JP2014118512A - Method for manufacturing amphoteric ion exchange resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method for manufacturing an amphoteric ion exchange resin applicable to a wide range of resin particles.SOLUTION: The problem is solved with a method for manufacturing an amphoteric ion exchange resin by reacting a polymerizable monomer having an amphoteric ion exchange group with a resin made by polymerizing a polymerizable monomer having a carbon-hydrogen bond.

Description

  The present invention relates to a cationic functional group and an anionic functional group comprising reacting a resin (polymer) obtained by polymerizing a polymerizable monomer having a carbon-hydrogen bond with an amphoteric functional group introducing agent. The present invention relates to a method for producing a group-containing resin (amphoteric ion exchange resin).

  Amphoteric ion-exchange resins are used in chromatography fields (Patent Document 1 and Patent Document 2), rheology control agents, paints such as matting agents, chemical fields such as inks and adhesives, LCD spacers, surface modification for silver salt films. Electronic industry such as pesticides, film modifiers for magnetic tapes and thermal paper running stabilizers, medical fields such as fine particles for in vitro diagnostics using immunoassay, cosmetics such as slip agents and extender pigments, and unsaturated It is used in general industrial fields such as low shrinkage agents for resins such as polyester, paper, dental materials, antiblocking agents, light diffusing agents, matting agents, and resin modifiers.

  The amphoteric ion exchange resin has an anionic functional group and a cationic functional group introduced on its surface by chemical bonding. Conventionally, an amphoteric ion exchange resin is a method in which an alkyl halide is introduced into a resin produced by polymerizing a monomer and then reacted with an alkyl sultone through amination with a secondary amine (Patent Document 3), and the introduced functional group. A method in which an amino acid ester is further introduced into (halogenated alkyl) and then hydrolyzed (Patent Document 4), and an azo group is introduced into a resin and then a polymerizable monomer having an amphoteric ion exchange group is graft-polymerized (Patent Document 5). ).

  Among the above-described conventional techniques, the production method in which a cationic functional group and an anionic functional group are introduced separately requires a large number of steps, and thus requires a long time for production and is complicated. In addition, it is difficult to balance the amount of cationic functional group introduced and the amount of anionic functional group introduced, producing an amphoteric ion exchange resin that is electrically neutral (equal positive and negative charges). Difficult to do. Amphoteric ion exchange resins that are not electrically neutral can be separated as cationic or anionic exchangers when used as, for example, chromatographic packing materials, causing specific adsorption of analytes. End up. On the other hand, even in the method of polymerizing a polymerizable monomer having an amphoteric ion exchange group, reproducibility is maintained especially when a large amount of the zwitterion exchanger is produced because there are various parameters governing the reaction of the polymerization process called graft polymerization. And the performance of the amphoteric ion exchange resin produced tends to vary from production lot to production lot.

JP 2010-71707 A (page 20) JP-A-6-229994 (page 19) JP 2002-529714 A (page 46) JP 2000-126617 A (page 5) JP 2001-141710 A (page 7)

  The present invention has been made in view of the problems of the prior art, and the purpose thereof is an amphoteric functional group capable of simultaneously and simply introducing a cationic functional group and an anionic functional group into a resin. It is an object of the present invention to provide a method for producing an amphoteric ion exchange resin, wherein a cationic functional group and an anionic functional group are simultaneously introduced into a resin by a chemical reaction that is relatively easy to control using a group introducing agent.

The present invention has been made to achieve the above object, and a resin in which a polymerizable monomer having a carbon-hydrogen bond is polymerized is represented by the general formula (wherein R1 is H or CH ₃ , A is O or NH, X- represents SO ₃ ^— or COO ⁻ , R 2 and R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n represent an integer of 1 to 30). This is a method for producing an amphoteric ion exchange resin characterized by reacting with a zwitterionic functional group-introducing agent (hereinafter sometimes referred to as “compound of formula 1”). Hereinafter, the present invention will be described in detail.

