JP2002265633A - Organic liquid absorber and method for producing the same - Google Patents

Abstract

(57) [Summary] [Problem] The present invention is inexpensive, highly safe, and
It is an object of the present invention to provide an organic liquid absorber having a wide range of application, and which is less likely to lose its shape during transportation and storage, and a method for producing the same. SOLUTION: The organic liquid absorber and the water-insoluble resin, which comprise an organic liquid-absorbent resin comprising a water-insoluble resin into which a hydrophilic polar group is introduced, and a support. A method for producing an organic liquid absorber, comprising filling an organic liquid-absorbent resin obtainable by introducing a hydrophilic group and a support into an organic liquid-permeable bag.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an absorbent capable of absorbing various organic liquids, and more particularly, to an organic liquid absorbent that is not easily deformed during transportation and storage, and a method for producing the absorbent. About.

[0002]

2. Description of the Related Art At present, an organic liquid absorber generally comprises a monomer capable of dissolving a target organic liquid,
It is generally manufactured by adding a crosslinking monomer and polymerizing. In this case, the raw material monomer is often relatively expensive, and also after polymerization, the raw material monomer remains unpolymerized and partially remains in the product.
There are problems in terms of price and safety. In addition, the current organic liquid absorbing resin is designed and manufactured with only the target of absorption of a specific organic liquid as its target, so the liquid absorbing ability for organic liquids of non-target types is extremely reduced. Resulting in. However, in practical use, it is very often required to simultaneously absorb a plurality of types of organic liquids. Therefore, an organic liquid absorber having a wide application range is strongly desired. Furthermore, in order to improve the handling properties during transportation and storage of the organic liquid absorber, further improvements are desired so that the absorber is less likely to lose its shape during transportation and storage.

[0003]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention provides an organic material which is inexpensive, has high safety, has a wide range of application, and is hard to lose its shape during transportation and storage. It is an object to provide a liquid absorber and a method for producing the same. In addition, in the present invention, the weight and volume are small during transportation, and the weight and volume of the organic liquid are absorbed during use, and the function of conforming to the external shape is sufficiently satisfied.
It is an object of the present invention to provide an organic liquid absorber particularly useful as a sandbag substitute. Furthermore, the present invention aims at contributing to the global environment by utilizing polymer waste such as a water-insoluble resin or inorganic solid waste such as a metal or ceramic, which has been difficult to treat as waste. I do.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the achievement of the above-mentioned object, and as a result, have found that an organic liquid absorbing material which can be obtained by introducing a hydrophilic polar group into a water-insoluble resin. It has been found that the use of a water-soluble resin makes it possible to obtain an organic liquid absorber having high safety and a wide range of application.
In particular, they found that by using used resin or waste material as the water-insoluble resin as a raw material, they can be effectively reused, contribute to the global environment, and supply inexpensive products. .

[0005] The present inventors have further studied the collapse of the organic liquid absorber during transportation and storage. As a result, it has been found that if a support is present together with the absorber, the organic liquid absorber is less likely to collapse during transportation and storage. I got In particular, it has been found that if an organic liquid absorbing resin is supported by the support, the shape collapse during transportation and storage can be further prevented. The present inventors have further studied and completed the present invention.

That is, the present invention provides (1) an organic liquid absorbing resin comprising an organic liquid absorbing resin comprising a water-insoluble resin into which a hydrophilic polar group is introduced, and a support. (2) The organic liquid absorber according to the above (1), wherein the support is a flexible network.
(3) The organic liquid absorbent according to (1), wherein the organic liquid absorbent resin is supported by a support, and (4) the hydrophilic polar group forms a salt. A sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group, a -PO (OH) ₂ group which may form a salt, Wherein at least one kind of -OPO (OH) ₂ which may form a salt, a hydroxyl group which may form a salt, and an amine base which may form a salt is provided. (1) the organic liquid absorber described in (1), (5) the hydrophilic polar group is contained in an amount of 0.1 to 99 relative to all monomer units in the water-insoluble resin.
(1) The organic liquid absorber according to the above (1), wherein (6) the water-insoluble resin has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. And (7) at least one of the aromatic ring and the conjugated diene contained in the water-insoluble resin is a total monomer unit in the resin. The organic liquid absorber according to the above (6), which is 1 to 100% by mol with respect to (8), further comprising a solid having a specific gravity of 1 or more. 1) The organic liquid absorber described in (1), (9) Specific gravity 1
(8) The organic liquid absorber according to the above (8), wherein the solid is composed of a natural mineral, and (10) the solid is a waste having a specific gravity of 1 or more. (11) The organic liquid absorber according to (8), wherein the solid substance having a specific gravity of 1 or more is formed by binding waste.
2) The organic liquid absorber according to (8), wherein the solid having a specific gravity of 1 or more is made of magnetic waste.

