JPH06258203A - Cartridge column for solid phase extraction - Google Patents

Abstract

PURPOSE:To provide excellent recovery by using a cross-linked copolymer particle by means of copolymerization of several kinds of the specific materials. CONSTITUTION:Cross-linked copolymer particles 2 are composed by aqueous suspension copolymerization, in which 20-70 parts by weight of divinylbenzene, 30-80 parts by weight of polyhydric alcohol poly (meta) acrylic ester are used so that they make 100 parts by weight in total and other vinyl group monomers are used if necessary. These compounds are used solely or in combination of two or more, and aqueous suspension copolymerization is carried out under the existence of a polymerization starter. Azo group compounds such as benzoyl peroxide, dichlorobenzoyl peroxide, and the like are available for a polymerization starter. A solid phase extracting cartridge column 4 is made by filling the cross-linked copolymer particles 2 in a resin reservoir 3, in which a resin filter 1 is set, and then sealing the reservoir by a resin filter 1 from the upper side.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solid phase extraction cartridge column.

[0002]

2. Description of the Related Art Conventionally, a liquid-liquid extraction method has been often used for extracting a sample from a liquid, but there are problems such as complexity of work and use of a large amount of solvent. Nowadays, along with the development of methods for synthesizing silica-based and polymer-based porous particles, a solid-phase extraction method, which is easy to work with, uses a small amount of solvent, and can process a large amount of sample, has come to be used. The following particles are known to be used for solid phase extraction. (1) Silica gel or chemically bonded silica gel in which the surface of silica gel is chemically modified (2) Styrene-divinylbenzene copolymer (3) (Meth) acrylic acid ester copolymer

[0003]

However, when the chemically-bonded silica gel of (1) above is used for environmental analysis for analyzing agricultural chemicals on golf courses and residual synthetic antibacterial agents in meat, impurities contained in silica are There is a problem that some samples may be decomposed due to the influence. The styrene-divinyl copolymer of the above (2) has a problem that the workability at the time of treating an aqueous solution is deteriorated because of its strong hydrophobicity. The (meth) acrylic acid ester copolymer of the above (3) has a problem that the recovery rate of the sample is lowered due to its strong hydrophilicity. The present invention solves such problems and provides a solid-phase extraction cartridge column having an excellent recovery rate.

[0004]

The present invention comprises (a) 20 to 70 parts by weight of divinylbenzene, (b) 30 to 80 parts by weight of polyhydric alcohol poly (meth) acrylic acid ester ((a) + (b)). = 100 parts by weight) and (c) a solid-phase extraction cartridge column in which a resin-made reservoir is filled with a cross-linked copolymer particle obtained by copolymerizing another vinyl-based monomer used as necessary.

The (a) divinylbenzene used in the present invention is not particularly limited in purity, but it is preferable to use one having a purity of 60% by weight or more. The polyhydric alcohol poly (meth) acrylic acid ester (b) used in the present invention (herein, the notation of (meth) acrylic acid means acrylic acid and methacrylic acid) includes ethylene glycol diacrylate and ethylene glycol. Dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, glycerin di- or triacrylate, glycerin di- or trimethacrylate, trimethylolpropane Di- or triacrylate, trimethylolpropane di- or trimethacrylate, tetramethylolmethane di-, tri- or Tetraacrylate, di tetramethylolmethane, tri- or tetramethacrylate, and the like. Considering reactivity and swelling property of the produced copolymer particles, ethylene glycol dimethacrylate is preferable. These compounds can be used alone or in combination of two or more kinds.

In the present invention, (a) divinylbenzene and (b) polyhydric alcohol poly (meth) acrylic acid ester are (a) 20 to 70 parts by weight, (b) 30 to 80 parts by weight, and (a) + (B) = 100 parts by weight is used. (A) When the amount of divinylbenzene is too small, the hydrophilicity of the copolymer particles increases, the swelling and contraction between the solvents increase, and the recovery rate decreases. When the amount is too large, the hydrophobicity of the copolymer particles increases and the recovery rate varies. Occurs.

The aqueous suspension polymerization is carried out in the presence of a polymerization initiator. Examples of the polymerization initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and tert-butyl perbenzoate, organic peroxides such as methyl ethyl ketone peroxide and methyl cyclohexanone peroxide, and azobis. Examples thereof include azo compounds such as isobutyronitrile and dimethylazodiisobutyrate.
These may be used alone or in combination of two or more. The amount used is appropriately determined depending on the kind of the monomer, etc., but is 0.1% with respect to the total amount of the monomers.
It is preferable to use ˜4.0% by weight.