式１化合物は、前記一般式で表されるものであるが、前記一般式中、Ｒ^２、Ｒ^３において、炭素数１から４のアルキル基は、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ブチル等である。またｍ、ｎは1から３０の整数であるが、大きくなると製造される両性イオン交換樹脂の疎水性が増大し、両性イオン交換基に由来した静電的効果を低減させることから、１から１０であることが特に好ましい。

The compound represented by formula 1 is represented by the above general formula. In the above general formula, in R ² and R ³ , the alkyl group having 1 to 4 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, Butyl and the like. Further, m and n are integers of 1 to 30, but when they are increased, the hydrophobicity of the produced amphoteric ion exchange resin increases, and the electrostatic effect derived from the amphoteric ion exchange groups is reduced. It is particularly preferred that

  By reacting the compound of Formula 1 with a resin obtained by polymerizing a polymerizable monomer having a carbon-hydrogen bond, an amphoteric ion exchange resin can be produced. In the present invention, the resin in which a polymerizable monomer having a carbon-hydrogen bond is polymerized means a resin containing a polymerization component of a polymerizable monomer having a carbon-hydrogen bond on at least a part of the surface of the resin. For example, it may be a resin obtained by polymerizing only a polymerizable monomer having a carbon-hydrogen bond, or a polymerizable monomer having a carbon-hydrogen bond in a resin obtained by polymerizing any monomer by a so-called seed polymerization method. A resin containing a polymerization component of a polymerizable monomer having a carbon-hydrogen bond in a part of the surface of the resin, such as a resin that has been absorbed and polymerized, may be used.

  Examples of the polymerizable monomer having a carbon-hydrogen bond include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- n-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, methoxy styrene, Styrene derivatives such as p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and chloromethylstyrene, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride, vinyl acetate, vinyl propionate And vinyl esters such as vinyl butyrate, unsaturated nitriles such as acrylonitrile, ( T) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as dodecyl, stearyl (meth) acrylate, n = octyl (meth) acrylate, 2-chloroethyl (meth) acrylate, phenyl (meth) acrylate, methyl α-chloroacrylate, butadiene Conjugated dienes such as isoprene, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, N-vinyl pyrrole, N-vinyl carbazole, N- Trees polymerized with vinylindole It can be exemplified. These polymerizable monomers may have various functional groups, and may be used alone or in combination of two or more. The polymerization conditions may follow conventionally known conditions, and there are no special conditions in the present invention. The same applies when using a so-called seed polymerization method.

  In polymerizing the polymerizable monomer described above, a crosslinkable monomer can be added as necessary. Crosslinkable monomers include divinylbenzene, divinylnaphthalene, trimethylolpropane diacrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol. Polyfunctional monomers such as triacrylate, N, N-divinylaniline, divinyl ether and divinyl sulfite can be exemplified. These crosslinkable monomers may be used alone or in combination of two or more. There is no special restriction | limiting in the addition amount of the crosslinkable monomer with respect to a polymerizable monomer.

  In polymerizing the polymerizable monomer, for example, (meth) acrylic acid, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid Hydrophilic properties such as (meth) acrylic acid such as 2-hydroxyethyl and 2-hydroxypropyl (meth) acrylate and acid derivatives thereof, N-vinyl compounds such as maleic acid, fumaric acid and N-vinylpyrrolidone, and vinyl naphthalene salts A monomer can also be used in combination. In the above examples, “(meth) acryl” means “acrylic or methacrylic”.

  Although this invention manufactures an amphoteric ion exchange resin by making the above resin and Formula 1 compound react, there is no special restriction | limiting in the shape and dimension of resin. If the produced amphoteric ion exchange resin is used as a filler for liquid chromatography, for example, it can be exemplified that a resin in the form of particles having an arbitrary diameter is subjected to the reaction.

  The compound of formula 1 may be added directly to the reaction system, that is, the dispersion in which the resin is dispersed, but may be added in a state dissolved in a solvent such as water or alcohol. Examples of the amount of the compound of formula 1 used include 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the resin. When the amount of the compound of Formula 1 used is less than 0.1 parts by weight with respect to 100 parts by weight of the resin, the introduction amount of the cationic functional group and the anionic functional group is reduced, and the electrostatic as a zwitterion exchange resin This is because the effect tends to be insufficient, and the amount of ionic functional groups introduced into the resin does not increase corresponding to the amount of use even if the amount is more than 200 parts by weight. In addition, the amphoteric ion exchange resin produced becomes softer when the amount of the compound of formula 1 is increased. However, when used as a packing material for liquid chromatography, the operability of chromatography decreases with the softened resin. The use amount within the above range is particularly preferred.

