KR101720310B1 - Absorbent crosslinked polymer and absorbent material comprising the same - Google Patents

Abstract

The present invention relates to an adsorbable crosslinkable polymer capable of selectively adsorbing and removing an oil component or an organic solvent component contained in a trace amount in wastewater, and reusable, and an adsorbent containing the crosslinkable polymer. The adsorbable crosslinking polymer is prepared by reacting a predetermined acrylamide-based monomer, an aromatic vinyl monomer and an alkyl (meth) acrylate having 8 to 20 carbon atoms in the presence of a polyfunctional (meth) acrylate-based or polyfunctional acrylamide- Wherein the molar ratio of the first monomer to the second monomer is 1.5: 8.5 to 6.5: 3.5, and the amount of the second monomer is 5 wt% or less. The organic solvent component or the oil component is selectively adsorbed from the wastewater containing the oil component or the organic solvent component.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adsorbent crosslinked polymer and an adsorbent containing the crosslinkable polymer,

The present invention relates to an adsorbable crosslinkable polymer capable of selectively adsorbing and removing an oil component or an organic solvent component contained in a trace amount in wastewater, and reusable, and an adsorbent containing the crosslinkable polymer.

Recently, the use of organic solvents and petroleum is rapidly increasing due to the development of industry, and environmental pollution problem caused by wastewater or sewage including this is increasing. Particularly, a considerable part of pollution sources such as industrial wastewater and domestic sewage are organic components such as oil components such as waste oil or waste organic solvents, and the above-mentioned oil component or organic solvent component contained in the wastewater at a relatively small concentration There is a continuing need for a technique for selectively removing the material.

Conventionally, a surfactant is added to wastewater to induce fine dispersion or decomposition of a hydrophobic oil or an organic solvent component contained in wastewater, or to use water as a main component in wastewater and the boiling point difference of the oil or organic solvent component And thus volatilizing such oil or organic components has been mainly applied. However, the first method is highly likely to cause secondary contamination by the surfactant, and the second method may consume enormous energy costs due to the heat required for volatilization. Moreover, the known methods, including these two methods, show good effects in some cases on some oil components or organic solvent components, so that they can be separated from wastewater containing various types of oil components and organic components, The technology capable of removing the components and the organic components together has not yet been properly developed.

For example, wastewater generated from the polycarbonate (PC) resin manufacturing process contains some organic solvent / oil components mainly including dichloromethane and triethylamine as contaminants. However, since dichloromethane and triethylamine exhibit different characteristics, it has been difficult to simultaneously remove them from the wastewater. Therefore, conventionally, wastewater generated in the PC resin manufacturing process has been treated by using a complicated wastewater treatment apparatus including two or more kinds of apparatuses for removing the wastewater.

More specifically, the dichloromethane contained in the wastewater was mainly removed by volatilization using a column or a device including a distillation column, and in the case of the triethylamine, the dichloromethane was mainly removed through filtration using neutralization and a filter. However, there has been a disadvantage in that a complicated apparatus and an expensive treatment cost are required in the wastewater treatment process. For example, in order to volatilize the dichloromethane, a high energy cost (such as steam generation and treatment cost) is required. In order to neutralize the triethylamine, a large amount of sodium hydroxide has to be used. Frequent filter replacement was required.

Therefore, it is possible to more effectively remove these various oil components and organic components from wastewater containing various kinds of oil components and organic components such as wastewater generated in the PC resin production process described above, and to further reduce the process cost and the like The development of technologies that can be used in the future is continuously being requested.

The present invention is to provide an adsorptive crosslinkable polymer which can more simply and selectively adsorb and remove various oil components and / or organic solvent components contained in a trace amount in wastewater, while being reusable.

The present invention also provides an adsorbent which can be used more effectively for selectively adsorbing and removing these adsorbent crosslinked polymers from waste water containing various oil components and / or organic solvent components.

The present invention relates to a process for producing an acrylate-based monomer composition comprising, in the presence of a polyfunctional (meth) acrylate-based or polyfunctional acrylamide-based crosslinking agent, an acrylamide-based monomer represented by the following formula (1), an aromatic vinyl monomer and an alkyl (meth) Wherein the molar ratio of the first monomer to the second monomer is 1.5: 8.5 to 6.5: 3.5, and the amount of the second monomer is 5 wt% or less. By weight based on the weight of the oil component or the organic solvent component.

 [Chemical Formula 1]

R is hydrogen or methyl,

,

,

또는

이고, R 'is selected from X,

,

,

or

ego,

X is -Z-R ", < RTI ID = 0.0 &

Y is alkylene having 1 to 10 carbon atoms,

Z is arylene having 6 to 20 carbon atoms,

R "is a linear or branched hydrocarbon having 10 to 20 carbon atoms.

The present invention also provides an adsorbent comprising the adsorptive crosslinked polymer.

Hereinafter, the adsorptive crosslinked polymer according to the specific embodiment of the present invention and the adsorbent containing the same will be described.

As described above, the adsorptive crosslinked polymer according to one embodiment of the present invention comprises the acrylamide-based first monomer of Formula 1 and a predetermined second monomer, that is, an aromatic vinyl monomer, or a long chain alkyl group having 8 to 20 carbon atoms (Meth) acrylate-based monomer or a mixture thereof in the presence of a polyfunctional (meth) acrylate-based or polyfunctional acrylamide-based cross-linking agent.

