JPH09100386A - Polymer composite and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polymer composite which can easily desorb an org. material and has an anion exchange capacity by impregnating a styrenic basic anion exchange resin with particular two monomers and conducting copolymn. in the presence of an insoluble medium. SOLUTION: A styrenic basic anion exchange resin (A) is impregnated with a monovinyl unsatd. monomer (B) selected from (meth)acrylic acid derivatives having a group represented by formula N<+> R1 R2 R3 or NR1 R2 (wherein R1 , R2 , and R3 represent H, an alkyl, or an alkanol, provided that R1 , R2 , and R3 do not simultaneously represent H) (e.g. dimethylaminopropylacrylamide), a cross- linkable polyvinyl unsatd. monomer (C) selected from poly (meth)acrylic acid derivatives (e.g. N,N-methylenebisacrylamide), and a polymn. initiator (D) (e.g. potassium persulfate). Copolymn. is conducted in the presence of a medium which does not dissolve the components (B) and (C) (e.g. toluene) to prepare a polymer composite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an anion exchange resin, and more particularly to a polymer composite used as an anion exchange resin having excellent adsorption and desorption properties of organic matter in water.

[0002]

2. Description of the Related Art Conventionally, most ion exchange resins have been produced by having a copolymer of styrene and divinylbenzene as a matrix structure and imparting various ion exchange groups to the copolymer. The matrix structure of this styrene-based copolymer is physically, chemically and thermally stable, and can be said to be a structure suitable as the matrix structure of the ion exchange resin. This ion exchange resin has been used for various purposes such as production of demineralized water and purification of various organic substances.

[0003]

However, the ion exchange resin has a structure in which hydrophobic irreversible adsorption of organic substances is unavoidable due to the matrix structure of the styrene copolymer, and at the same time, it has an affinity for hydrophilic substances. Sex also decreases. Therefore, a structure having a certain degree of hydrophilicity has been desired depending on the use of the ion exchange resin. Also,
The basic performance of the ion exchange resin is determined by the neutral salt decomposition capacity, the water content, the particle size and the like. When the ion exchange resin is modified by various methods to add new physical properties, it is necessary to maintain these basic performances.

Further, in the production of demineralized water using an ion exchange resin, if the raw water contains an organic matter, the organic matter is irreversibly adsorbed to the ion exchange resin, and this contamination significantly reduces the desalination performance of the ion exchange resin. In such a case, there has been a demand for a resin in which the adsorbed organic matter is easily desorbed by the regeneration operation of the ion exchange resin. The present inventors have prepared a polymer obtained by copolymerizing a lower (meth) acrylic monovinyl unsaturated monomer having a tertiary amino group or a quaternary ammonium group and a crosslinkable polyvinyl unsaturated monomer, and By obtaining a polymer composite of a styrene-based strongly basic anion exchange resin, the present invention, which is a polymer composite having excellent adsorption and desorption of organic substances in water and having anion exchange performance, was completed.

[0005]

In order to solve the above-mentioned problems, the present invention provides the chemical formula -N ⁺ R ₁ R ₂ R ₃ in Claim 1.
Alternatively, —NR ₁ R ₂ (In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group or an alkanol group.
However, not all of R ₁ , R ₂ and R ₃ are hydrogen atoms at the same time. ) A copolymer of a monovinyl unsaturated monomer selected from (meth) acrylic acid derivatives having a group represented by and a crosslinkable polyvinyl unsaturated monomer selected from polyvalent (meth) acrylic acid derivatives. There is provided a polymer composite comprising a polymer and a styrene-based strongly basic anion exchange resin.

Further, in the present invention, a styrene-based strongly basic anion exchange resin is impregnated with a monovinyl unsaturated monomer, a crosslinkable polyvinyl unsaturated monomer and a polymerization initiator, and these monomers are substantially contained. The method for producing a polymer composite according to claim 1, wherein the copolymerization is carried out in the presence of a medium which does not dissolve.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. An object of the present invention is to obtain a polymer composite which is a resin composition having excellent adsorption and desorption properties of organic substances while maintaining the physical, chemical and thermal stability of a styrene-based strongly basic anion exchange resin. This was achieved by introducing a hydrophilic group having an ion exchange ability in order to suppress hydrophobic adsorption of organic substances in the matrix structure of the styrene-based strongly basic anion exchange resin. That is, the present invention is a polymer composite comprising a polymer obtained by copolymerizing a specific monovinyl unsaturated monomer and a specific crosslinkable polyvinyl unsaturated monomer, and a styrene-based strongly basic anion exchange resin. Exist in.