Further, the present invention provides (13) an organic solvent comprising an organic liquid absorbing resin comprising a used water-insoluble resin having a hydrophilic polar group introduced therein, and a support. (14) The organic liquid absorber according to (13), wherein the support is a flexible network, and (15) the organic liquid absorbent resin is supported by the support. (13) The organic liquid absorber according to (13), wherein the hydrophilic polar group is a sulfo group which may form a salt, or a sulfuric acid which may form a salt Group, carboxyl group which may form a salt, amide group, nitro group, -PO (OH) _{2 which} may form a salt
At least one of a group, a -OPO (OH) ₂ group which may form a salt, a hydroxyl group which may form a salt, and an amine base which may form a salt. (17) The organic liquid absorber according to the above (13),
(13) The organic liquid absorber according to the above (13), wherein the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble resin. Wherein the resin has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain thereof; At least one of the aromatic ring and the conjugated diene contained in 1 to 1 to all the monomer units in the resin.
The organic liquid absorber according to the above (18), which is 100 mol%, and (20) an organic liquid absorber according to the above (13), further comprising a solid having a specific gravity of 1 or more. (21) The organic liquid absorber according to (20), wherein the solid substance having a specific gravity of 1 or more is made of a natural mineral, and (22) a solid substance having a specific gravity of 1 or more is a waste. (20) The organic liquid absorber according to (20), wherein the solid substance having a specific gravity of 1 or more is formed by binding waste. (24) The organic liquid absorber according to (20), wherein the solid having a specific gravity of 1 or more is made of magnetic waste.

The present invention also provides (25) an organic liquid-absorbing resin obtainable by introducing a hydrophilic group into a water-insoluble resin, and a support filled in an organic liquid-permeable bag. (2) a method for producing an organic liquid absorber,
6) The method for producing an organic liquid absorber according to the above (25), wherein the support is a flexible network.
7) The method for producing an organic liquid absorber according to the above item (25), wherein the organic liquid absorbent resin is supported by a support, and (28) the hydrophilic polar group forms a salt. Sulfo group which may be formed, sulfate group which may form a salt,
Carboxyl group, amide group, nitro group which may form a salt, -PO (OH) ₂ group which may form a salt, -OPO (OH) group ₂ which may form a salt, salt (25) The method for producing an organic liquid absorber according to the above (25), wherein at least one of a hydroxyl group which may form a salt and an amine base which may form a salt is used.
9) The method for producing an organic liquid absorber according to the above item (25), wherein the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble resin.
(30) The method for producing an organic liquid absorber according to (25), wherein the water-insoluble resin has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. (30) wherein at least one of the aromatic ring and the conjugated diene contained in the water-insoluble resin accounts for 1 to 100 mol% based on all monomer units in the resin. The method for producing an organic liquid absorber according to the item (32), wherein the solid material having a specific gravity of 1 or more is filled in the organic liquid permeable bag.
5) The method for producing an organic liquid absorbent according to the above, (33) the method for producing an organic liquid absorbent according to the above (32), wherein the solid having a specific gravity of 1 or more is made of a natural mineral.
(34) The method for producing an organic liquid absorber according to the above (32), wherein the solid having a specific gravity of 1 or more is made of waste. (35) The solid having a specific gravity of 1 or more binds the waste. (32) The method for producing an organic liquid absorber according to the above (32), wherein the solid substance having a specific gravity of 1 or more is made of magnetic waste. 32) A method for producing an organic liquid absorber according to the above.

The present invention further provides (37) an organic liquid-absorbing resin obtainable by introducing a hydrophilic group into a used water-insoluble resin, and a support comprising an organic liquid-permeable bag. (38) The method for producing an organic liquid absorber according to (37), wherein the support is a flexible network. (39) The method for producing an organic liquid absorber according to the above (37), wherein the organic liquid absorbent resin is supported by a support, (40) the method wherein the hydrophilic polar group is a salt. A sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group, and a salt which may form -PO (OH )
_{Two or} more groups, -OPO (OH) which may form a salt, _two or more hydroxyl groups which may form a salt, and at least one kind of an amine base which may form a salt (37) The method for producing an organic liquid absorbent according to the above (37), wherein (41) the hydrophilic polar group is 0.1 to 99 mol% with respect to all monomer units in the water-insoluble resin. (37) The method for producing an organic liquid absorber according to the above (37), wherein (42) the water-insoluble resin has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. (37) The method for producing an organic liquid absorber according to the above (37), wherein (43) at least one or more of an aromatic ring and a conjugated diene contained in the water-insoluble resin is contained in all monomer units in the resin. Before being characterized by being 1 to 100 mol% with respect to (44) The method for producing an organic liquid absorber according to the above (42), (44) the organic liquid permeable bag-like body is further filled with a solid having a specific gravity of 1 or more. Method for producing organic liquid absorber, (4
5) The method for producing an organic liquid absorbent according to the above (44), wherein the solid having a specific gravity of 1 or more is made of a natural mineral. (46) The solid having a specific gravity of 1 or more is made of waste. (44) The method for producing an organic liquid absorber according to the above (44), wherein (47) the solid material having a specific gravity of 1 or more is formed by binding and forming waste.
(48) Specific gravity 1
The present invention relates to the method for producing an organic liquid absorber according to the above (44), wherein the solid substance is made of magnetic waste.