When the resin and the compound of formula 1 are reacted, a radical generator is allowed to coexist in the reaction system.
The radical generator coexisting in the reaction system may be a conventionally known one, and may be appropriately selected according to the type of resin and the selected reaction temperature. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, methyl ethyl ketone peroxide, t-butylperoxy-2-ethylhexa Organic peroxides such as noate, di-t-butyl peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide and diisopropylbenzene hydroperoxide, azobisisobuty Ronitrile, azobiscyclohexacarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′- Zobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2-isopropylbutyronitrile), 1,1'-azobis (Cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4′-azibis (4-cyanovalerin) Acid) and azo compounds such as dimethyl-2,2′-azobisisobutyrate.

  The resin, the compound of formula 1 and the radical generator are removed from the reaction solution using a rotary evaporator, for example, and heated under vacuum conditions, and then the produced resin is dispersed in an organic solvent miscible with water. It can be exemplified that the amphoteric ion exchange resin is produced by washing and drying with water and an organic solvent. For the purpose of preventing deformation of the resin, the heating is preferably 25 to 120 ° C, more preferably 50 to 100 ° C. In addition to the vacuum conditions, for example, the inside of a vessel such as a reaction flask containing a reaction solution may be replaced with an inert gas such as nitrogen, argon, or helium and heated. In this case, the heating temperature is preferably 25 to 100 ° C, more preferably 50 to 80 ° C.

  According to the present invention, it is possible to introduce both an anionic functional group and a cationic functional group into a general resin particle having a carbon-hydrogen bond by a one-step reaction. Moreover, the reaction for introducing the zwitterionic functional group is simple in operation and control, in which the reaction is carried out in a vacuum or an inert gas atmosphere to a temperature in a range usually employed in the process of industrial production. It is possible to easily deal with mass production of the active ion exchanger. As a result, according to the present invention, it is possible to produce a uniform amphoteric ion exchanger with no difference between production lots at low cost and in large quantities. In addition, in the present invention, since the zwitterionic functional group is introduced using an introducing agent having a pair of cationic functional group and anionic functional group, a zwitterion exchange pair in which a positive charge and a negative charge are balanced is obtained. It is possible to manufacture.

  Thus, the present invention is excellent in uniformity, has a balance between positive charge and negative charge, and enables easy and large-scale production of amphoteric ion exchange resins. Paints such as matting agents, chemical fields such as inks and adhesives, LCD spacers, surface modifiers for silver salt films, film modifiers for magnetic tapes, thermal paper running stabilizers, and other electronic industries, immunoassays For medical use such as fine particles for in-vitro diagnostic drugs, cosmetics such as slip agents and extender pigments, and low shrinkage agents for resins such as unsaturated polyester, paper, dental materials, anti-blocking agents, light diffusing agents, mats This is a technique useful in general industrial fields such as an agent and a resin modifier.

FIG. 1 shows the results (chromatogram) of liquid chromatography obtained using the resin particles produced in Example 1, wherein 1 is toluene, 2 is uracil, and 3 is cytosine. It shows elution.

  Hereinafter, examples will be described to describe the present invention in more detail, but the present invention is not limited to these examples. In Examples and Comparative Examples, the manufactured zwitterion exchanger was evaluated by carrying out hydrophilic interaction chromatography described below and comparing the retention of polar compounds.

