compound with a disubstituted halocarbon compound to prepare an ionic liquid monomer compound represented by the following formula (A). Then, self-polymerization is carried out at 100 ° C in an ethylene glycol solution to obtain a polyionic liquid as shown in the formula (B), and then the polyionic liquid represented by the formula (B) and LiN (SO ₂ CF _{3 ) are obtained. 2} , LiN(SO ₂ CF ₂ CF ₃ ) ₂ , CF ₃ SO ₃ Na, anion exchange of the plasma compound, thereby obtaining a main chain type imidazolium salt type polyionic liquid as shown in formula (C), The reaction is represented by the following reaction mechanism.

Preferably, in order to impart basic membrane support to the main chain type imidazolium salt-type polyionic liquid, the molecular weight thereof is not less than 20,000; more preferably, the main chain type imidazolium salt-type polyionic liquid has a molecular weight of not less than 30,000. And R _{1 is} selected from hydrogen, or a C ₁ -C ₁₀ alkyl group, Y is selected from a C ₃ -C ₂₀ single bond alkyl group, and R ₂ and R ₃ are each independently hydrogen or a C ₁ -C ₁₀ alkyl group. Or, in the formula (III), R ₆ to R ₉ are each independently hydrogen or a C ₁ to C ₁₀ alkyl group.

The polydialkyl diallyl ammonium ionic liquid has a repeating unit represented by the following formula (II), wherein R ₄ and R ₅ are C ₂ -C ₁₀ alkyl groups, and X ^{- is} selected from N (SO ₂ CF) ₃ ) ₂ ^- , N(SO ₂ CF ₂ CF ₃ ) ₂ ^- , CF ₃ SO ₃ ^- , or a combination thereof.

Formula (II)

In order to impart better film stability to the chromatographic stationary phase material, the molecular weight of the polydialkyl diallyl ammonium ionic liquid is not less than 500,000. In addition, in order to make the chromatographic static phase material have both membrane stability and thermal stability without affecting the analysis effect of the main chain type imidazolium salt polyionic liquid, preferably, the polydialkyldiene The molecular weight of the quaternary ammonium ionic liquid is between 500000 and 2000000; more preferably, the molecular weight of the polydialkyl diallyl ammonium ionic liquid is between 900,000 and 2,000,000, and the polydialkyl diallyl ammonium ion The weight ratio of the liquid to the main chain type imidazolium salt polyionic liquid is between 1:2 and 1:5. Still more preferably, the main chain type imidazolium salt type polyionic liquid, and the anion (Z ^- , X ^- ) of the polydialkyl diallyl ammonium ion liquid are simultaneously selected from N(SO ₂ CF ₃ ) ₂ ^- (indicated by NTf ₂ ^- ).

Specifically, the polydialkyl diallyl ammonium ionic liquid having an anion of NTf ₂ ^- is prepared by first preparing a predetermined number of molar polydialkyl diallyl ammonium ionic liquids (anion is Cl ^- ) Dissolved in water, slowly added to an aqueous solution containing LiNTf ₂ , stirred at room temperature, suction filtered, and dried to obtain a white powder to obtain a polydialkyl diallyl ammonium ionic liquid having an anion of NTf ₂ ^- .

The present invention utilizes a polydialkyl diallyl ammonium ionic liquid having a high molecular weight to improve the membrane stability and thermal stability of the chromatographic stationary phase material, and because of the polydialkyl diallyl ammonium ion The structure of the liquid and the imidazolium polyionic liquid are both main chain type ammonium ion liquids, so the mixing effect of the main chain type imidazolium salt polyionic liquid is not affected after the mixing. The chromatographic static phase material of the present invention can also have both film stability and thermal stability while maintaining superior separation effect.

When the chromatographic static phase material is actually used as the static phase layer material of the chromatography column, the chromatographic static phase material is coated on the inner wall surface of a hollow body, and a static phase layer is formed on the inner wall surface. A chromatographic column for chromatography is obtained. Specifically, the body may be a hollow capillary column made of fused-silica.