[0010]

Embodiments of the present invention will be described below in detail with reference to the drawings. Hereinafter, an organic liquid absorber 1 as shown in FIGS. 1 and 2 will be described as an organic liquid absorber to which the present invention is applied. Here, the "organic liquid absorber" in the claims and the detailed description of the invention has a function as a so-called sandbag for preventing the organic liquid from leaking to a storage area or outside a factory (sandbag substitute). ), Or those having a function of removing unnecessary organic liquid remaining due to leakage of the organic liquid. An organic liquid absorber 1 according to the present invention includes an organic liquid permeable bag 2, an organic liquid absorbent resin 3 contained in the organic liquid permeable bag 2, and a support 4. . In a dry state, the organic liquid absorber 1 is composed of an organic liquid absorbent resin 3a in a dry state, a support 4, and an organic liquid permeable bag 2 as shown in the cross-sectional view of FIG. Fig. 2 in the liquid swelling state
As shown in the cross-sectional view of FIG. 2, the liquid absorbent resin is composed of an organic liquid absorbing resin 3b in a liquid absorbing and swollen state, a support 4 and an organic liquid permeable bag 2. FIG. 3 is a cross-sectional view in a dry state of the organic liquid absorber 1 according to the present invention in which soil and a solid material 5 having a specific gravity of 1 or more are contained, and FIG. 4 is a cross-sectional view in a liquid-absorbing swelling state.

The organic liquid absorbing resin used in the present invention is usually produced by introducing a hydrophilic polar group into a water-insoluble resin. The water-insoluble resin used as a raw material is not particularly limited, but it is preferable to use a water-insoluble resin obtained from an inexpensive general-purpose monomer as a raw material. Specific examples of such a general-purpose water-insoluble resin include the following resins. For example, ABS (acrylonitrile-butadiene-styrene) resin, high impact polystyrene (HIPS), styrene-butadiene elastomer (SBC), SAN (styrene-acrylonitrile) resin, polyacrylonitrile resin (PA
N), polyacrylonitrile-butadiene (nitrile rubber), polystyrene (PS), nylon resin, polyolefin (eg, polyethylene, polypropylene, polyisoprene, etc.) resin, vinyl chloride (PVC), polyphenylene ether (PPE), polyphenylene sulfide (PPS) ), Polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polysulfone, polyallylsulfone, polyethersulfone, polythioethersulfone, polyetherketone, polyetherimide, polyetheretherketone, polyamide (nylon ), Polyamide imide, polyimide, polyarylate, aromatic polyester, polyurethane, polyvinyl chloride, chlorinated polyether, polychloro Methylstyrene, polyacrylic acid ester, polymethacrylic acid ester, celluloid, various liquid crystal resin, methacrylic resin (PMMA), succinic resins, terpene resins, epoxy resins, phenol - formaldehyde resins, and melamine resins.

As the water-insoluble resin used as a raw material, among the above resins, those having an aromatic ring or a conjugated diene structure into which a hydrophilic polar group described later can be easily introduced are more preferable. The content of the aromatic ring and / or conjugated diene unit in the water-insoluble resin is desirably about 1 to 100 mol% based on all monomer units in the resin. The number of hydrophilic polar groups introduced into the water-insoluble resin decreases, and as a result, the absorbability to an organic liquid (also referred to as a polar solvent) decreases, or the hydrophilic polar group is introduced into the water-insoluble resin. Even after the above, the content of the water-insoluble resin is preferably about 1 mol% or more in order to prevent the water-insoluble resin from being dissolved in various organic liquids.

The molecular weight (Mw) of the water-insoluble resin is not particularly limited, but has a weight average molecular weight (Mw) of about 1,000 to 20,000,000, and more preferably about 1 to 20,000,000.
The range is generally about 000 to 1,000,000. When the molecular weight is higher than 1,000, the compound is completely dissolved in water or an organic liquid due to the introduction of a hydrophilic polar group, and it becomes impossible to obtain an organic liquid-absorbing resin (that is, after the resin has absorbed the liquid). Inconvenience can be avoided. When the molecular weight is lower than 20,000,000, introduction of a hydrophilic polar group is facilitated, which is more practical.

