JPH07300509A - Bead polymer - Google Patents

Abstract

PURPOSE:To produce a copolymer of high mechanical strength by copolymerizing glycidyl (metha)acrylate or (metha)allyl glycidyl ether and vinyl (metha)acrylate or divinyl spirobi-m-dioxane. CONSTITUTION:A bead copolymer is produced by copolymerizing glycidyl (metha)acrylate or (metha)allyl glycidyl ether (A) with 5 to 50wt.% of vinyl (metha)acrylate or divinylspirobi-m-dioxane (B) and another type of monomer, as required, in the presence of 0.2 to 2.0wt.% of an oil-soluble free-radical polymerization initiator in an aqueous solvent kept at a pH level of 2 to 9, under the conditions of agitation speed: 50 to 500rpm, temperature: 80 deg.C or lower and reaction time: 0.5 to 5hr, the product copolymer having structures cross- linked by the component (B), the epoxy group derived from the component (A) being modified to have the ring cleaved, particle size of 10mum or more and gel water content of 30 to 2000%.

Description

TECHNICAL FIELD The present invention relates to a bead-like polymer suitable as a modifier for a liquid chromatography gel in which an epoxy group is ring-opened and modified, an ion exchange resin, a plastic and the like. . (Prior Art) A polymer containing a bond with an epoxy group has a possibility that it can be applied to various fields of application by introducing various functional groups due to its reactivity.
Japanese Patent Publication No. 7-96261 discloses a technique for producing immunoactive particles by reacting glycidyl acrylate (GA) or glycidyl methacrylate (GMA) polymer particles with an immunoactive substance having an amino group. According to the publication, polymerization is carried out in a medium in which a monomer is dissolved but a produced polymer is precipitated and precipitated, and a fine particle GA or G having a particle size of 0.03 to 10 .mu.
Although it is described that an MA polymer can be obtained, in such means, since an organic solvent is used in the polymerization medium, washing, etc., there are points to be noted on the industrial scale such as odor work environment and safety. Not a few. Also, the Chemical Society of Japan, 1979, (12), P. 1756 to 1759 GM as a substrate for producing a chelating ion exchange resin
A method for producing a spherical polymer is disclosed, but in order to obtain a spherical polymer, a large amount of sodium sulfate and calcium carbonate are used as a dispersant together with gelatin, in order to decompose and remove calcium carbonate from the produced polymer. Add hydrochloric acid to
It requires a complicated operation of hot water washing. Further, in recent years, liquid chromatography is not only used as one of analysis means, but is also industrially used in many fields such as food industry, pharmaceutical industry, synthesis and purification of intermediate products of chemical industry, inorganic industry, textile industry. Application as one of the separation means has been advanced, and as such gel for liquid chromatography, dextran cross-linked polymer gel, acrylamide cross-linked polymer gel, cross-linked polystyrene gel, cross-linked polyvinyl acetate gel, cross-linked polyethylene glycol dimethacrylate gel. Various developments have been made such as gels and silanol / polyoxyethylene gels. However, a gel having high separation performance and high processing capacity is generally expensive,
For example, Pharmacia Fine chemicala
Sephadex gel (dextran cross-linked polymer gel) manufactured by Company I has excellent performance, but is very expensive, and is a problem in industrial applications where a huge column is packed in a large amount and used. Then, the present inventors propose, for example, in JP-A-59-232104, a bead-like polymer based on GA or GMA (hereinafter referred to as G (M) A), which is particularly inexpensive and has high separation performance. did. (Problems to be solved by the invention) However, G (M)
The bead-shaped polymer based on A also has insufficient mechanical strength when used as a gel for high performance liquid chromatography, and such insufficient mechanical strength is caused by a large amount of crosslinking agent such as alkylene glycol divinyl ester. Although the cross-linking structure is dense and hard and the degree of swelling is reduced by the means for polymerizing, it is improved, but on the other hand, problems such as a decrease in the content of epoxy groups and a decrease in hydrophilicity and separation performance are caused. That is, an object of the present invention is to provide a bead-shaped polymer which can be widely used for various purposes and has excellent mechanical strength and high separation performance which are particularly suitable as a gel for high performance liquid chromatography. (Means for Solving the Problems) The above-mentioned objects of the present invention are (meth) allyl glycidyl ether and (A) G
(M) A or (B) 5 to 50% by weight based on the total amount of monomers
0.2 to 2.0% by weight of an oil-soluble radical polymerization initiator based on the total amount of the monomer containing vinyl (meth) acrylate or divinylspirobimetadoxane as a main component.