  That is, the manufactured resin was packed in a stainless steel column having an inner diameter of 4.6 mm and a length of 100 mm to obtain an evaluation column. The column for evaluation was connected to an HPLC system (trade name CCP & 8020 series, manufactured by Tosoh Corporation), and eluents (0.1 mol / L ammonium formate and acetonitrile, 9: 1 (volume ratio) dissolved in toluene, uracil, and cytosine, respectively. ) Was passed through a column maintained at 40 ° C. at a flow rate of 0.5 mL / min, and the separated components were detected and measured by absorbance measurement at 254 nm. The hydrophobic polarity of uracil and cytosine, which are highly polar, is stronger (longer) and the surface polarity of the amphoteric ion exchange resin is higher, that is, more cationic and anionic functional groups are introduced. Indicates that

Example 1
After mixing 220.0 parts by weight of water, 30.0 parts by weight of benzyl methacrylate and 1.50 parts by weight of 2-ethylhexyl thioglycolate in a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen gas introduction tube The inside of the container was replaced with a nitrogen atmosphere. An aqueous solution in which 1.20 parts by weight of potassium persulfate was dissolved in 25.0 parts by weight of water was added to this solution, and heated to 70 ° C. to conduct a polymerization reaction for 16 hours. After cooling, spherical polymer particles (seed particles) having a solid content concentration of 9.7% by weight were obtained. The obtained seed particles had an average particle size of 0.68 μm and a coefficient of variation of 5.2%.

  As the polymerizable monomer, 160.1 parts by weight of 95% by weight divinylbenzene was used, and 252.9 parts by weight of toluene, 1.80 parts by weight of 2,2′-azobis-2,4-dimethylvaleronitrile, dodecyl sulfate 1.50 parts by weight of sodium and 416.3 parts by weight of ion-exchanged water were mixed and treated with an ultrasonic homogenizer to obtain an emulsion.

  Next, after adding 37.5 parts by weight of a dispersion of seed particles to 1200 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol (Kuraray Co., Ltd., trade name POVAL 224), the emulsion prepared above was added. The mixture was added at room temperature and stirred for 16 hours, and oil droplets in the emulsion were absorbed by the seed particles.

  Then, it heated at 70 degreeC, stirring, and performed the polymerization reaction for 8 hours, and obtained the resin particle. After the resin particles were isolated, the resin particles were dispersed in 1000 parts by weight of 1,4-dioxane, stirred for 1 hour in an ultrasonic bath, and the polymer derived from the seed particles was extracted and removed to isolate the resin particles. .

  When the particle size distribution of the obtained resin particles was measured with a Coulter counter (manufactured by Coulter Co., Ltd.), the average particle size was 3.3 μm.

  After 4.1 parts by weight of benzoyl peroxide and 20 parts by weight of acetone were dissolved in a reaction vessel and dissolved, 240 parts by weight of a 5% methanol solution of carboxybetaine monomer (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name GLBT) and After 10.0 parts by weight (dry weight) of the resin particles obtained above were put into a uniform slurry, the reaction vessel was attached to a rotary evaporator, and the solvent was removed while reducing the pressure with an aspirator. The reaction vessel was put into a vacuum dryer and heated at 90 ° C. for 16 hours in a vacuum state. After standing to cool, it was isolated by washing with methanol and washing with water to obtain resin particles.

  The results of evaluating the surface polarity of the amphoteric ion exchange resin produced as described above are shown in Table 1. The obtained chromatogram is shown in FIG.

Comparative Example 1
Resin particles were obtained in the same manner as in Example 1 except that the compound of formula 1 (divinylbenzene) was not used. The results of evaluating the surface polarity of the resin thus produced are shown in Table 1.

Example 2
As a compound of formula 1, 12.5 parts by weight of 2-hydroxylethyl methacrylate and 77.5 parts by weight of diethylene glycol dimethacrylate were used, and 90.0 parts by weight of chlorobenzene, 2,2′-azobis-2,4-dimethylvaleronitrile 0 60 parts by weight, 0.50 parts by weight of sodium dodecyl sulfate, and 181.0 parts by weight of ion-exchanged water were mixed and treated with an ultrasonic homogenizer to obtain an emulsion.

  Next, after adding 20.3 parts by weight of the dispersion of seed particles obtained in Example 1 to 400 parts by weight of an aqueous solution of 2% by weight of polyvinyl alcohol (trade name POVAL 224, manufactured by Kuraray Co., Ltd.), The prepared emulsion was added, added at room temperature and stirred for 16 hours, and oil droplets in the emulsion were absorbed by the seed particles.