These water-insoluble resins may be freshly produced unused granular resins (virgin pellets), or may be used water-insoluble resins or waste materials molded for specific applications. There may be. As the waste material,
For example, there are waste products (semi-finished products) in the production process of resin raw materials and molded products, housings and various parts materials already used for electric products and automobiles, or tubes, hoses, and various cushioning materials. The used water-insoluble resin refers to a water-insoluble resin recovered from the above waste materials and the like. The place where the waste material is discharged may be from a factory, a store, a household, or the like. However, a waste collected from a factory, a store, or the like (for example, odd ) Are more desirable because they often have relatively uniform compositions.

The water-insoluble resin may be an alloy with another resin, such as a face dye, a stabilizer, a flame retardant,
It may be a waste material or a used water-insoluble resin containing additives such as a plasticizer, a filler, a curable adhesive, and other auxiliary agents. Alternatively, a mixture of a used water-insoluble resin or a waste material and a virgin material may be used.

In the present invention, conversion to an organic liquid absorbing resin is aimed at by introducing a hydrophilic polar group into the water-insoluble resin described above. In this case, the hydrophilic polar group contributes to both an effect of increasing the absorbability to the organic liquid and an effect of preventing the water-insoluble resin from being dissolved in various organic liquids.

The hydrophilic polar group includes a polar group such as an acidic group or a basic group. The acidic group or the basic group may form a salt. Specific examples of such a hydrophilic polar group include a compound of the formula —SO ₃ M (where M is a hydrogen atom or a cation such as a metal such as sodium and potassium).
A sulfo group which may form a salt represented by the formula: -OS
A sulfate group which may form a salt represented by O ₃ M (where M is as defined above), a formula —PO (OM ₁ ) (OM ₂ ) or a formula —OPO (OM ₁ ) (OM ₂ ) (Where M ₁ and M
₂ is the same or different and has the same meaning as M above), and may form a salt represented by the formula M.
_The hydroxyl group which may form a salt represented by ₃ (wherein M ₃ has the same meaning as M) and the like may be mentioned as an acidic group which may form a salt. Further, for example, a salt such as an amino group, a secondary amino group (eg, a methylamino group), a tertiary amino group (eg, a dimethylamino group), for example, a quaternary ammonium group (eg, a trimethylammonium chloride group) may be formed. Examples of the basic group which may form a salt include an amine base. Other hydrophilic polar groups include an amide group and a nitro group.

A method for introducing a sulfo group and / or a sulfo group forming a salt into the water-insoluble resin is as follows.
Preferably, the water-insoluble resin having an aromatic ring is directly reacted with a sulfurating agent such as concentrated sulfuric acid (more preferably about 70% by weight or more), sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid or the like. Alternatively, a sulfo group is introduced by reacting the resin with a sulfonating agent in a state of being dissolved or dispersed in an organic solvent, and subsequently the sulfo group is converted to a basic substance (eg, sodium hydroxide or potassium hydroxide). It is possible to convert to a sulfonic acid salt by neutralizing with sulfonic acid. The reaction temperature at the time of sulfonation varies greatly depending on whether or not an organic solvent is used, but is generally about 0 to 200 ° C, preferably about 30 to 120 ° C. When the temperature is about 0 ° C. or higher, the reaction rate becomes sufficiently high, and an organic liquid-absorbing resin having better performance is obtained. When the temperature is about 200 ° C. or lower, the molecular chains in the resin are cut. The above range is preferable, since it is difficult to dissolve in water or an organic liquid. The reaction time varies greatly depending on the reaction temperature, but is generally about 1 minute to 40 hours, preferably 5 minutes to 2 hours. This condition is preferable because the reaction proceeds more sufficiently and the production efficiency is good.

As a method for introducing a sulfate group which may form a salt, preferably, a sulfate group is first introduced by reacting a water-insoluble resin having an unsaturated bond with a high-temperature sulfuric acid aqueous solution. By reacting with a basic compound (for example, sodium hydroxide or potassium hydroxide), a sulfate can be obtained. As a method for introducing a carboxyl group which may form a salt, n-butyllithium is preferably added to a water-insoluble resin having an aromatic ring, and then the carboxyl group is first reacted with dry ice to thereby convert the carboxyl group. It can be introduced, and then can be converted to a carboxylate by reacting with a basic compound (eg, sodium hydroxide or potassium hydroxide).

The amide group can be introduced, for example, by hydrolyzing the water-insoluble resin having a nitrile group with heated concentrated sulfuric acid or a heated alkali (eg, aqueous sodium hydroxide solution or aqueous sodium hydroxide solution). Obtainable. The method for introducing a nitro group is preferably achieved by reacting a water-insoluble resin having an aromatic ring with fuming nitric acid or a mixture of nitric acid and sulfuric acid. As a method for introducing a —PO (OH) ₂ group which may form a salt, a method of introducing —PO (OH) ₂ by adding phosphorus trichloride to a water-insoluble resin having an aromatic ring, followed by hydrolysis. ) ₂ groups are introduced, followed by a basic compound (eg sodium hydroxide or potassium hydroxide, etc.)
To form the same salt. As a method for introducing a -OPO (OH) ₂ group which may form a salt, a method of introducing -OPO (OH) ₂ group preferably by adding phosphorus trioxide to a water-insoluble resin having an unsaturated bond followed by hydrolysis,
An O (OH) ₂ group is introduced, and then the salt can be obtained by reacting with a basic compound (for example, sodium hydroxide or potassium hydroxide).