The monovinyl unsaturated monomer in the present invention has the chemical formula -N ⁺ R ₁ R ₂ R ₃ or -NR ₁ R ₂ (wherein
R ₁ , R ₂ , and R ₃ each represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, or an alkanol group. Where R ₁ ,
R ₂ and R ₃ are not all hydrogen atoms at the same time. )
It is selected from a (meth) acrylic acid derivative having a group represented by Specific examples of monovinyl unsaturated monomers include N, N-dimethylaminopropyl acrylamide,
Trimethylammoniopropyl acrylamide chloride,
Dimethylaminoethyl acrylate (meth), trimethylammonioethyl acrylate (meth) chloride, (meth)
Examples thereof include acrylamide, N-hydroxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like. These may be one kind or a mixture of two or more kinds. Preferably, N, N- having anion exchange capacity
Examples include dimethylaminopropyl acrylamide and trimethylammoniopropyl acrylamide chloride.

The crosslinkable polyvinyl unsaturated monomer in the present invention is selected from polyvalent (meth) acrylic acid derivatives having two or more vinyl groups in the molecule.
Specific examples of the crosslinkable polyvinyl unsaturated monomer include:
Examples thereof include N, N-methylenebis (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and the like. These are 1
It may be one kind or a mixture of two or more kinds. Preferably, N, N-methylenebis (meth) acrylamide is used.

As the styrene-based strongly basic anion exchange resin in the present invention, known ones (see, for example, "Chelate Resin, Ion Exchange Resin", Kodansha, Ltd., edited by Tadashi Hojo) can be used. In addition, the usual anion exchange resins include a gel type having micropores and macropores as a pore structure and having only micropores and a porous type having both micropores and macropores. The strongly basic anion exchange resin may be either gel type or porous type.
Further, the counter ion species in the ion exchange group of the anion exchange resin, there is a Cl type having Cl ions, OH type having OH ions, etc., and as the styrene-based strongly basic anion exchange resin of the present invention, it is particularly distinguished. Any kind can be used without.

The polymer composite of the present invention comprises a styrene-based strongly basic anion exchange resin, a monofunctional unsaturated monomer which is a monovinyl unsaturated monomer and a polyfunctional monomer which is a crosslinkable polyvinyl. The mixture of the unsaturated monomer and the polymerization initiator is impregnated, the resulting impregnated anion exchange resin is separated by filtration from the monomer mixture, and then the monomer mixture is not substantially dissolved in the presence of a medium. It can be produced by heating and polymerizing.

The method for producing the polymer composite of the present invention will be specifically described below with reference to embodiments. For the impregnation of the monomer mixture in the present invention, it is preferable to use a solvent that can dissolve the above-mentioned monomers. Water can be preferably used as the solvent. The composition ratio of the monomer mixture or the like in the present invention is adjusted such that the monovinyl unsaturated monomer is a solution of 1% by weight or more, preferably 10% by weight or more with respect to the solvent, and the crosslinkable polyvinyl unsaturated monomer is added. An amount in the range of 0.1 to 20% by weight based on the monovinyl unsaturated monomer is preferably dissolved in the above solution. Further, the polymerization initiator is dissolved in the above solution in an amount in the range of 0.01 to 10% by weight based on the monovinyl unsaturated monomer. Then, the solution prepared here is added to the styrene-based strongly basic anion exchange resin in an amount not less than twice the volume, and the dispersion is shaken,
The monomer mixture is impregnated into the anion exchange resin. The impregnation is carried out at room temperature at a shaking speed of 50-100 rpm for 1-24 hours. Examples of the polymerization initiator include water-soluble ones such as potassium persulfate and ammonium persulfate.

Further, the styrene-based strongly basic anion exchange resin impregnated with the monomer mixture is filtered and separated from the above dispersion solution, and the monomer mixture having a volume of 2 to 10 times the volume of the impregnated anion exchange resin is substantially obtained. Disperse and suspend in a medium that does not dissolve,
Heat to polymerize. The medium that does not substantially dissolve the monomer mixture, for example, toluene, dichloroethane,
Hexane and the like can be mentioned. The polymerization conditions in the method of the present invention are appropriately selected depending on the type and addition amount of the polymerization initiator, but usually they may be copolymerized at 50 to 80 ° C. for 1 to 24 hours. After the copolymerization reaction, the obtained polymer composite is filtered and washed into a product.