A bead-shaped polymer, which is a water-based copolymer, wherein the copolymer is cross-linked by the component (B) and the epoxy group based on the component (A) is ring-opening modified. Achieved by Here, the ratio of the component (A) to the component (B) needs to be set within the range of approximately 5 to 50%, preferably 5 to 40% of the weight of the copolymer (B). is there. The component (B) is a cross-linking agent, and the bead-like polymer is made into a cross-linking copolymer. However, when the bead-like polymer of the present application is post-processed and modified with a specific cross-linking agent recommended in the present application, water is often added. The effect of being familiar with (high gel water content) and having high mechanical strength can be exhibited. In addition, (A),
In addition to both components (B), other monomers copolymerizable with component (A) may be used in combination as appropriate. Examples of such monomers include vinyl halides and vinylidene halides; acrylic acid. Unsaturated carboxylic acids such as methacrylic acid, maleic acid and itaconic acid and salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
(Meth) acrylic esters such as butyl acrylate, octyl (meth) acrylate, methoxyethyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate; methyl vinyl ketone, phenyl vinyl ketone Unsaturated ketones such as methyl isopropenyl ketone; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate; methyl vinyl ether,
Vinyl ethers such as ethyl vinyl ether; acrylamide and its alkyl-substituted compounds; unsaturated hydrocarbon sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, p-styrene sulfonic acid, and salts thereof; styrene, α-methyl Styrene such as styrene and chlorostyrene and alkyl or halogen substituted products thereof; allyl alcohol and its esters or ethers; basic vinyl compounds such as vinyl pyridine, vinyl imidazole and dimethylaminoethyl methacrylate; acrolein, methacrolein, vinylidene cyanide , Vinyl compounds such as methacrylonitrile, and the like. The production of a beaded polymer composed of the above monomers is carried out by water-based polymerization, but in general, when water-based polymerization of an epoxy group-containing monomer is performed, the resulting polymer is strongly sticky and aggregates to form a rice cake. Since it is easy to agglomerate, 0.2 to
A means for carrying out aqueous suspension polymerization under a specific pH and stirring conditions in the presence of a specific water-soluble polymer using 2.0% by weight of an oil-soluble radical polymerization initiator is preferably adopted. In some cases, a water-insoluble organic solvent can be added to the polymerization system in order to control the porous structure (in particular, to increase the pore size). The amount of such a diluent to be used needs to be changed depending on the application field of the filler, the required amount of pores (porosity), the diameter of the pores, etc., and it is difficult to unambiguously define it, but it is generally the monomer. And diluent in a weight ratio of 10/1 to
It is desirable to set it within the range of 1/10, more preferably 5/1 to 1/5. Further, as the type of such a diluent, a poorly water-soluble organic solvent that does not seriously affect the polymerization reaction is used. Among them, an epoxy group is contained in the compound, and the ring-opening of the epoxy group, A compound that can be converted into a water-soluble compound that can be easily extracted with water by hydrophilization can be advantageously used, and examples thereof include epichlorohydrin or glycidyl ethers represented by the following general formulas (I) to (III). . Among them, epichlorohydrin or glycidyl ether represented by the above general formula (I) is preferable as a diluent from the viewpoint of separation performance of the final product and industrial viewpoint. The water-soluble polymer to be present in the polymerization system is a monomer unit (a component) consisting essentially of an ethylenically unsaturated carboxylic acid or salt thereof and a monomer unit consisting of an ethylenically unsaturated sulfonic acid or salt thereof ( And a component (b), which can be produced by copolymerizing the component (a) and the component (b) by a known method (particularly, solution polymerization using water as a polymerization medium). It should be noted that copolymers obtained by copolymerizing unsaturated carboxylic acid esters such as acrylic acid or methacrylic acid esters are hydrolyzed to introduce the component (i) into the polymer, and the sulfonation of the polymer is used to introduce the component. It goes without saying that methods such as introducing components can also be adopted. The composition ratio of such a water-soluble polymer is generally a component / b component = 3.