As a method for introducing a hydroxyl group which may form a salt, preferably, a hydroxyl group can be first introduced by reacting a water-insoluble resin having an unsaturated bond with an aqueous sulfuric acid solution, and then a basic group is added. The salt can be obtained by reacting with a compound (for example, sodium hydroxide or potassium hydroxide). As a method for introducing a tertiary and / or quaternary amine base, preferably, a water-insoluble resin having an aromatic ring is subjected to chloromethylation by Friedel-Crafts reaction, and then reacted with ammonia or various amine compounds. Thus, tertiary and quaternary amine bases can be introduced. Introduction of a primary amino group or a secondary amino group, and conversion of these amino groups into salts may be carried out according to a method known per se.

The hydrophilic polar group-introducing agent or basic compound may be a virgin agent, a waste liquid discharged from a factory, or a recycled product. From the viewpoint of effective use of resources, it is more preferable to use the waste liquid for producing the organic liquid absorbing resin used in the present invention. In addition, only one type of these hydrophilic polar groups may be introduced into the water-insoluble resin, or two or more types may be introduced. The amount of the hydrophilic polar group introduced into the water-insoluble resin is preferably about 0.1 to 99 mol% based on all monomer units in the resin. The above range is preferable in order to prevent the water-insoluble resin after the introduction of the hydrophilic polar group from being dissolved in water, and to have good absorbability to an organic liquid.

The organic liquid absorbing resin obtained by the above-described method may be further subjected to a treatment known per se. In a preferred embodiment, the reaction product, which is usually a gel, obtained by the above-described hydrophilic polar group introduction reaction is preferably filtered, washed with water, and then dried or dehydrated to obtain an excellent organic substance. A resin having a liquid absorbing ability is obtained. In addition, it goes without saying that the organic liquid absorbing resin of the present invention may be produced by polymerizing a monomer having the above-mentioned hydrophilic polar group introduced into the main chain and / or the side chain according to a means known per se.

The organic liquid absorbing resin of the present invention may optionally contain other components, for example, a conventionally known organic liquid absorbing resin (eg, a polymer obtained by adding a crosslinking monomer and polymerizing),
It may be further compounded with a stabilizer, a hygroscopic agent and the like. Regardless of the method, preferably by introducing a hydrophilic polar group into a water-insoluble resin by the method described above, it becomes possible to produce a resin having excellent organic liquid absorbability.

Specifically, examples of the organic liquid that can be absorbed by the organic liquid absorbing resin obtained by the present invention include the following.・ Hydrocarbons: propane, butane, pentane, 2-methylbutane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptane isomer, octane, 2,2,3- Trimethylpentane, isooctane, nonane, 2,2,5-trimethylhexane, decane, dodecane, unsaturated aliphatic hydrocarbon, benzene, toluene, xylene, o-xylene, m-xylene, p-xylene, ethylbenzene, cumene, mesitylene , Naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, biphenyl, styrene,
Cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-
Mentane, bicyclohexyl, cyclohexene, α-pinene, dipentene, decalin, petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene,
Solvent naphtha, camphor oil, turpentine oil, pine oil,

Halogenated hydrocarbons: methyl chloride, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-
Tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene, propyl chloride, isopropyl chloride, 1,2-dichloropropane, 1 , 2,3-trichloropropane, allyl chloride, butyl chloride, sec-butyl chloride, isobutyl chloride, tert-butyl chloride, 1-chloropentane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1 , 2,4-trichlorobenzene,
o-chlorotoluene, p-chlorotoluene, 1-chloronaphthalene, chlorinated naphthalene, methyl bromide, bromoform,
Ethyl bromide, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, propyl bromide, isopropyl bromide, bromobenzene, o-dibromobenzene, 1-bromonaphthalene, fluorobenzene, benzotrifluoride , Hexafluorobenzene, chlorobromomethane, trichlorofluoromethane, 1-bromo-2-chloroethane, 1,1,2-trichloro-1,
2,2-trifluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane,

Alcohols: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2- Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1- Octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5,5-
Trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4- Methylcyclohexanol, α-terpineol, abietinol, fusel oil, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-
Diol, 2-methyl-2,4-pentanediol, 2-ethyl-
1,3-hexanediol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,2,6-hexanetriol,

Phenols: phenol, cresol, o-cresol, m-cresol, p-cresol, xylenols, ether, acetal diethyl ether,
Dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratol, propylene oxide, 1 , 2-epoxybutane, dioxane,
Trioxane, furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, cineol, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, Glycerin ether, crown ether, methylal, acetal,

