JPH05126816A - Filler for liquid chromatography - Google Patents

Abstract

PURPOSE:To obtain filler for liquid chromatography having a fluoroalkyl group, which has high hydrophobic property ad is strongly bonded to a carrier having a hydroxyl group by directly introducing a specified fluorosilicon-based compound to the carrier. CONSTITUTION:Filler for liquid chromatography is obtained by introducing the fluorosilicon-based compound expressed by formula I into a carrier. R1 in the formula represents hydrogen atom or methyl group. R2 and R3 are the same or different groups and represent trimethylsilyl oxy group, alkyl group having the carbon number of 1-4, alkyl-carbonyl oxy group or alkoxyl group. RF expressed by formula II or formula III. (In the formulas, X represent hydrogen atom, fluorine atom or chlorine atom, n1 represents the integer of 1-10 and n2 represents the integer of 0-8). In the formulas, (m) represents the integer of 1-10, and l represents 1 or 0. When l is 0, R1 represents hydrogen atom. Since the fluoroalkyl group is directly introduced into the carrier by chemical bonding, the strong bonding to the carrier is imparted, and the high hydrophobic property and oil repelling porperty are shown. Therefore, this filler is useful as the filler for the liquid chromatography for which the hydrophobic property is required.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel packing material for liquid chromatography.

[0002]

2. Description of the Related Art Conventionally, as a packing material for liquid chromatography, a packing material in which a hydrophobic alkyl group, a phenyl group or the like is introduced into a carrier having a hydroxyl group such as porous silica has been widely used. However, the above-mentioned filler has problems that it is not sufficiently hydrophobic and that it is modified depending on the type of component to be separated and purified.

Therefore, recently, in order to solve the above-mentioned problems, a packing material for liquid chromatography in which a fluoroalkyl group is introduced into a carrier by using a fluorosilane coupling agent having a fluoroalkyl group has been proposed [Japanese Patent Laid-Open No. Hei 10-1999] 2-287151, JP-A-63-16327
4, Gazette, Anal. Chem., Volume 52, 1990 (1980); Journal of
Chromatography, Volume 218, 443 (1981), etc.]. However, since the fluorosilane coupling agent used in the filler has one silane coupling group capable of binding to the carrier per one fluoroalkyl group, the binding ability to the carrier is insufficient. There is a problem.

Therefore, at present, there is a strong demand for the development of a fluoroalkyl group-containing filler for liquid chromatography in which a fluoroalkyl group is introduced into a carrier by using a fluorosilane coupling agent having a high binding ability to the carrier. is there.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a packing material for liquid chromatography having a highly hydrophobic fluoroalkyl group strongly bonded to a carrier having a hydroxyl group such as porous silica. Especially.

[0006]

According to the present invention, a fluorosilicone compound represented by the following general formula 2 (hereinafter referred to as fluorosilicone compound 1) is introduced into a carrier for liquid chromatography. A filler is provided.

[0007]

[Chemical 2]

The present invention will be described in more detail below.

The packing material for liquid chromatography of the present invention is characterized by introducing a specific fluorosilicone compound into a carrier.

The specific fluorosilicone compound introduced into the carrier in the packing material for liquid chromatography of the present invention is the fluorosilicone compound 1 represented by the general formula 2. The fluorosilicone compound 1
In, when R ₂ or R ₃ has 5 or more carbon atoms, the production is difficult, and when n ₁ exceeds 10 or n ₂ exceeds 8, the solubility in a solvent decreases. Because it cannot be used. Further, when m exceeds 10, the production is difficult. Furthermore, the average molecular weight of the fluorosilicone compound 1 is preferably in the range of 500 to 10,000. When the average molecular weight is out of the above range, the production is difficult, which is not preferable.

In the fluorosilicon compound 1, the applicable RF, namely,-(CF ₂ ) n ₁ X or the following general formula 3 is specifically listed. F ₃ C-, F (C
_{F 2) 2 -, F (} CF 2) 3 -, F (CF 2) 4 -, F (CF
₂ ) ₅ −, F (CF ₂ ) ₆ −, F (CF ₂ ) ₇ −, F (C
_{F 2) 8 -, F (} CF 2) 9 -, F (CF 2) 10 -, HCF 2
_{-, H (CF 2) 2} -, H (CF 2) 3 -, H (CF 2)
_{4 -, H (CF 2)} 5 -, H (CF 2) 6 -, H (CF 2) 7
_{-, H (CF 2) 8} -, H (CF 2) 9 -, H (CF 2) 10
_{-, ClCF 2 -, Cl (} CF 2) 2 -, Cl (CF 2) 3
_{-, Cl (CF 2) 4} -, Cl (CF 2) 5 -, Cl (CF
_{2) 6 -, Cl (CF} 2) 7 -, Cl (CF 2) 8 -, Cl
(CF ₂ ) ₉ −, Cl (CF ₂ ) ₁₀ −, the following chemical formula 4,
Chemical formula 5, Chemical formula 6, Chemical formula 7, Chemical formula 8, Chemical formula 9, Chemical formula 10, Chemical formula 11, Chemical formula 1
It is 2.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