Next, the chromatographic stationary phase material of the present invention will be more clearly understood by the following four specific examples and one comparative example.

Preparation of main chain type imidazolium salt polyionic liquid

Imidazole (1.4g, 15.0mmole) was added to tetrahydrofuran (10mL) and stirred at 50 ° C to completely dissolve, and lithium hydride (0.14g, 18.0mmole) was added to tetrahydrofuran (5mL) solution, and the lithium hydride / tetrahydrofuran solution was obtained. The solution was maintained at 0 ° C, and then the imidazole solution was added to the lithium hydride / tetrahydrofuran solution, and the solution was stirred at 0 ° C for 10 minutes, after which it was heated to 50 ° C and stirred for 30 minutes before adding 1-bromo-6. - chlorohexane (3.29 g, 16.5 mmole) was reacted for 24 hours. The reaction was quenched with EtOAc (EtOAc (EtOAc) The ionic liquid monomer (1-(6-chlorohexanyl)imidazole, expressed as ImC ₆ Cl) was obtained by silica gel flash chromatography (ethyl acetate: n-hexane, 2:1).

2.37 g (10.0 mmole) of the above ionic liquid monomer (ImC ₆ Cl) was added, and ethylene glycol (1 mL) was added thereto, and polymerization was carried out at 100 ° C for 24 to 72 hours. After completion of the reaction, it was cooled to room temperature, and completely dissolved by adding methanol (5 mL). The methanol solution was then slowly added dropwise to acetone (100 mL) and stirred to give a white powder. After filtering, the white powder was washed with acetone and dried under vacuum to obtain a polyionic liquid (expressed as P[ImC ₆ ][Cl]).

Finally, 0.57 g of the above polyionic liquid (P[ImC ₆ ][Cl]) was dissolved in a mixed solvent of 20 mL (methanol:water, 2:1, v/v) to obtain LiN(SO ₂ CF ₂ CF ₃ ) ₂ (2.87 g, 10.0 mmole) was dissolved in deionized water (20 mL). Further, the above P[ImC ₆ ][Cl] solution was slowly added to the LiN(SO ₂ CF ₂ CF ₃ ) ₂ solution, and the mixture was vigorously stirred at room temperature for 7 days for anion exchange. After the reaction was completed, the mixture was suction filtered and dried. A polyionic liquid having an anion of N(SO ₂ CF ₂ CF ₃ ) ₂ ^- (chemically represented by P[ImC ₆ ][NTf ₂ ]) can be obtained.

Preparation of polydimethyldipropenyl ammonium ionic liquid

8.1 g of an aqueous solution of polydimethyldipropenyl ammonium ion (anion of Cl ^- , molecular weight 400,000 to 500,000, 20 wt% aqueous solution) was slowly added to 30 ml of an aqueous solution containing LiNTf ₂ (3.44 g, 12 mmole), and stirred at room temperature for one day. The white powder of polydimethyldipropylenealkylammonium ion (anion is NTf ₂ ^- , represented by P[DADMA][NTf ₂ ]) can be obtained by suction filtration and drying. After theoretical calculation, the molecular weight is 1,000,000~ 1,250,000.

Chromatography column preparation

First, set the film thickness of the static phase layer required for the chromatography column, calculate the weight of each component when the concentration of the static phase layer material to be prepared (C) is calculated by the following formula (1), prepare a static phase solution, and then The static phase solution is filled into the capillary Then, the solvent is drained by a vacuum pumping motor, and the static phase layer having a predetermined film thickness is formed on the capillary wall to prepare the chromatography column.

In the following specific examples and comparative examples, the selected column length was 5 m, the inner diameter was 320 μm, and the film thickness of the static phase layer was set to 0.25 μm, and acetone was used as a solvent.

C (mg/mL) static phase concentration = 2000ρd _f /r (1)

d _f : film thickness of the column (μm)

r: hollow cylinder radius ( μ m)

ρ : static phase material density (g/mL)

Specific example 1

The above-prepared P[ImC ₆ ][NTf ₂ ] and P[DADMA][NTf ₂ ] were dissolved in an acetone solution at a weight ratio of 1:1 to prepare a static phase solution.