In the polymer composite of the present invention, the respective composition ratios of the polymer and the styrene-based strongly basic anion exchange resin can be determined by the following method. The neutral salt decomposition capacity per weight of the polymer composite of the present invention and the raw material styrene-based strongly basic anion exchange resin is measured and determined according to the method described in the DIAION Manual issued by Mitsubishi Chemical Corporation. Further, the neutral salt decomposing capacity of the polymer of the present invention can be determined from the charged composition ratio of the impregnated monomer mixture. The neutral salt decomposition capacity per weight of the obtained styrene-based strongly basic anion exchange resin was calculated as a (meq
/ g), the neutral salt decomposition capacity per weight of polymer is b (meq /
g), the neutral salt decomposition capacity per weight of the polymer complex is c (m
eq / g), the content weight fraction x (wt%) of the polymer in the polymer composite is expressed by the following equation. x = ((c−a) / (b−a)) * 100 In the present invention, the content weight fraction of the polymer in the polymer composite obtained by the above formula is in the range of 0.1 to 30 wt%. Is preferably included. When the content weight fraction of the polymer is less than 0.1% by weight, the effect of the polymer composite is reduced, and when it exceeds 30% by weight, the physical, chemical and thermal stability of the polymer composite is deteriorated. It may decrease, which is not preferable.

When the polymer composite of the present invention is put to practical use as a resin composition having anion exchange ability,
It is desirable that the polymer composite has a water content of 40 to 80% and a particle size of 100 to 1000 μm. Further, the polymer composite of the present invention has an ion exchange capacity substantially equivalent to that of conventional anion exchange resins, and physical, chemical,
It has thermal stability. Further, the polymer composite of the present invention,
It has improved hydrophilicity compared to conventional anion exchange resins, and has improved adsorption to humic acid, which is a typical organic substance in water, and improved desorption by a regenerant. Therefore, the industrial utility value of the present invention is extremely high.

[0016]

EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, in the following examples, the neutral salt decomposition capacity and the water content were measured in accordance with the DIAION Manual issued by Mitsubishi Chemical Corporation. The evaluation of the organic contamination resistance of the obtained polymer composite and ion exchange resin was carried out by the following adsorption / desorption test method of humic acid as an index of organic matter in water.

[Adsorption and desorption test method] 0.1 g of humic acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 100 ml of 1N NaOH, filtered through a membrane filter, and cation exchange resin DIAION SK
After passing through 500 ml of 1B (H), the pH was adjusted to around 7 with NaOH. This humic acid solution was diluted to a concentration of 25 ppm to prepare a humic acid standard solution. On the other hand, after adjusting the samples of the polymer complex and the anion exchange resin to the OH type, 10 ml was collected in an Erlenmeyer flask. In the humic acid adsorption test, the amount of humic acid adsorbed was calculated by measuring the absorbance at a wavelength of 350 nm by mixing the above sample with 300 ml of a humic acid standard solution by stirring at 25 ° C. for 24 hours. In the humic acid desorption test, the sample after the humic acid adsorption test was separated by filtration, added to 300 ml of 10% NaCl, and
The desorbed amount of humic acid was calculated by mixing again by shaking at 24 ° C. for 24 hours and measuring the absorbance at a wavelength of 350 nm again.

Example 1 Anion exchange resin DIAION SA10A (DIAION is a trademark of Mitsubishi Chemical Co., Ltd.) was adjusted to a Cl type. After dehydrating 30 ml of the obtained resin in a centrifuge, put it in a 200 ml glass Erlenmeyer flask and
0 wt% trimethylammoniopropylamide chloride and
Monomer mixture containing 0.5wt% methylenebisacrylamide
100 ml was added, and the mixture was shaken at 25 ° C. for 16 hours at 100 rpm. Further, add 0.5 wt% potassium persulfate aqueous solution for 1 hour at 25 ° C and 100
Shaking was carried out under the condition of rpm, and then filtration was carried out to obtain an impregnated resin. Furthermore, the above impregnated resin (about 30 ml) and 100 ml of toluene were added to a 500 ml four-necked flask, and the mixture was polymerized by holding it at 70 ° C for 7 hours while stirring in a nitrogen atmosphere, and then washing with water to obtain the desired polymer complex. Got The polymer salt had a neutral salt decomposition capacity of 3.59 meq / g, a water content of 45.8% and a particle size of 300 to 600 μm. In addition, the infrared absorption (IR) spectrum of the polymer composite (FIG. 1) was not found in the anion exchange resin as a raw material.
Absorption derived from an amide bond at 0 cm ^-1 was confirmed. From the values of the neutral salt decomposing capacity of Example 1 and Comparative Example 1, it was found that the polymer composed of trimethylammoniopropylacrylamide chloride and methylenebisacrylamide was contained in the polymer composite in an amount of 3.6% by weight. There was found.