Specific examples of the fluorosilicone compound 1 include those represented by the following general formulas, 13, 14, 15, 15, 17, 18, 19, 19, 20, and 2.
1, chemical formula 22, chemical formula 23, chemical formula 24, chemical formula 25, chemical formula 26, chemical formula 2
7, Chemical 28, Chemical 29, Chemical 30, Chemical 31, Chemical 32, Chemical 3
3, Chemical formula 34, Chemical formula 35, Chemical formula 36, Chemical formula 37, Chemical formula 38 and the like can be mentioned (where m is an integer of 1 to 10).

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

[0039]

[Chemical 29]

[0040]

[Chemical 30]

[0041]

[Chemical 31]

[0042]

[Chemical 32]

[0043]

[Chemical 33]

[0044]

[Chemical 34]

[0045]

[Chemical 35]

[0046]

[Chemical 36]

[0047]

[Chemical 37]

[0048]

[Chemical 38]

To prepare the fluorosilicone compound 1, a difluoroalkanoyl peroxide represented by the following general formula 39 and a vinyl group-containing organosilicon compound represented by the following general formula 40 are preferably used in a molar ratio. At 1: 1.0
To 10.0, particularly preferably 1: 1.2 to 5.0
In the range of, preferably reaction temperature -20 to +15
It can be obtained by reacting in the range of 0 ° C., particularly preferably in the range of 0 to 100 ° C., preferably for 30 minutes to 20 hours, and particularly preferably for 3 to 10 hours.

[0050]

[Chemical Formula 39]

[0051]

[Chemical 40]

Further, RF in the above difluoroalkanoyl
Is the same as RF specifically listed in the fluorosilicon compound 1, and specific examples of the difluoroalkanoyl 2 include diperfluoro-2-methyl-3-oxahexanoyl peroxide and diperfluoro-2-methyl-3-oxahexanoyl peroxide. Perfluoro-2,5-dimethyl-3,6-dioxanonanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide, peroxide Preferred examples include diperfluoroheptanoyl and the like. Further, as the organosilicon compound, trimethoxyvinylsilane, 3-methacryloxypropyltrimethoxysilane, triethoxyvinylsilane, triisopropoxyvinylsilane, 3-
Methacryloxypropyldiethoxymethylsilane and the like can be preferably mentioned.

The carrier into which the fluorosilicone compound 1 is introduced in the packing material for liquid chromatography of the present invention is not particularly limited as long as it is one that is usually used as a packing material for liquid chromatography. Particularly, a polymer compound which is chemically stable and has a large number of hydroxyl groups on the surface can be preferably used. Specific examples of the polymer compound preferably include silica gel, porous glass, polyacrylate gel, polyvinyl alcohol gel, and the like. The average pore diameter and the average particle diameter of the carrier are not particularly limited, but the average pore diameter is 50 to 50.
00Å, and the average particle size is preferably 100 μm or less.

In order to introduce the fluorosilicone compound 1 into the carrier in the present invention, it is obtained by dispersing it in a solvent such as toluene, m-xylene, o-xylene, p-xylene, dimethylsulfoxide or tetrahydrofuran. A fluorosilicone compound is added to the resulting dispersion solution, preferably 1 to 4 in the range of 20 to 150 ° C.
It can be introduced by a silylation reaction for 0 hours. It is also possible to improve the hydrophobicity of the carrier by treating the unreacted hydroxyl group by treating the carrier after the silylation reaction with a hydrophobic capping agent such as trimethylchlorosilane.

The packing material for liquid chromatography of the present invention can be widely used in the usual manner as in the conventionally known packing material for liquid chromatography.

[0056]

EFFECT OF THE INVENTION The packing material for liquid chromatography of the present invention has a strong binding ability to the carrier because the fluoroalkyl group is directly introduced into the carrier by a chemical bond, and further has high hydrophobicity and oil repellency. Indicates. Therefore, it is useful as a packing material for liquid chromatography that requires hydrophobicity, particularly as a packing material for separating fluorine-containing compounds.