It is desirable to be in the range of 0 to 80% / 70 to 20%. Further, depending on the type of other monomer, it may be used as a water-soluble polymer in addition to the components (a) and (b) in addition to a hydrophobic monomer such as vinylidene chloride. In some cases, a better bead-shaped polymer can be obtained by using a water-soluble polymer obtained by copolymerizing or graft-polymerizing a small amount of the monomer. Incidentally, as the component (i), unsaturated monovalent carboxylic acids such as acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid and salts thereof; maleic acid, fumaric acid, itaconic acid, aconitic acid, citraconic acid, mesaconic acid, etc. Examples of the unsaturated polycarboxylic acid and salts thereof include the introduction of a monomer unit composed of methacrylic acid and a salt thereof particularly from the viewpoint of bead-like polymer-forming property. Also, as the B component,
Sulfonated unsaturated hydrocarbons such as sulfonated styrene, allyl sulfonic acid and methallyl sulfonic acid and salts thereof; sulfoalkyl esters of acrylic acid or methacrylic acid such as methacrylic acid sulfoethyl ester and methacrylic acid sulfopropyl ester, and These salts etc. can be mentioned. Although it is difficult to unambiguously define the amount of the water-soluble polymer to be used, it is preferable to use 5 to 50% by weight based on the amount of the monomer. Further, by using together with the water-soluble polymer, polyvinyl alcohol (PVA) having a polymerization degree of 500 to 2000 and a saponification degree of 85 to 95% with respect to the monomer in an amount of 0.1 to 5% by weight, particularly good results can be obtained. Can be brought. The oil-soluble radical polymerization initiator can be used without any limitation as long as the object of the present invention can be achieved, but preferable examples include 2,2′-azobisisobutyronitrile. 2,2'-azobis (2-methyl-valeronitrile), 2,2'-azobis (2,4-dimethylbutyronitrile), 2,2'azobis (2,4-
Dimethylvaleronitrile), 2,2′-azobis (2,2
4-dimethyl-4-ethoxyvaleronitrile), 2,
Azo compounds such as 2'-azobis (2,4-dimethyl-4-n-butoxyvaleronitrile), for example, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate. Diacyl peroxides such as; t-butyl peroxyisobutyrate, t-
Organic peroxides such as peroxyesters such as butyl peroxypivalate, t-butyl peroxy neodocanoate and t-butyl peroxy laurate can be used. It is difficult to unambiguously define the amount of the initiator used, but the amount of the initiator to be used should be approximately 0.
Used in the range of 2 to 2.0% by weight. Regarding the pH of the polymerization system, if the acidity is too strong, the ring-opening of the epoxy group is caused during the polymerization reaction, and if the alkalinity is too strong, the resulting polymer is hydrolyzed, so that the pH is 2 to 9, preferably 2. It is desirable to set within the range of ~ 7. The stirring conditions that play an important role in adjusting the particle size of the finally obtained bead-shaped polymer to preferably 10 μm or more are changed depending on the shape of the blade, the presence or absence of a baffle plate, the desired particle size, etc. Although it is necessary and uniquely difficult to specify, the stirring speed is generally 50 to 500 r.p.m. p.