Ketones: acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, mesityl oxide, holon, isophorone, Cyclohexanone, methylcyclohexanone, acetophenone, camphor, cyclopentanone, alkyl ethers: dimethyl ether, diethyl ether, ethyl methyl ether, tetrahydroxyfuran (THF), dioxane, fatty acids, acid anhydrides: formic acid, acetic acid, propionic acid, butyric acid , Isobutyric acid, pivalic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylbutyric acid, caprylic acid, 2-ethylhexanoic acid, oleic acid, acetic anhydride, propionic anhydride, butyric anhydride

Esters: methyl formate, ethyl formate,
Propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, sec-hexyl acetate, cyclohexyl acetate, acetic acid Benzyl, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate, isobutyl propionate, butyrate, isobutyrate, isovalerate, Stearic acid esters, benzoic acid esters, ethyl cinnamate, abietic acid esters, bis (2-ethylhexyl) adipate, γ-butyrolactone, oxalic acid esters, diethyl malonate, maleic acid esters, dibutyrate tartrate , Tributyl citrate,
Sebacic acid esters, phthalic acid esters, ethylene glycol monoacetate, ethylene diacetate, ethylene glycol esters, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, diethyl carbonate, ethylene carbonate, propylene carbonate, borate esters, Phosphate esters

Nitrogen compounds: nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-tolunitrile, Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine, se
c-butylamine, tert-butylamine, dibutylamine, diisobutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, allylamine, aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, o-toluidine, m-toluidine, p-toluidine, cyclohexylamine, dicyclohexylamine, pyrrole, piperidine, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2,6 -Lutidine, quinoline, isoquinoline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N -Dimethyl Acetamide, N-methylpropioamide, N, N, N ', N'-tetramethylurea, 2-pyrrolidone, N-methylpyrrolidone, ε-caprolactam, carbamate, urea, acrylamide acrylamide,

Sulfur compounds: carbon disulfide, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone, compounds having two or more functional groups: 2-methoxyethanol , 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isoproxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 2-phenoxyethanol, 2- (benzyl) (Oxy) ethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol Monomethyl ether, tetraethylene glycol, polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polypropylene Glycol, poly (oxyethylene-oxypropylene) derivative, diacetone alcohol, 2-chloroethanol, 1-chloro-2-propanol, 3
-Chloro-1,2-propanediol, 1,3-dichloro-2-propanol, 2,2,2-trifluoroethanol, 3-hydroxypropiononitrile, acetone cyanohydrin, 2-
Aminoethanol, 2- (dimethylamino) ethanol, 2-
(Diethylamino) ethanol, diethanolamine, N-
Butyldiethanolamine, triethanolamine, triisopropanolamine, isopropanolamine,
2,2'-thiodiethanolamine, furfural, bis (2-
(Chloroethyl) ether, epichlorohydrin, o-nitrosoanisole, morpholine, N-ethylmorpholine, N-
Phenylmorpholine, lactic acid, lactic acid esters, methyl salicylate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, methyl acetoacetate , Ethyl acetoacetate, methyl cyanoacetate, ethyl cyanoacetate, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, o-chloroaniline, hexamethylphosphoric triamide, silicone oils, choline chloride Amides can be mentioned.

It is a surprising effect that the organic liquid absorbing resin according to the present invention has an excellent organic liquid absorbing ability for such a wide range of organic liquids. Since the hydrophilic liquid-absorbing resin has, in the molecule, a lipophilic site or a polar site based on a water-insoluble resin and a hydrophilic site or a non-polar site based on a hydrophilic polar group, a wide variety of liquids such as solvents This is probably because organic compounds such as gas and gas can be absorbed or adsorbed. There is no particular problem even if these organic liquids are in a gas, liquid or solid state at room temperature. In the case of a liquid, the organic liquid can be absorbed by bringing the organic liquid absorber according to the present invention containing the organic liquid absorbing resin into contact with the organic liquid as it is. In the case of a gas, the gas is liquefied and absorbed as described above, or the organic liquid absorber according to the present invention containing the organic liquid absorbing resin is brought into contact with a gaseous organic liquid. Can be absorbed. In the case of a solid, it can be absorbed by the organic liquid absorber according to the present invention containing the organic liquid absorbing resin in a state of being dissolved or melted in another organic liquid.

As a material of the organic liquid permeable bag 2 of the present invention, a cloth of natural fibers or synthetic fibers is used.
Examples of the natural fiber include cotton, hemp, and silk. Examples of the synthetic fiber include polyamide, polyimide, polyester, polyethylene, and polypropylene. It is preferable that these fibers are singly or mixed and knitted or woven into a cloth.
However, in some cases, it may be a nonwoven fabric. Further, depending on the case, it may be one in which pores penetrating the front and back of the film-like body are formed.