[0057]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0058]

Example 1 2.3 g of trimethoxyvinylsilane (1
5.4 mmol) to diperfluoro-2-methyl-peroxide
1,1,2-Trichlorotrifluoroethane solution containing 5.1 g (7.7 mmol) of 3-oxahexanoyl 150
g was added and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed, and then the residue was purified by distillation to obtain 4.5 g of a fluorosilicone compound represented by the following structural formula 41.

[0059]

[Chemical 41]

Next, spherical silica gel (average pore size 12
10 g (0Å, average particle size 5 μm) was heated and dried at 120 ° C. for 4 hours to be activated. Next, the activated silica gel was added and dispersed in 50 g of xylene to obtain a dispersion solution. The obtained dispersion solution was charged with 9.5 g of the fluorofluorosilicon compound and reacted at 130 ° C. for 20 hours. After the reaction was completed, the product was filtered and dried under vacuum to obtain silylated silica gel. The obtained silylated silica gel was put into a xylene solution containing 5 g of trimethylchlorosilane, reacted at 130 ° C. for 12 hours to cap the residual silanol groups, and then dried to obtain a packing material for liquid chromatography. Obtained. The IR spectra of the obtained filler and untreated silica gel were measured. As a result, it was found that the absorption due to the fluoroalkyl group in the obtained filler was 1335 cm to ¹ (C
F ₃₎ and 1240 cm ~ observed ¹ (CF _2), further, it has been found that the absorption of silanol groups found in 3450 cm ~ ¹ on silica gel untreated is significantly lost.

[0061]

EXAMPLE 2 2.5 g (10 mmol) of 3-methacryloxypropyltrimethoxysilane was added to 4.4 g of diperfluoro-2-methyl-3-oxahexanoyl peroxide.
50 g of a 1,1,2-trichlorotrifluoroethane solution containing 7 mmol) was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed, and the residue was purified by distillation (boiling point: 220 ° C./25 mmHg) to obtain 3.0 g of a fluorosilicone compound represented by the following structural formula 42.

[0062]

[Chemical 42]

Then, silylation and capping were carried out in the same manner as in Example 1 except that the obtained fluorosilicone compound was used to obtain a packing material for liquid chromatography with a yield of 17.2 g. Further, when the IR spectrum was measured, it was found that the absorption due to the fluoroalkyl group was 1340 cm to ¹ (CF ₃ ) and 1230 cm to ¹ (CF ₂ ).
Was recognized by.

[0064]

Example 3 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl diperfluoro-2,5-peroxide
Other than dimethyl-3,6-dioxanonanoyl,
A reaction was carried out in the same manner as in Example 1 to obtain the following structural formula 43
5.7 g of fluorosilicone compound represented by
Obtained.

[0065]

[Chemical 43]

Then, silylation and capping were performed in the same manner as in Example 1 except that the obtained fluorosilicone compound was used to obtain a packing material for liquid chromatography with a yield of 15.9 g. Further, the IR spectrum was measured to find that the absorption due to the fluoroalkyl group was 1350 cm to ¹ (CF ₃ ) and 1235 cm to ¹ (CF ₂ ).
Was recognized by.

[0067]

Example 4 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl diperfluoro-2,5-peroxide
Other than dimethyl-3,6-dioxanonanoyl,
Reaction was carried out in the same manner as in Example 2 to obtain the following structural formula:
Yield 4.1g of fluorosilicone compound
Obtained.

[0068]

[Chemical 44]

Then, silylation and capping were carried out in the same manner as in Example 1 except that the obtained fluorosilicone compound was used to obtain a packing material for liquid chromatography with a yield of 18.0 g. Further, the IR spectrum was measured to find that the absorption due to the fluoroalkyl group was 1345 cm to ¹ (CF ₃ ) and 1225 cm to ¹ (CF ₂ ).
Was recognized by.

[0070]

Example 5 The filler obtained in Example 1 was packed in a stainless steel column (4.5 mmφ × 25 cm), and a mixture of fluorobenzenes was added with methanol / water (60/40;
Reverse phase partition chromatography was obtained using (w / w) as the eluent. The results are shown in Figure 1.

[0071]

Comparative Example 1 A mixture of fluorobenzenes was subjected to reverse phase partition chromatography measurement in the same manner as in Example 1 except that a known ODS (octadecyl group-introduced silica gel) filler was used. The results are shown in Figure 2.

As is clear from these results, when the filler of the present invention is used, the peaks of the respective components are clearly separated, and the separation accuracy is superior to the conventional fillers. ..

[Brief description of drawings]

FIG. 1 is a chromatography chart measured using the filler of the present invention.

FIG. 2 is a chromatography chart measured using an ODS packing material.

Claims (1)

[Claims] 1. A packing material for liquid chromatography obtained by introducing a fluorosilicone compound represented by the following general formula 1 into a carrier. [Chemical 1]