After the above-mentioned chromatography column preparation method is used, the static phase solution is filled into the capillary tube, and then the solvent is drained by a vacuum pumping motor to form a static phase layer on the inner wall surface of the capillary tube to obtain a chromatography column.

Specific example 2~4

The specific examples 2 to 4 are substantially the same as the configuration and preparation method of the specific example 1, except that the P[ImC ₆ ][NTf ₂ ] and the P[DADMA][NTf ₂ ] are respectively in a weight ratio of 2:1, 4 : 1, 9:1 mixed.

Comparative example 1

The previously prepared P[ImC ₆ ][NTf ₂ ] was dissolved in an acetone solution to prepare a static phase solution.

After the static phase solution was filled into the capillary tube, the solvent was drained by a vacuum pumping motor to form a static phase layer on the capillary wall to prepare a chromatography column.

Comparative example 2

The previously prepared P[DADMA][NTf ₂ ] was dissolved in an acetone solution to prepare a static phase solution.

After the static phase solution was filled into the capillary tube, the solvent was drained by a vacuum pumping motor to form a static phase layer on the capillary wall to prepare a chromatography column.

Next, P[ImC ₆ ][NTf ₂ ], P[DADMA][NTf ₂ ], and the specific examples 1 to 4 described above, and in Comparative Example 1, the P[ImC ₆ ][NTf ₂ ]/P[DADMA The mixture of [NTf ₂ ] weight ratios of 1:1, 2:1, 4:1, and 9:1 was measured by TGA, and the measurement results were summarized in Table 1 and Figure 1 below.

From the results of TGA analysis in Figure 1 and Table 1, it can be seen that the thermal cracking (Td) of P[ImC ₆ ][NTf ₂ ] and P[DADMA][NTf ₂ ] can be greater than 380 ° C, and P[ImC ₆ ][ NTf _2] and P [DADMA] [NTf _2] after blending, _{P [ImC 6] [NTf 2} ] the higher the content, the more excellent thermal stability, and when _{P [ImC 6] [NTf 2} ] and P [ When the blending ratio of DADMA][NTf ₂ ] is 1:1, the thermal stability can be maintained above 380 °C. However, since the separation effect of P[DADMA][NTf ₂ ] is not good, the separation effect and heat resistance are considered, and the chromatography column of the specific examples 3 and 4 is selected for subsequent sample separation and membrane stability measurement. .

Next, the following samples 1 to 4 were separated by the chromatography column prepared in the above Specific Examples 3 and 4 and Comparative Examples 1 and 2. It should be noted that in the following samples, the numbers before the respective components are the labels corresponding to the peaks in the drawings.

Sample 1 (linear alkane mixture, solvent: hexane): (1) ~ (15) C ₁₂ ~ C ₂₆ , (16) ~ (20): C ₂₈ , C ₃₀ , C ₃₂ , C ₃₄ , C ₃₆ .

Sample 2 (n-alcohol mixture, solvent: methanol): (1) 1-butanol/n-butanol, (2) 1-hexanol/n-hexanol, (3) 1-octanol/n-octanol, (4) 1- Nonanol / n-nonanol, (5) 1-decanol / n-nonanol, (6) 1-dodecanol / n-dodecanol mixture.

Sample 3 (polycyclic aromatic hydrocarbon mixture, solvent: acetone): (1) acenaphthylene/decene, (2) fluorene/fluorene, (3) phenanthrene/phenanthrene, (4) anthracene/蒽, (5) pyrene/芘(6) benzo[a]anthracene/1,2-benzopyrene, (7) chrysene/1,2-benzophenanthrene, (8)benzo[b]fluoranthene/benzo[b]fluoranthene, (9) ) Benzo[k]fluoranthene/benzo[k]fluoranthene, (10)benzo[a]pyrene/benzo[a]pyrene, (11)indeno(1,2,3-cd)pyrene/茚[1, 2,3-cd]芘, (12) dibenzo[a,h]anthracene/dibenzo[a,h]蒽, (13)behzo[ghi]perylene/benzo[ghi]perylene.