The shape or material of the support 4 of the present invention is not particularly limited as long as it can support the organic liquid absorbing resin. Here, "support" means that the modified polymer compound is attached or impregnated in order to prevent the modified polymer compound from being extremely inclined in the organic liquid-permeable bag-like body 2. . As the support, specifically, a flexible network is preferable. Flexible mesh 4
A cloth made of natural fibers or synthetic fibers is used.
As the material, the same material as the material of the organic liquid permeable bag 2 can be used. That is, examples of the natural fiber include cotton, hemp, and silk. Examples of the synthetic fiber include polyamide, polyimide, polyester, polyethylene, and polypropylene. It is preferable that these fibers are singly or mixed and knitted or woven into a cloth. However, in some cases, nonwoven fabric or paper may be used. Further, depending on the case, it may be one in which pores penetrating the front and back of the film-like body are formed.

In this case, the occupation ratio of the through holes in the support 4, preferably the flexible network, is preferably higher than that of the organic liquid permeable bag 2, whereby By attaching or impregnating the support with the organic liquid absorbing resin, the organic liquid absorbing resin can be fixed to the support. Thus, when the organic liquid absorber according to the present invention is transported and stored, it is possible to prevent the organic liquid absorbent resin from being out of shape, such as being unbalanced, inside the organic liquid absorber. Further, even if the organic liquid absorbent is used repeatedly by absorbing the liquid, drying after use, and reusing the organic liquid absorbent, the organic liquid absorbent resin may lose its shape inside the organic liquid absorber. Can be prevented, and the number of times of repeated use can be increased.

As a method for fixing the support of the present invention by adhering or impregnating the organic liquid-absorbent resin, the support may be provided with an aqueous dispersion of the organic liquid-absorbent resin in a liquid-swelled state. Is applied and dried. Further, as the method, a method in which a dispersion system of the organic liquid absorbing resin in a non-swelling state in an organic liquid is applied to the support and dried. As a result, the operation of coating and drying can be simplified and the energy used can be reduced, so that it is suitably used in the present invention. Further, as the method, a method in which water or an organic liquid is contained in the support, and the organic liquid absorbing resin in a dry state is attached to the support and dried. The sheet-like body fixed by attaching or impregnating the organic liquid absorbing resin to the support by the method as described above can be obtained by performing a compressing operation using a static pressure press or a roller. In this case, the heating can be performed at room temperature, but it is more effective to perform the heating at room temperature or higher.

In the present invention, soil and / or solid matter having a specific gravity of 1 or more can be contained in the organic liquid permeable bag in addition to the organic liquid absorbing resin. By doing so, there is an advantage that the organic liquid absorber according to the present invention is less likely to flow into the organic liquid or the like, especially in the initial stage of installation. Examples of the solid having a specific gravity of 1 or more include those formed of natural minerals, those formed of waste, and those formed by binding waste. These materials include plastics, metals, ceramics or glass, and mixtures thereof. For such binding, a polymer material having a specific gravity of 1 or less can be used. The polymer material used for the binding is not particularly limited. For example, polystyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene- Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, polyester resin, polyvinyl alcohol, water-soluble resin such as casein or sodium polyacrylate, alcohol-soluble resin such as copolymerized nylon or methoxymethylated nylon, polyurethane, Curable resins that form a three-dimensional network structure, such as melamine resin or epoxy resin, and the like can be given.

In the present invention, a magnetic substance having a specific gravity of 1 or more can be used. Due to this magnetism, there is an advantage that the organic liquid absorber according to the present invention can be magnetically sucked and mobile transportation can be performed with a crane or the like. In addition, there is an advantage that the organic liquid absorber can be identified by the magnetism. Those having magnetism include those having ferrimagnetism, ferromagnetism, or parasitic magnetism. More specifically, as the ferromagnetic material, iron, nickel, cobalt or an alloy thereof, or an alloy containing these,
Further, a transition metal or an alloy thereof, and an alloy containing a rare earth element can be given. further,
Ferrite magnetic materials include magnetite, maghemite,
Examples include hematite, manganese zinc ferrite, manganese nickel ferrite, barium ferrite, and strontium ferrite. These may be those made of natural minerals, those made of waste, and those formed by binding waste. These are capable of increasing the weight of the sandbag significantly in comparison with a general inorganic material, and have an effect of relatively increasing the weight of the sandbag even in a liquid absorbing state.
In addition, since these materials can be obtained from inductor elements of used electric devices, deflection yokes of speakers and televisions, and are difficult to process in disassembly processing of electronic devices, they are also useful from the viewpoint of effective utilization. is there.