  Then, it heated at 70 degreeC, stirring, and performed the polymerization reaction for 8 hours, and obtained the resin particle. After the resin particles were isolated, the resin particles were dispersed in 1000 parts by weight of 1,4-dioxane, stirred for 1 hour in an ultrasonic bath, and the polymer derived from the seed particles was extracted and removed to isolate the resin particles. .

  When the particle size distribution of the obtained resin particles was measured with a Coulter counter (manufactured by Coulter, Inc.), the average particle size was 3.5 μm.

  After 4.1 parts by weight of benzoyl peroxide and 20 parts by weight of acetone were dissolved in a reaction vessel and dissolved, 240 parts by weight of a 5% methanol solution of carboxybetaine monomer (manufactured by Osaka Organic Chemical Industry, trade name: GLBT) and the above After 10.0 parts by weight (dry weight) of the obtained resin particles were put into a uniform slurry, the reaction vessel was attached to a rotary evaporator, and the solvent was removed while reducing the pressure with an aspirator. The reaction vessel was put into a vacuum dryer and heated at 70 ° C. for 24 hours in a vacuum state. After standing to cool, it was isolated by washing with methanol and washing with water to obtain resin particles.

  The results of evaluating the surface polarity of the amphoteric ion exchange resin produced as described above are shown in Table 1.

Example 3
Example 2 except that 240 parts by weight of a 5% methanol solution of 2-methacryloyloxyethyldimethyl-3-sulfopropylammonium hydroxide (manufactured by Sigma-Aldrich, trade name sulfobetaine monomer) was used instead of the carboxybetaine monomer. Thus, resin particles were obtained.

  The results of evaluating the surface polarity of the amphoteric ion exchange resin produced as described above are shown in Table 1.

Comparative Example 2
Resin particles were obtained in the same manner as in Example 2 except that the compound of formula 1 (carboxybetaine monomer, manufactured by Osaka Organic Chemical Industry, trade name GLBT) was not used. The results of evaluating the surface polarity of the resin thus produced are shown in Table 1.

表１において、比較例１及び比較例２で製造した樹脂粒子（式１化合物を使用しないことにより、陽イオン交換性官能基及び陰イオン性官能基のいずれも導入していない樹脂粒子）を充填したカラムでは、極性が異なるにもかかわらずウラシルとシトシンの保持時間はほぼ同一であった。また疎水性の高いトルエンが樹脂粒子と強く相互作用し、極性化合物であるウラシルやシトシンよりも長く保持された。一方、実施例１から実施例３で製造した本発明の樹脂粒子を充填したカラムでは、ウラシル、シトシンの保持時間がその極性に応じて長くなり、またその強い疎水性にもかかわらずトルエンの保持時間はウラシルやシトシンよりも短かった。この結果から、実施例１から実施例３で製造した樹脂粒子は、式１化合物を使用することによって陽イオン交換性官能基と陰イオン性官能基が一度に導入され、粒子の表面極性が増大する一方、疎水性が低下していることが分かる。

In Table 1, filled with resin particles produced in Comparative Example 1 and Comparative Example 2 (resin particles in which neither a cation-exchange functional group nor an anionic functional group has been introduced by not using the compound of Formula 1) The uracil and cytosine retention times were almost the same for the columns that differed in polarity. In addition, highly hydrophobic toluene interacted strongly with the resin particles and was retained longer than polar compounds such as uracil and cytosine. On the other hand, in the column packed with the resin particles of the present invention produced in Examples 1 to 3, the retention time of uracil and cytosine becomes longer depending on the polarity, and the retention of toluene despite its strong hydrophobicity. The time was shorter than uracil and cytosine. From this result, the resin particles produced in Example 1 to Example 3 were introduced with a cation-exchange functional group and an anionic functional group at a time by using the compound of formula 1, and the surface polarity of the particles was increased. On the other hand, it can be seen that the hydrophobicity is lowered.

Claims (1)

Carbon - a resin polymerizable monomer is polymerized with hydrogen bonds, the following general formula (wherein, R1 is H or _CH 3, A is O or NH, X- is SO ₃ ^- or ^COO -, R2 and R3 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n each represents an integer of 1 to 30). A method for producing an amphoteric ion exchange resin.

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