m. It is set within the range of. In addition, as the shape of the wing,
A paddle type or turbine blade is suitable because it is easy to obtain a uniform particle size distribution. The polymerization temperature depends on the kind of the initiator, but as the temperature increases, the ring-opening reaction of the epoxy group occurs, or a part of the monomer is emulsified to cause emulsion polymerization to form a latex fine polymer. To cause the problem of
A temperature range of approximately 80 ° C or lower, preferably 40 to 70 ° C is recommended. Industrially, water is preferably used as the polymerization medium, but if desired, a water-miscible organic solvent may coexist, or an electrolyte salt may coexist. In this way, a bead-shaped polymer containing an unopened epoxy group is formed, but the present invention is one in which the epoxy group is further subjected to ring opening modification. As a typical example of ring-opening modification,
Examples thereof include hydrolysis, addition of polyhydric alcohol, addition of alkyl alcohol, addition of hydroxycarboxylic acid, addition of amine, addition of mercaptan, addition of acidic sulfurous acid or sulfurous acid or salts thereof. Depending on the field of application such as a gel for liquid chromatography, when introduction of a nonionic hydrophilic group is required, ~ and method are selected, and from the purpose of introducing an ionic hydrophilic group, and method are appropriately selected. Although it can be used, if a gel with high gel moisture content is required,
The method is not preferred. Regarding the above-mentioned method,
Formic acid, acetic acid, hydroxyacetic acid, sulfuric acid, nitric acid as a catalyst,
Acids such as hydrochloric acid and perchloric acid; alkalis such as sodium hydroxide, potassium hydroxide and ammonia; zinc borofluoride, boron trifluoride ether salt, zinc chloride and the like, preferably at a temperature of 5
By allowing the reaction to proceed for approximately 0.5 to 5 hours under the condition of 0 ° C. or higher, the ring opening of the epoxy group and the introduction of the hydrophilic group (hydroxyl group) can be achieved industrially advantageously. Examples of the polyhydric alcohol used in the above method include glycols such as ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, polyethylene glycol and polypropylene glycol; and 3 such as glycerin and 1,2,3-butanetriol. Examples thereof include polyhydric alcohols; tetrahydric alcohols such as erythritol and pentaerythritol; alcohols having a valence of 5 or more such as mannitol; and glycols and trihydric alcohols are preferable. As the above method, tertiary amines such as benzyldimethylamine, tributylamine and tris (dimethylamino) methylphenol; quaternary ammonium salts such as triethylbenzylammonium chloride and tetramethylammonium chloride; 2-
In the presence of a catalyst such as imidazoles such as methylimidazole and 2-methyl-4-ethylimidazole, oxymonocarboxylic acids such as hydroxyacetic acid, lactic acid, α, β-dioxyisobutyric acid and gluconic acid; malic acid, oxyglutaric acid , Monooxypolycarboxylic acids such as citric acid; tartaric acid, α, β-dioxyglutaric acid, oxycitric acid,
Hydroxycarboxylic acids such as polyoxypolycarboxylic acids such as trioxybutyric acid can be added. Further, as the above method, amines such as ammonia, hydroxylamine, hydrazine, monoethanolamine, diethanolamine, triethanolamine, 2-oxy-2-methylpropylamine, urea, thiourea, and thiourea dioxide can be used. As the method, methyl mercaptan, monothioethylene glycol, thioglycolic acid,
Mercaptan such as ethanedithiol and 1,4-butanedithiol can be easily added without using a catalyst. In addition, in any of the above-mentioned methods, conditions of temperature and time that are substantially the same as those in the above-mentioned methods can be adopted. When water is used as a medium for carrying out the ring-opening of the epoxy group and the introduction reaction of the hydrophilic group, the hydrolysis reaction preferentially proceeds to cause an addition reaction (introduction of a functional group other than the hydroxyl group). Since it is unlikely to occur, it is preferable to use an organic solvent such as methyl ethyl ketone, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or ethylene carbonate to carry out the reaction in a homogeneous system or, in some cases, a heterogeneous system. In addition, the amount of water should be kept to the minimum necessary. When the ring-opening modification of the epoxy group is carried out in this way, the particle size is generally 10 to 500 μm, preferably 3
