TW555595B - Anion exchangers and processes for preparing them - Google Patents

Abstract

An object of the present invention is to provide an anion exchanger having a high ion exchange capacity by introducing larger amounts of anion exchange groups than in conventional ion exchange resins without causing the problem of the amine odor. Anion exchangers of the present invention comprise a graft polymer side chain derived from a styrene compound having a haloalkyl group on the benzene ring on a backbone of an organic polymer base characterized in that a functional group derived from a polyamine compound having one tertiary amino group and one or more primary, secondary or tertiary amino groups and/or quaternary ammonium groups has been introduced onto said graft polymer side chain.

Description

555595 V. Description of the invention (1) [Field of the invention] The present invention relates to an adsorbent exchanger capable of being adsorbed and a method for producing the same. Youzi exchanger and its manufacturing method. [Prior art] It is generally known that ion exchangers are strongly basic anion exchange trees with strong acidic cations such as sulfo groups, ion exchange resin groups, and tertiary lipid groups. Among them, the most widely used exchange resins and strongly basic anions are used in the preparation of these acid-exchange tree-crosslinked polystyrene spheres. Strongly acidic cation-exchange resins. The basic resin is sulfonated to obtain strong acidity. When a cation-exchange tree is a strong anion-exchange resin, it is basicized and then used with a tertiary amine to obtain a strong basic anion-exchange tree. ). When a strong alkaline anion salt needs a larger amount, this 'i try to introduce more ion components in the air or water from the ionization.' The present invention relates to a novel anionized ion The exchange resin is mainly composed of eight ion exchange resin groups, and a weakly basic anion exchange tree ion exchange resin having a quaternary ^ lipid group having a weak acidic amine group such as a carboxyl group is a strongly acidic cation exchange resin. When using grease, it is usually used with divinyl base resin. When it is desired to prepare a maple group, for example, a sulfonating agent such as sulfuric acid or gas is used to introduce maple group into a basic resin, and the resin is made of a lipid. When it is desired to prepare a quaternary base, for example, this base resin is subjected to a reaction of monomethylamine to give a quaternary grease. Usually has 1.2 meq / mL of neutral salt ion exchange resin (about the exchange of resin used in the treatment of water treatment. This leads to the problem of increased cost. Because the exchange of the base into the base resin to reduce

555595 V. Description of the invention (2) The problem of enhanced trimethylamine odor caused by the introduction of a large amount of quaternary ammonium groups into the basic resin. This is due to the so-called Hofmann degradation ', which refers to the elimination of the quaternary ammonium group by heating or the like, which is due to the low chemical stability of the quaternary f group to heat. This problem of amine odor is not only the main issue when introducing a large amount of quaternary ammonium groups to the basic resin, but also the main issue of strong basic anion exchangers generally having quaternary ammonium groups. [Disclosure of the invention] The present invention is a careful study by the inventors of the present case to obtain a novel novel high-neutral salt splitting capacity by introducing a large amount of anion exchange groups into the basic resin without causing the problem of amine odor due to Huffman degradation The results of the strongly basic anion exchanger were achieved. In order to solve the above problems, the present invention relates to an anion exchanger comprising a graft polymer side chain derived from a styrene compound having a dentyl alkyl group on a benzene ring on the main chain of an organic polymer base material. Functional groups from a polyamine compound having one secondary amine group and one or more primary, secondary or tertiary amine groups and / or quaternary ammonium groups have been introduced into the graft polymer side chain. [Best Specific Examples of the Invention] Hereinafter, aspects of the invention will be described in detail. In the following description, "a stupid ethylene compound having a halo group on a benzene ring" is simply referred to as "haloalkyl-substituted styrene". The organic polymer binder used to prepare the anion exchanger of the present invention is preferably a polyene-based organic polymer binder. Polyolefin-based organic polymer binders are suitable for introduction into the graft side by radiation-induced graft polymerization