Sample 4 (plasticizer, solvent: methanol): (1) diethylphthalate / diethyl phthalate, (2) di-n-butylphthalate / dibutyl phthalate, (3) di-n-octylphthalate / Dioctyl phthalate, (4) bis (2-ethylhexyl) phthalate / bis(2-ethylhexyl phthalate).

Refer to Table 2, Table 2 for the parameter conditions for separating samples 1~4.

2 to 5, FIGS. 2 to 5 are the results of analysis of the samples 1 to 4 by using the chromatography columns of the specific examples 3 and 4 and the comparative examples 1 and 2, and in FIGS. 2 to 5, respectively, from top to bottom. The separation results of the specific examples 3 and 4 and the comparative examples 1 and 2.

It can be seen from the separation results of Figures 2 to 5 that when pure P[ImC ₆ ][NTf ₂ ] is used as the material of the static phase layer, the separation effect is excellent, and pure P[DADMA][NTf ₂ ] is used as the static phase layer material. From the results of the separation of Figures 2 to 5, it is known that the effect is not good, and even there is no separation effect on the sample 2 (alcohol mixture); however, P[ImC ₆ ][NTf ₂ ] and P[DADMA][NTf ₂ ] The separation results after blending showed that excellent separation results were obtained, which were not affected by the blending, and even when the blending ratio was 4:1, the samples were maintained and P[ImC ₆ ][NTf ₂ ] is the separation property of a stationary phase chromatography material. Therefore, it is presumed that the structure of the polydimethyldiallylammonium ionic liquid and the imidazolium polyionic liquid should be the main chain type ammonium ionic liquid, and therefore, the main chain type imidazolium salt is not easily affected after the blending. The separation effect of the polyionic liquid-like liquid can make the chromatographic static phase material of the present invention have superior separation.

Next, after the chromatography columns of the specific examples 3 and 4 and the comparative example 1 were allowed to stand for a while, the samples 1-4 were further separated under the same conditions to examine the separation properties and film stability of the static phase layers. Sex. The separation of the chromatography column and the film stability results are summarized in Figures 6-17. 6 to 8 are the separation results of the sample 1 (alkane mixture) in the specific examples 3 and 4 and the comparative example 1, and the samples of the specific examples 3 and 4 and the comparative example 1 are shown in FIGS. 9 to 11 respectively. 2 (Alcohol mixture) separation results, FIGS. 12 to 14 are the separation results of the sample 3 (polycyclic aromatic hydrocarbon mixture) in the specific examples 3 and 4 and the comparative example 1, respectively, and FIGS. 15 to 17 are specific examples. 3, 4 and Comparative Example 1 The results of the separation of the sample 4 (plasticizer), and in Figures 6 to 17, the following figure is the original analysis results, the above figure is after the column is allowed to stand for 2 months. Analysis results.

From the analysis results of the retention time of each peak in FIGS. 6 to 17, it can be seen that when the main chain type imidazolium-based polyionic liquid is used as the stationary phase layer, it is referred to FIG. 8, 11, 14, and 17, although the sample 1 is used. The separation effect of ~4 is good, but after 60 days of standing, it is affected by gravity due to insufficient stability of the membrane, resulting in displacement of the material of the static phase layer, which affects the uniformity of the film of the static phase layer. After 60 days of standing, the sample was analyzed by the same sample and the same separation conditions, and the retention time of each peak was compared with the original residence time, and the problem of offset was generated; and the specific example 3, 4 was produced. The analysis results of the obtained chromatography column show that the chromatographic static phase material obtained by blending P[ImC ₆ ][NTf ₂ ] with P[DADMA][NTf ₂ ] has not only the main chain type imidazole. The salt polyion liquid has a considerable separation effect, and the residence time of each peak after 60 days of standing is very close to the original residence time, and the analysis of the chromatography column prepared in the specific example 3 is performed. The results are almost consistent with the retention results of the peaks of the original analysis. This shows that the stationary phase layers other than having excellent separation, the film may have excellent stability.