The aqueous suspension polymerization is carried out in the presence of a dispersant.
Examples of the dispersant include water-soluble cellulose derivatives such as polyvinyl alcohol, alkyl cellulose, hydroxyalkyl cellulose and carboxyalkyl cellulose, and polymeric protective colloids such as sodium polyacrylate. The dispersant is preferably used in the range of 1 to 0.001% by weight with respect to water. If necessary, an anionic surfactant may be added to the polymerization system as a dispersion aid to adjust the particle size, or the solubility of the monomer or organic solvent in water may be reduced to improve the solubility of the water-soluble inorganic substance. Salts can be added to the polymerization system.

The copolymer produced can be made porous by adding an organic solvent which is incompatible with water during the polymerization. The organic solvent that is incompatible with water used in the present invention,
The amount dissolved in 100 g of water at 25 ° C. is 15 g or less, and examples thereof include toluene, diethylbenzene, dodecane, isoamyl alcohol, ethyl acetate, propyl acetate, butyl acetate, and cellosolve acetate. You may use these solvents individually or in combination of 2 or more types. These are preferably used in an amount of 0 to 300% by weight based on the total amount of monomers.

The polymerization reaction is usually carried out in the temperature range of 70 to 90 ° C. for 5 to 8 hours. The spherical copolymer particles having a particle size of 10 to 200 μm, preferably 30 to 100 μm, obtained as described above are classified as necessary and used as cross-linked copolymer particles for solid phase extraction. The resin-made reservoir is insoluble in an organic solvent, and the cross-linked copolymer particles need not flow out of the resin-made reservoir during the sample concentration operation, and the material and shape thereof are not particularly limited. Examples of such a material include a syringe type syringe having a volume of 1 to 500 ml, preferably 5 to 50 ml, such as polypropylene or polyethylene, and a resin filter set therein. The filling amount of the crosslinked copolymer particles in the resin reservoir varies depending on the bulk density of the particles and the concentration of the sample, but is usually 300 to 2000 mg, preferably 400 to 10 mg per 8 ml volume of the resin reservoir.
Fill to 00 mg.

[0011]

EXAMPLES Next, the present invention will be described with reference to examples.

Example 1 100 g of divinylbenzene (manufactured by Sankyo Kasei Co., Ltd.) having a purity of 60% by weight, 1 part of ethylene glycol dimethacrylate
00g, butyl acetate 200 as an organic solvent insoluble in water
g, 50 g of isoamyl alcohol and 1.0 g of azobisisobutyronitrile are suspended in 1 liter of a 0.2% by weight aqueous solution of methylcellulose, and stirred at 70 ° C. under high speed stirring (1500 rpm) using a homomixer. After stirring for a minute, the particle size was adjusted to 30 to 100 μm. Then, the mixture was transferred to a propeller stirrer and reacted at 80 ° C. for 6 hours while stirring (200 rpm) to obtain copolymer particles for solid phase extraction. Filter the particles into 2 liters of water,
Then, the mixture was ultrasonically washed with 2 liters of acetone, filtered for 1 hour, air-dried and vacuum-dried (yield was 98%). The obtained particles were classified to 40 to 90 μm to obtain crosslinked copolymer particles for solid phase extraction cartridge column. As shown in FIG. 1, the cross-linked copolymer particles 2 are made of resin (made of polypropylene) in which a resin filter 1 is set.
0.5 g was filled in the reservoir 3 of the above, and the cartridge column 4 for solid-phase extraction was obtained by capping with the resin filter 1 from above. Using this solid-phase extraction cartridge column 4, the pesticide was concentrated and the recovery rate was measured by the following procedure. (1) The solid phase extraction cartridge column 4 is set in the suction manifold 6 as shown in FIG. (2) Set the receiving measuring flask 7 in the suction manifold 6. (3) Start suction and reduce the pressure to adjust the inside of the suction manifold 6 to 11 to 13 mmHg. (4) Reservoir 5 for sample injection with 5 ml of acetonitrile
And open the two-way cock 8 to suck. (5) Continuously, pass 30 ml of pure water. (6) 6m standard sample containing 6 kinds of pesticides adjusted to 10ppm
200 ml of samples containing 6 kinds of pesticides prepared to 0.25 ppm each by diluting 1 to 40 times with a 200 ml volumetric flask is put into the sample injection reservoir 5 to set the solid extraction cartridge column 4. The pesticide components are passed through the liquid and concentrated (by adsorption) into the cross-linked copolymer particles 2 in the solid extraction cartridge column 4. (7) After the liquid has passed through the solid extraction cartridge column 4, the two-way cock 8 is closed, the solid-phase extraction column 4 is moved to the next side while the sample injection reservoir 5 is attached, and the two-way cock 10 is attached. Install. (8) Add 5 ml of acetonitrile to the sample injection reservoir 5 and open the two-way cock 10 to elute the concentrated pesticide components and guide them to the measuring flask 9 (at this time, the cross-linked polymer in the solid phase extraction cartridge column 4). All pesticides that have been concentrated (by adsorption) in particles 2 are desorbed and eluted). (9) 20 μl of the concentrated pesticide ingredients after shaking and stirring
Are separated by high performance liquid chromatography (HPLC) and the area value is determined. (10) 20 μl of 7 kinds of pesticide-containing samples (standard samples) prepared to 10 ppm each are separated by high performance liquid chromatography (HPLC) and the area value is obtained. (11) Obtain the recovery rate by the area value of the concentrated component / the area value of the standard sample. Concentration capacity of cross-linked copolymer particles (adsorption capacity or desorption capacity)
If it is weak, the pesticide in the sample is not adsorbed on the cross-linked copolymer particles, or the adsorbed one is not smoothly desorbed, and the recovery rate is lowered. The results of recovery measurements are shown in Table 1. Since all of the recoveries were 85% or more, it was found that the sample had an excellent concentration ability.