313717.ptd Page 10 555595 V. Description of the invention (3) The purpose of the chain is because it is not degraded by radiation. Specific examples of polyolefin-based polymer materials that are very suitable for use as the organic polymer binder for preparing the anion exchanger of the present invention include, but are not limited to, polyolefins such as polyethylene and polypropylene, and halogenated polyolefins such as pTFE And polygas ethylene; and dilute smoke-dentified olefin copolymers such as ethylene-tetrafluoroethylene copolymers and ethylene-vinyl alcohol copolymers (EVA). These organic polymer binders are preferably in the form of a polymer composed of a material, a porous membrane, and the like. In the existing ion exchange resins, the capacity and regeneration efficiency are important. This is because the sub-exchanger of the regenerant with a small amount of Greek liquid is designed for one-way use. In the form of trace metal ions and polymer anion exchangers in the form of polymer base materials, porous membranes, etc., this can be easily calcined when compared with conventional resins. The conventional bead from its components, nets, membrane basic fibers or fabrics or non-woven weaving-recycling cycles is because the ion exchange per packed column is expected to increase the amount per cycle as much as possible. However, the reason for the present invention is that it is specifically intended to be effective in applications other than previously, eliminating or transferring liquid, or catalysis. From this point of view, the present invention is preferably a fibrous material, a mesh, because it is easy to control burning during processing. In addition, these forms of polymer 555595 V. Description of the invention-^ ^ 1 The organic polymer material of the present invention used in the form of a filter is used as a base material for the radiation-induced graft polymerization reaction and is lightweight because of its combination. It is easy to form a filter. The anion exchanger invented by the person is characterized in that, as described above, a graft socket side chain derived from a halogenated styrene substituted on the main bond of the organic polydione and the anion exchange group is introduced onto the side chain. . In the present invention, a preferred means for introducing the side chain of the graft polymer to the bond of the organic polymer base is radiation-induced graft polymerization. Radiation-induced graft polymerization is a method of introducing a desired graft polymer side chain into an organic polymer base by irradiating the base material to generate free radicals and reacting it with the graft monomer. For the purposes of this method, this method is the best because the number or length of the graft chains is relatively freely controllable and the polymer side chains can be introduced into existing polymer materials of various shapes. The radiation that can be used for the radiation-induced graft polymerization reaction that is very suitable for the purpose of the present invention includes α-rays, y5-rays, rays, electron rays, UV rays, and the like. Among them, it is preferred to use r-rays and electron rays in the invention. . Radiation-initiated graft polymerization reactions include pre-irradiation graft polymerization that covers pre-irradiation of the graft base material and then bringing it into contact with the reacted polymerizable monomer (graft monomer), and coverage of simultaneous irradiation of the base material and monomers. Simultaneous irradiation of the graft polymerization reaction, and any of these methods can be used in the present invention. Radiation-initiated graft polymerization includes various contact methods between the monomer and the base material, such as liquid phase graft polymerization with the base material immersed in the monomer solution, so that the base material and the monomer vapor contact Gas-phase graft polymerization, or immerse the base material in the monomer solution, and then

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Removal of the immersion gas phase Invention.

最佳 It is used in the graft polymerization reaction, and the fiber and fabric / non-woven iron system composed of fiber components are used in any method ^ ", the best material for the organic polymer base that hurts the anion exchanger of the present invention It is particularly suitable for use in immersion gas phase graft polymerization because it is easy to maintain a monomer solution. ^ Grafting on the polymer backbone of the organic polymer base introduced into the anion exchanger of the present invention The polymer side chain is derived from dentyl-substituted styrene. This polymer side chain is introduced by graft polymerizing dentyl-substituted styrene onto the main chain of the organic polymer base. It is preferably used in An example of the alkyl-substituted styrene of the present invention is n-haloalkyl-substituted styrene represented by the following formula:

X = CIP Brp I; π = 1-7〇 Particularly preferred is chloromethylstyrene represented by the following formula:

Among them, chloromethylbenzene is particularly preferred because of its high chemical durability. It has vinyl and aerosol in the para position because it can be used to form an excellent agent. The polymer-substituted styrene introduced into the organic polymer base and another polymerizable polymer such as 'aeromethylstyrene' and hydrophilic are copolymerized onto the organic polymer base to increase the degree of polymerization. The anion exchange of the present invention] and one or more functional groups of the primary, secondary, or amine compound have been generally introduced with a graft polymer side chain to the graft polymer side bond. Usable chain or branched chain polyamines such as diethylene triamine-like polyamines are triethylene ethylene as shown in the following formula, because it can increase the degree of polymerization. Methylstyrene, which is an anion-exchange graft polymer side chain with ion-removing properties, may also be a graft copolymer side chain of a haloalkane monomer. For example, a polymerizable monomer such as acrylamide can be grafted to impart additional functionality to the base material or derived from as many polyamines as having one tertiary amino secondary amine group and / or quaternary ammonium group. The polyamine compound introduced into the present invention by reacting the compound with an organic polymer binder as described above includes straight and diethylenetriamine; and cyclic or polycyclic diamine:

One of the following formulas, the general name is " diazabicyclic eleven carbon dilute

313717.ptd Page 14 555595 V. Description of Invention (7)

And hexamethylenetetramine shown by the following formula:

In particular, the polyamine compounds exemplified by the above-mentioned chemical formula have lone pairs called bridgeheads, making them highly reactive. Therefore, it can be easily quaternized to greatly contribute to increase the ion exchange capacity while having a highly reactive amine group which is not used for bonding to the side chain of the graft polymer. When a polyamine compound having at least one tertiary amine group and one or more primary, secondary or tertiary amine groups and / or quaternary ammonium groups is reacted to the side chain of a graft polymer derived from a haloalkylstyrene The tertiary amine group is quaternized to cause a link at this site. However, other amine or ammonium groups contained in the polyamine compound remain unreacted. That is, two or more amine or ammonium groups are introduced per haloalkyl molecule, and as a result, two or more times of anion exchange groups are introduced as compared with conventional ion exchange resins. Polyamine compounds can also be introduced into conventional spherical bead-shaped ion exchange resins, but the increase in polymerization degree or ion exchange capacity is obviously lower than that of the anion exchanger of the present invention. This may be because the crosslinked structure of the base material of the bead-shaped ion exchange resin prevents the polyamine compound from entering the resin or causes the polyamine compound itself to crosslink. However, in the anion exchanger of the present invention, the polyamine compound has been

313717.ptd Page 15 555595 V. Description of the invention (8) Introduce the side chain of the graft polymer of the organic polymer base material, so that the site where the polyamine compound has been introduced has a higher charge and repel each other to expand the connection. The distance between the side chains of the branch polymer allows the polyamine compound to easily enter. This has not only an effect of increasing the degree of polymerization but also an effect of suppressing cross-linking, and as a result, an ion exchanger having a very high ion exchange capacity can be obtained. In contrast to the conventional spherical bead-shaped ion exchange resins in which the polymer main chains are crosslinked with each other to compensate for the deterioration of the physical strength of the matrix introduced with the ion exchange group, the anion exchanger of the present invention can be provided on the polymer main chain of the base material. Contains side chains in the form of polymer chains of anion exchange groups to impart high anion exchange capacity on the organic polymer binder while maintaining the physical strength of the polymer backbone. In the anion exchanger of the present invention, the main chain plays a role of maintaining physical strength or maintaining shape. '[Advantages of the present invention] In the anion exchanger of the present invention, a high degree of amination is achieved by introducing a polyamine compound into the graft polymer side chain of an organic polymer base to solve the conventional method of introducing more amines Inevitably, the problem of lowering strength is inevitable. The present invention also solves the problem that the amine odor of the conventional method increases with the degree of amination. This edible 1 is because a compound having two or more amine groups in one molecule used in the present invention has a Buddha point which increases with the number of functional groups to reduce the vapor pressure, thereby suppressing the emission of amine odor. In addition, the anion exchanger of the present invention can be easily cleaned by calcination or other means and is lighter and less expensive than conventional ion exchange resins. The anion exchanger of the present invention can be used as a material for removing metal ions in water or adsorbing trace gas components in the air.