[0040]

As described above, the organic liquid absorbing material according to the present invention has an organic liquid absorbing resin in an organic liquid permeable bag-like body, and further has the organic liquid absorbing resin. The resin is obtained by introducing a hydrophilic polar group into a water-insoluble resin, and contains a modified polymer compound that exhibits a gel state by absorbing liquid. Therefore, the organic liquid absorber according to the present invention can absorb a wide range of various organic liquids and leaks the organic liquid to the storage area or the outside of the factory more efficiently than the conventional organic liquid absorber. Can be prevented. In addition, the organic liquid absorber according to the present invention has a small weight and a small volume during transportation, while it absorbs the organic liquid during use and sufficiently satisfies the function of following the weight, volume and external shape. Also, it is hard to lose its shape during transportation and storage.

The organic liquid absorber according to the present invention can be produced by using a used resin or a waste material, and a solid substance having a specific gravity of 1 or more, which is contained as desired, is hardly treated in the dismantling treatment of electronic equipment. Since it can be manufactured using members, these waste materials and the like can be effectively reused, and there is an advantage that they can contribute to the global environment.

[Description of the drawings]

FIG. 1 shows a cross-sectional view of an organic liquid absorber according to the present invention when it is dried.

FIG. 2 is a cross-sectional view of the organic liquid absorber according to the present invention at the time of liquid absorption swelling.

FIG. 3 is a cross-sectional view of an organic liquid absorber according to the present invention containing soil and / or a solid having a specific gravity of 1 or more, when dried.

FIG. 4 is a cross-sectional view of the organic liquid absorber according to the present invention containing soil and / or a solid having a specific gravity of 1 or more when the liquid is swollen.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 Organic liquid absorber 2 Organic liquid permeable bag 3 Organic liquid absorbent resin 4 Support 5 Soil or solid material having specific gravity of 1 or more

Continued on front page F-term (reference) 4F072 AB03 AB04 AB05 AB06 AB07 AB28 AB29 AD04 AD05 AD06 AD09 AD13 AD21 AD23 AD37 AD41 AD42 AD43 AD44 AD45 AD46 AD53 4G066 AC13B AC14B AC17B AC39A AD01B AD06B AD11B AD15B AD20B BA12 CA25 CA52 CA52 CA33

Claims (16)

[Claims] 1. An organic liquid absorber comprising an organic liquid absorbing resin comprising a water-insoluble resin into which a hydrophilic polar group is introduced, and a support. 2. The organic liquid absorber according to claim 1, wherein the support is a flexible network. 3. The organic liquid absorber according to claim 1, wherein the organic liquid absorbing resin is supported by a support. 4. The hydrophilic polar group may be a sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group,
A salt-forming -PO (OH) ₂ group, a salt-forming -OPO (OH) ₂ group, a salt-forming hydroxyl group, and a salt-forming 2. The method of claim 1, wherein the at least one kind of amine base is at least one kind.
The organic liquid absorber according to the above. 5. The organic liquid absorber according to claim 1, wherein the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble resin. 6. The organic liquid absorber according to claim 1, wherein the water-insoluble resin has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. 7. The method according to claim 1, wherein at least one of the aromatic ring and the conjugated diene contained in the water-insoluble resin accounts for 1 to 100 mol% based on all monomer units in the resin. 6. The organic liquid absorber according to 6. 8. An organic liquid absorber comprising a used organic liquid absorbing resin comprising a used water-insoluble resin into which a hydrophilic polar group has been introduced, and a support. 9. An organic liquid-permeable bag-like body comprising an organic liquid-absorbent resin obtainable by introducing a hydrophilic group into a water-insoluble resin and a support. Method for producing ionic liquid absorber. 10. The method for producing an organic liquid absorber according to claim 9, wherein the support is a flexible network. 11. The method for producing an organic liquid absorbent according to claim 9, wherein the organic liquid absorbent resin is supported by a support. 12. The hydrophilic polar group may be a sulfo group which may form a salt, a sulfate group which may form a salt, a carboxyl group which may form a salt, an amide group, a nitro group, A salt-forming -PO (OH) ₂ group, a salt-forming -OPO (OH) ₂ group, a salt-forming hydroxyl group, and a salt-forming The method for producing an organic liquid absorber according to claim 9, wherein the organic liquid absorber is at least one kind of a good amine base. 13. The method for producing an organic liquid absorber according to claim 9, wherein the hydrophilic polar group accounts for 0.1 to 99 mol% based on all monomer units in the water-insoluble resin. . 14. The method for producing an organic liquid absorber according to claim 9, wherein the water-insoluble resin has at least one kind of an aromatic ring and a conjugated diene in a main chain and / or a side chain. Method. 15. The method according to claim 1, wherein at least one of the aromatic ring and the conjugated diene contained in the water-insoluble resin accounts for 1 to 100 mol% based on all monomer units in the resin. 15. The method for producing an organic liquid absorber according to 14. 16. An organic liquid-absorptive resin obtainable by introducing a hydrophilic group into a used water-insoluble resin, and a support are filled in an organic liquid-permeable bag. A method for producing an organic liquid absorber.