A bead-like polymer having a gel water content of 0 to 300 μm and a gel water content of 30 to 2000%, preferably 50 to 1000%, which is suitable as a gel for liquid chromatography, can be industrially advantageously produced. (Effect of the invention) As described above, the epoxy group is ring-opened and modified, and the epoxy group is easily compatible with water, and has high pressure resistance and excellent separation ability. It is a remarkable effect of the present invention that a bead-shaped polymer that can be suitably used as an ion exchange resin can be provided. (Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by the description of these Examples. In the examples, parts and percentages are by weight unless otherwise specified. The gel moisture content and the mechanical strength are measured or calculated by the following methods. (1) Gel Moisture Content (%) Polymer particles that have reached a sufficient equilibrium with deionized water are subjected to a centrifugal effect 2000 G centrifuge to remove water adhering to the particle surface, and then the weight (W ₁ ) thereof is taking measurement. The polymer particles are then dried and weighed (W ₂ )
It was calculated by the following formula. (2) Mechanical strength (Kg / cm ² ) 100 mesh and 200 mesh sieved bead polymer
The intermediate product of the mesh is used as a test sample, and the sample is packed in a stainless steel column having an inner diameter of 2.5 cm and a height of 50 cm. Deionized water was passed through this column at different flow rates, the pressure inside the column at this time was read to obtain a flow velocity-pressure diagram, and the pressure at the inflection point (pressure resistance limit point) in the diagram was determined as the mechanical strength. The value was (Kg / cm ² ). Example 1 Methacrylic acid / sodium p-styrene sulfonate = 70 /
20 parts of 30 water-soluble polymer and PVA (polymerization degree 100
0, saponification degree 87%) was dissolved in 778 parts of water and charged into a polymerization tank equipped with a paddle type stirrer. Next, 180 parts of GMA and 20 parts of divinylspirobimetadoxane were added to 2,2-
Azobis- (2,4-dimethylvaleronitrile) (2 parts) and epichlorohydrin (150 parts) as a diluent were dissolved and charged into a polymerization tank, and the stirring conditions were changed as shown in Table 1 below to conduct polymerization at 60 ° C. for 2 hours ( pH = 3). The gel moisture content of the obtained bead-shaped polymer (Nos. 2 to 4) was measured and found to be 11%. Next, No. After filtering and washing the beaded polymer of No. 3, pH =
Reslurry in water adjusted to 1.5, 80 ℃ x 3
As a result of heat treatment for a period of time, a water-swollen bead-like polymer (No. 6) was obtained. The water content of gel of this polymer (No. 6) was 73%. Example 2 No. 1 Example except that the type of the cross-linking agent was changed. Five types of beaded polymers (Nos. 7 to 11) were prepared in the same manner as in 6. The results of evaluating the mechanical strength of the polymers (Nos. 6 to 11) are shown in Table 2 below. From the above table, it is understood that the products of the present invention (6 to 8) have excellent mechanical strength. Example 3 No. 1 Example except that the amount of the crosslinking agent used was changed. 5 kinds of beaded polymers (No. 12 to 16) in the same manner as 6
Was produced. Table 3 shows the evaluation results of the gel moisture content and the mechanical strength. From the above table, it can be understood that the products of the present invention (Nos. 13 to 16) have excellent gel moisture content and mechanical strength. Example 4 Example 1 No. 6 and Example 3 No. Regarding 13 and 14, the performance as a gel for liquid chromatography was evaluated as follows. That is, a glass column with an inner diameter of 1.5 cm and a height of 30 cm has 150 mesh and 350 mesh.
The intermediate of the mesh is packed and the column is filled with NaCl, Na
An elution curve shown in FIGS. 1 to 3 was obtained by charging 1 cc of an aqueous solution containing 5% of SCN and using deionized water as an eluent and operating at an elution rate of 2 ml / min. It is understood that all the products of the present invention have excellent separation ability.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 to FIG. 6 and Example 3N
o. 11 shows the elution curves obtained with the beaded polymers of 13 and 14.

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Claims (1)

[Claims] 1. (A) Glycidyl (meth) acrylate or (meth) allyl glycidyl ether, and (B) 5 to 50 wt% of vinyl (meth) acrylate or divinylspirobimethedioxane with respect to the total amount of monomers as a main component. The monomer is an aqueous copolymer obtained by using an oil-soluble radical polymerization initiator in an amount of 0.2 to 2.0% by weight based on the total amount of the monomers, and the copolymer is composed of the component (B). A bead-shaped polymer which is crosslinked and has an epoxy group based on the component (A) which is ring-opening modified. 2. The beaded polymer according to claim 1, wherein the particle size of the polymer is 10 μm or more.