555595 V. Description of the invention (9) The following examples illustrate various specific examples of the invention, however, the invention is not limited thereto. [Example]

Implementation of JLL The use of hot-melt nonwoven fabrics with a density of 55 g / m2 and a thickness of 0-35 mm made of polyethylene (shell) / polypropylene (core) composite fibers with about 7 # m straight as the organic polymer Binder. This nonwoven substrate was irradiated with electron rays of 150 kGy in a nitrogen atmosphere. Gas-methylstyrene

Chemical (trade name: CMS-AM) was passed through a packed bed of activated alumina to remove the polymerization inhibitor, and then deoxidized by blowing nitrogen gas. The irradiated nonwoven substrate was immersed in this chloromethyl styrene solution and allowed to react for another 6 hours at 5 t. The non-woven fabric was removed from this solution and immersed in toluene for 3 hours to remove the homopolymer. The degree of grafting calculated from the weight obtained after drying was 16 10/0. The grafted non-woven fabric was immersed in a 10% aqueous solution of triethylenediamine and reacted at 80 ° C for 3 hours. After the reaction, the nonwoven substrate 'was washed with water and then regenerated by immersion in a 5% sodium hydroxide aqueous solution for 1 hour. Rinse thoroughly with pure water and dry in a vacuum dryer at 50 ° C for 3 hours. 1. Obtain a strong anion-exchange nonwoven fabric with a neutral salt splitting capacity of l_67meq / g and a density of 3.43meq / g to 1. That is, it contains a quaternary ammonium group capable of splitting a neutral salt at I67 med / g and an unreacted tertiary amine group at 1 to 76 meq / g, which corresponds to the difference between the total exchange capacity and the neutral salt splitting capacity. Therefore, the amount of quaternary ammonium and tertiary amine groups is approximately the same.

3l37l7.ptd Page 17 555595 V. Description of the Invention (ίο) etc. shows that triethylenediamine was introduced without being crosslinked. The degree of polymerization of the graft-polymerized chloromethylstyrene calculated from the weight change was as high as 94%. The non-woven fabric was regenerated in a sodium hydroxide solution, dried, and then stored in a zippered plastic bag. When the plastic bag was opened after one month, no amine odor was noticed. Comparative Example 1 The gas methylstyrene-grafted nonwoven fabric in Example 1 was quaternized by immersion in a 10% trimethylamine solution at 50 ° C for 3 hours. The regeneration process was performed in the same manner as in Example 1. A strongly basic anion exchange nonwoven fabric having a neutral salt splitting capacity of 2.2 meq / g was obtained. The neutral salt has a high splitting capacity per unit weight and the degree of polymerization of methylstyrene per graft polymerized gas calculated from the weight change is 96%, which is sufficiently compared with the value of Example 1. The non-woven fabric was regenerated in a sodium hydroxide solution, dried, and then stored in a zippered plastic bag. When the plastic bag was opened after one month, heavy amine odor was noticed. Rinse with water and store in a plastic bag in the same way, then open it and notice the same amine odor. Based on the fact that the strongly basic anion exchange nonwoven fabrics of Example 1 and Comparative Example 1 have almost the same length and width, the ions per unit area of the strongly alkaline anion exchange nonwoven fabrics of Example 1 and Comparative Example 1 are compared. The exchange capacity shows that the neutral salt splitting capacity is almost comparable and the total exchange capacity is approximately twice as high. It is also speculated that the strongly basic anion-exchange nonwoven fabric of Example 1 is not only recyclable, has no amine odor, is easy to handle, but also has characteristics of low gas emission in air.

313717.ptd Page 18 555595 V. Description of the invention (11) Example 2 The strong alkaline anion-exchange nonwoven fabric (renewable) sample obtained in Example 1 was assembled on a 5 cm diameter polyacetic acid fluorene column In the gas removal performance test apparatus shown in Fig. 1, a hydrogenated gas removal test was performed. The reference numerals in Figure 1 indicate the following components: 1: a pipe string, 2: a nonwoven fabric sample, 3: a sampling port for measuring the inlet concentration, 4: a sampling port for measuring the outlet concentration, 5: a pump, 6: Permeator, 7: Filter support. The permeator was controlled to adjust the gaseous hydrogen gas concentration at the inlet of the column to 1 ppm, and the column was ventilated under an air flow of 15 L / min. At the beginning, no hydrogen gas was detected at the outlet, and the hydrogen chloride gas concentration at the outlet remained below 0.1 ppm after 3,4 · 5 hours of ventilation. Comparative Example 2 The strongly alkaline anion-exchange nonwoven fabric obtained in Comparative Example 1 was subjected to a hydrogenated gas gas removal test in the same manner as in Example 2. Initially, no hydrogen gas was detected at the outlet, but the gasification of rat gas at the outlet after 18 · 1 hour of ventilation remained below Q. 1 p p m. When Example 2 and Comparative Example 2 are compared, the anion exchanger of the present invention has a specific ratio, the anion exchanger of the example is approximately twice as long as the ion removal gas performance represented by the service life. In both cases, the initial removal performance was 99% or less.