In summary, the present invention utilizes a polydialkyldiene by selecting a polydialkyl diallyl ammonium ionic liquid and a main chain type imidazolium salt-type polyionic liquid. The high molecular weight of the propyl ammonium ionic liquid maintains thermal stability, and the structure of the polydialkyl diallyl ammonium ionic liquid and the imidazolium salt polyionic liquid are both of the main chain type ammonium ionic liquids, and the mixture is mixed. After that, the characteristics of the separation effect of the main chain type imidazolium salt-type polyionic liquid are not affected, and the static phase chromatography material of the present invention can be made not only It can have a superior separation effect, and can also have both thermal stability and film stability, so that the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (9)

A chromatographic stationary phase material comprising a main chain type imidazolium salt type polyionic liquid having a repeating unit represented by the following formula (I), and a polydialkyl group having a repeating unit represented by the following formula (II) An allyl ammonium ionic liquid, wherein R ₁ of the formula (I) is hydrogen or an alkyl group, and each of R ₂ and R _{3 is} independently hydrogen, an alkyl group, or a benzene ring-substituted group, Y is selected From C ₁ to C ₂₀ alkyl, R ₄ and R _{5 of} formula (II) are each a C ₁ -C ₁₀ alkyl group, and Z ^- and X ^- are each selected from N(SO ₂ CF ₃ ) ₂ ^- , N(SO ₂ CF ₂ CF ₃ ) ₂ ^- , CF ₃ SO ₃ ^- , or a combination thereof, the molecular weight of the polydialkyl diallyl ammonium ionic liquid is not less than 500,000, and the main chain type imidazolium salt is polycondensed The weight ratio of the ionic liquid to the polydialkyl diallyl ammonium ionic liquid is between 1:1 and 10:1. The chromatographic stationary phase material according to claim 1, wherein the polydialkyl diallyl ammonium ionic liquid has a molecular weight of from 500,000 to 2,000,000. The chromatographic stationary phase material according to claim 2, wherein the polydialkyl diallyl ammonium ionic liquid has a molecular weight of not less than 900,000. The chromatographic stationary phase material according to claim 1, wherein the polydialkyldiene The weight ratio of the allyl ammonium ionic liquid to the main chain type imidazolium salt polyionic liquid is between 1:2 and 1:5. The chromatographic stationary phase material according to claim 1, wherein the main chain type imidazolium salt polyionic liquid has a molecular weight of not less than 20,000, and R ₁ , R ₂ , and R ₃ are each selected from hydrogen or C ₁ to C. An alkyl group of ₁₀ , and Y is a single bond alkyl group selected from C ₃ to C ₂₀ . The chromatographic stationary phase material according to claim 1, wherein the main chain type imidazolium salt type polyionic liquid has a molecular weight of not less than 20,000, R _{1 is} selected from hydrogen, or a C ₁ to C ₁₀ alkyl group, R ₂ and R ₃ together constitutes a benzene ring-substituted group to form a benzimidazole structure represented by the following formula (III), and R ₆ to R _{9 are each} independently selected from hydrogen or a C ₁ -C ₁₀ alkyl group, and Y is selected from the group consisting of a single bond alkyl group of C ₃ to C ₂₀ . The chromatographic stationary phase material of claim 1, wherein Z ^{- is} selected from the group consisting of N(SO ₂ CF ₃ ) ₂ ^- . The chromatographic stationary phase material of claim 1, wherein X ^{- is} selected from the group consisting of N(SO ₂ CF ₃ ) ₂ ^- . A chromatography column comprising a hollow tubular body and a static phase layer formed on an inner wall surface of the body, wherein the static phase layer is composed of a chromatographic stationary phase as claimed in claim 1 material.