Example 2 Synthesis and recovery were measured in the same manner as in Example 1 except that 140 g of divinylbenzene having a purity of 60% by weight and 60 g of ethylene glycol dimethacrylate were used, and the results are shown in Table 1. . The recovery rate was excellent as in Example 1.

Comparative Example 1 Synthesis and recovery were measured in the same manner as in Example 1 except that 200 g of divinylbenzene having a purity of 60% by weight was used, and the results are shown in Table 1. Part of the recovery rate was low and reproducibility was poor.

Comparative Example 2 Synthesis and recovery were measured in the same manner as in Example 1 except that 160 g of ethylene glycol dimethacrylate, 40 g of stearyl methacrylate and 200 g of butyl acetate were used, and the results are shown in Table 1. Similar to Comparative Example 1, a part of the recovery rate was low and the reproducibility was poor.

[Table 1] The HPLC measurement conditions are as follows: Column: Excelpak GLF-R27 (5 mmφ x 250 m
Mobile phase: acetonitrile / 25 mM KH ₂ PO ₄ (pH 3.
15) Flow rate: 1.0 ml / min Detector: Ultraviolet absorption detector Wavelength: UV220nm Injection volume: 20 μl

[0016]

The solid-phase extraction cartridge column of the present invention is compact, inexpensive, and disposable. In addition, since the adsorption and desorption properties are good and the recovery rate is excellent, samples of dilute solutions of environment-related compounds such as agricultural chemicals and halogenated solvents can be easily concentrated with good workability, and the concentrated samples are suitable for various analyzes. It can be used and various analyzes can be easily performed.

[Brief description of drawings]

FIG. 1 is a schematic view of a solid phase extraction cartridge column of the present invention.

FIG. 2 is a schematic diagram showing an example of an apparatus for concentrating and recovering a sample using the solid phase extraction cartridge column of the present invention.

[Explanation of symbols]

 1 Filter 2 Crosslinked Copolymer Particles 3 Resinous Reservoir 4 Cartridge Column for Solid Phase Extraction 5 Reservoir for Sample Injection 6 Suction Manifold 7 Volumetric Flask 8 Two-way Cock 9 Two-way Flask 10 Two-way Cock 11 Three-way Cock 11

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Hirai 4-13-1, Higashimachi, Hitachi-shi, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Institute (72) Inventor Yoshinori Inoue 1-16-1, Nakamachi, Musashino-shi, Tokyo No. 10 Yokogawa Analytical Systems Co., Ltd. (72) Inventor Hiroki Kumagai 1-16-10 Nakamachi, Musashino-shi, Tokyo Yokogawa Analytical Systems Co., Ltd.

Claims (1)

[Claims] 1. (a) 20 to 70 parts by weight of divinylbenzene, (b) 30 to 80 parts by weight of a polyhydric alcohol poly (meth) acrylic acid ester ((a) + (b) = 100 parts by weight) and (c). ) A solid-phase extraction cartridge column in which a resin-made reservoir is filled with cross-linked copolymer particles obtained by aqueous suspension-copolymerizing other vinyl-based monomers used as necessary.