tJkMA was irradiated with r-rays at a temperature of 100 kGy under dry ice in a nitrogen atmosphere, and the heat-fusible nonwoven fabric used in Example 4 was irradiated. Then, polymer gas methylstyrene was grafted in the same manner as in the example to obtain a degree of grafting of 138%.

Page 19 555595

Non-woven fabrics grafted with chloromethylstyrene. This grafted nonwoven fabric was immersed in a 20% 'dilute solution of diazabicycloundecunde in diamidoxamine at 80 ° C for another 6 hours. This nonwoven fabric was regenerated with sodium hydroxide, and the ion exchange capacity was measured. An anion-exchange nonwoven fabric having both a strongly basic anion exchange group and a weakly basic anion exchange base was obtained at a neutral salt splitting capacity of 1. 41 meq / g and a total exchange capacity of 2. 65 meq / g. That is, it contains a quaternary ammonium group capable of splitting a neutral salt at 14imeq / g and an unreacted tertiary amine group at 1.24 meq / g, which corresponds to the total exchange capacity and the neutral salt splitting capacity. The difference. Therefore, the amount of the quaternary ammonium group is about the same as that of the secondary amine group, indicating that diazabicycloundecene was introduced without being crosslinked. / The non-woven fabric was regenerated in a sodium hydroxide solution and dried, and then stored in a zippered plastic bag. When the plastic bag was opened after one month, no amine odor was noticed. ^ Example Left The same procedure as in Example 2 was used for the anion obtained in Example 3, and the nonwoven fabric was replaced with a hydrogenated hydrogen gas removal test. Initially, hydrogen chloride was detected at the outlet, but the concentration of hydrogen gas at the outlet remained below 0 · 1ppm after 3 hours of ventilation, showing the effect of using polyamine compounds. defeat

555595 Brief description of drawings [Simplified description of drawings] Fig. 1 is a schematic diagram showing a gas removal performance test device used in the embodiment of the present invention. [Explanation of component symbols] 1 String 2 Non-woven fabric sample 3 Sampling port for measuring inlet concentration 4 Sampling port for measuring outlet concentration 5 Pump 6 Permeator 7 Filter support

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Claims (1)

六 、 Application for Benley & Phoenix 1. An anionic phenylene ring on the main chain of the side chain of one or more compounds 2. If applying for a special compound side chain machine polymer 3. If applying for a special compound system Methyltetramine 4. If you are applying for a special compound, choose methyltetramine 5. — a preparation method of grafting the polymer chain, and then react to introduce the secondary and secondary energy groups 6. If you apply for a special injection Its first-class functional niche is a niche material, niche has the characteristics of the three agents, the second base has been used in the main range, the second range of ethylene benefits, and the third patent application, including the combination of organic and then by The graft polymerization is derived from the graft polymerization of tertiary or tertiary amines to the range of the grafting advantage. The amendment includes the graft polymerization of the styrene compound having a ii alkyl group in the organic polymer base. A polyamine having a tertiary amine group and a primary or tertiary amine group and / or a quaternary ammonium group is introduced into the graft polymer side chain. The anion exchanger according to item 1, wherein the graft polymerization reaction initiated by the graft polymerization is introduced into a chain. The anion exchanger according to item 1, wherein the polyamined diamine, diazabicycloundecene, and hexamethylene anion exchanger, wherein the polyamined diamine, diazabicycloundecene is dilute and The anion exchange of any of the six sub-ranges 1 to 4 on a styrene compound polymer base having an ii alkyl group on a benzene ring to form a graft polymer side, the graft polymer side chain and the polyamine compound Polyamine compounds having a tertiary amine group and one or more mono- and / or quaternary ammonium groups are on the side chain of the official polymer. The method according to item 5, wherein the graft polymerization is carried out using a radial reaction. 313717. ptc Page 1 2003. 04. 07. 022