Example 2 In Example 1, Diaion SA10A was used as the porous anion exchange resin Diaion HPA.
A polymer composite was obtained in the same manner as in Example 1 except that the number was changed to 25. The neutral salt decomposition capacity of the obtained polymer composite was 3.
22 meq / g, water content 57.9%, particle size 150
Was about 600 μm. IR spectrum (Fig. 2) is 1
Absorption derived from an amide bond at 650 cm ^-1 was observed. From the values of the neutral salt decomposing capacity of Example 2 and Comparative Example 2, the content of the polymer in the polymer composite was 26.5% by weight.

Comparative Example 1 Diaion SA10A used in Example 1 was used as it was as a sample. The ion exchange resin had a neutral salt decomposing capacity of 3.55 meq / g, a water content of 45.6%, and a particle size of 300 to 600 μm.

Comparative Example 2 Diaion HPA25 used in Example 2 was used as a sample as it was. The ion exchange resin had a neutral salt decomposing capacity of 2.70 meq / g, a water content of 65.3%, and a particle size of 150 to 600 μm.

[Results of humic acid adsorption / desorption test] When the amount of humic acid used for one measurement of the humic acid standard solution is 100%, the amount of humic acid adsorbed on each sample, the amount of desorption, and the desorption rate (desorption The amount / adsorption amount)% is shown in Table 1. As is apparent from Table 1, the polymer composite of the present invention has a large desorption rate and a very good humic acid desorption performance.

[0023]

[Table 1] Table 1 Resin Adsorption component Desorption component Desorption rate (%) Example 1 95% 39% 42 Example 2 100% 48% 48 Comparative Example 1 55% 17% 32 Comparative Example 2 99% 32% 32

[0024]

The polymer composite of the present invention has the same exchange capacity, water content and particle size as conventional anion exchange resins, and has physical, chemical and thermal stability. further,
The polymer composite of the present invention has a structure that is more hydrophilic than conventional anion exchange resins and has excellent adsorption / desorption properties of organic substances. Therefore, the polymer composite obtained by the method of the present invention is excellent in regeneration ability and can be used as an ion exchange resin for a long period of time, so that it has great industrial value.

[0025]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the polymer composite obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the polymer composite obtained in Example 2.

FIG. 3 is an infrared absorption spectrum obtained with a resin sample of Comparative Example 1.

FIG. 4 is an infrared absorption spectrum obtained with a resin sample of Comparative Example 2.

Claims (8)

[Claims] 1. Chemical formula-N⁺R₁R_TwoR_ThreeOr -NR₁R_Two
(Where R₁, R_Two, R_ThreeAre hydrogen atom, alkyl group,
Alternatively, it represents an alkanol group. Where R₁, R _Two, R_Threeof
Not all are hydrogen atoms at the same time. )
Selected from (meth) acrylic acid derivatives having a group
Is it a vinyl unsaturated monomer and a polyvalent (meth) acrylic acid derivative?
Copolymerized with a crosslinkable polyvinyl unsaturated monomer selected from
Polymer and styrene strong base anion exchange
A polymer composite comprising a resin. 2. A styrene-based strongly basic anion exchange resin,
The polymer composite according to claim 1, which is a gel type anion exchange resin. 3. A styrene-based strongly basic anion exchange resin,
The polymer composite according to claim 1, which is a porous anion exchange resin. 4. The monovinyl unsaturated monomer is selected from dimethylaminopropyl acrylamide and / or trimethylammoniopropyl acrylamide chloride, and any one of claims 1 to 3 is characterized. The polymer composite described. 5. The crosslinkable polyvinyl unsaturated monomer is one or more selected from N, N-methylenebis (meth) acrylamide, ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate. The polymer composite according to any one of claims 1 to 4, which is a mixture. 6. The polymer composite according to claim 1, wherein the polymer according to claim 1 is contained in the polymer composite in an amount of 0.1 to 30% by weight. 7. The polymer composite according to claim 1, wherein the polymer composite has a water content of 40 to 80% and a particle diameter of 100 to 1000 μm.
The polymer composite according to the item. 8. A styrene-based strongly basic anion exchange resin,
The monovinyl unsaturated monomer, the crosslinkable polyvinyl unsaturated monomer and a polymerization initiator are impregnated, and the copolymerization is carried out in the presence of a medium in which these monomers are not substantially dissolved. A method for producing a polymer composite.