As a result of experiments conducted by the present inventors, it has been confirmed that such an adsorptive crosslinked polymer exhibits excellent adsorption performance against various organic solvent components and / or oil components contained in wastewater. These properties are achieved by the use of the acrylamide-based first monomer and the second monomer mentioned above, and the use of the cross-linking agent having high compatibility with the first and second monomers as well as the use of the organic solvent and / It is predicted that not only the non-polarity and the hydrophobicity indicating mutual attractive force but also the network structure defining the void space in which the various organic components can be adsorbed and held in the crosslinked polymer can be formed. Here, the cross-linking agent having high compatibility with the first and second monomers refers to a cross-linking agent having high similarity to monomers in various characteristics such as chemical structure, solubility and reactivity of the molecule, Quot;

As described above, due to the excellent adsorptivity to various organic solvent components and / or oil components, the use of the crosslinked polymer makes it possible to use various organic solvents and / Lt; RTI ID = 0.0 > and / or < / RTI > oil components together. In particular, it is also possible to separate them from wastewater containing wastewater in the PC resin manufacturing process at a concentration of about 5% by weight, or less than about 2% by weight, or from about 100 ppmw to 1% by weight of various organic solvents and / It can be very advantageously used for adsorption and removal.

More specifically, when the adsorptive crosslinking polymer of one embodiment is used in the PC resin production process in which wastewater containing mainly triethylamine and dichloromethane is generated, the triethylamine and dichloromethane can be adsorbed and removed together with excellent efficiency . Therefore, a complicated wastewater treatment process or application of a complicated device, which was necessary in the conventional PC resin manufacturing process, is not required much, and the process cost required for the wastewater treatment can be greatly reduced.

In addition, as a result of experiments by the inventors described later, it was confirmed that the adsorbing crosslinked polymer can exhibit excellent adsorption to organic solvents and the like after a simple process such as drying, and as a result, can be reused many times.

Therefore, the adsorptive crosslinked polymer of one embodiment can be very effectively and preferably used to treat various plant wastewater or domestic wastewater containing various organic solvents and / or oil components at a relatively low concentration, and their processing cost is greatly reduced .

On the other hand, the adsorptive crosslinked polymer of one embodiment is obtained by copolymerizing the acrylamide-based first monomer and the predetermined second monomer of the formula (1) in the presence of a polyfunctional (meth) acrylate-based or polyfunctional acrylamide-based crosslinking agent by a free radical polymerization process ≪ / RTI > Due to such a manufacturing process, the adsorptive crosslinked polymer of one embodiment of the present invention is obtained by copolymerizing a repeating unit of the following formula (2) derived from the first monomer and a repeating unit of a (meth) acrylate-based repeating unit having an aromatic vinyl- And may have a structure in which they are connected. The crosslinked polymer may include a crosslinking structure derived from the polyfunctional crosslinking agent together with the repeating units, and the crosslinking structure may include polymer chains containing repeating units derived from the first and second monomers, You can have a chemical structure that connects to a network:

 (2)

In the above formula (2), n is an integer of 15 to 1800, and R and R 'are as defined in formula (1).

On the other hand, the acrylamide-based monomer (1) used in the preparation of the cross-linked polymer of one embodiment is known from Korean Patent Registration No. 1163659 of the present inventors.

), 메타페닐렌(meta-phenylene,

), 파라페닐렌(para-phenylene,

), 나프탈렌(naphthalene,

), 아조벤젠(azobenzene,

), 안트라센(anthracene,

), 페난스렌(phenanthrene,

), 테트라센(tetracene,

), 파이렌(pyrene,

) 또는 벤조파이렌(benzopyrene,

) 등을 들 수 있다. In the first monomer and the repeating unit structure of Formula 2 derived therefrom, Z may be an arbitrary arylene group having 6 to 20 carbon atoms. Examples of the arylene include ortho-phenylene,

), Meta-phenylene,

), Para-phenylene,

), Naphthalene (naphthalene,

), Azobenzene (azobenzene,

), Anthracene,

), Phenanthrene (phenanthrene,

), Tetracene (tetracene,

), Pyrene (pyrene,

) Or benzopyrene,

) And the like.

The above-mentioned R "is a substituent which is substituted at least at one or more of the ortho, meta and para positions of the aromatic ring included in Z, and each independently represents a linear or branched aliphatic hydrocarbon N-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, and the like. Long chain alkyl.

As such, the aromatic hydrocarbon functional group and the linear or branched hydrocarbon functional group coexist in the acrylamide-based first monomer of formula (1) and R ', which is the side chain of the repeating unit structure of formula (2) derived therefrom. Non-polar and hydrophobic may exhibit strong mutual attraction with organic solvents and / or oil components. In addition, due to the presence of the relatively bulky side chains, the side chains or the polymer main chains can not be closely attached to each other, and organic solvents and / or oils may be adsorbed in the empty space formed thereby. As a result, the adsorptive crosslinked polymer of one embodiment can exhibit excellent adsorption and removal performance against a wide variety of organic solvents and / or oil components contained in wastewater.

Of the second monomers copolymerized with the first monomer, the aromatic vinyl-based monomer may be at least one selected from the group consisting of styrene, alkylstyrene, and halogenated styrene. More specifically, the aromatic vinyl-based monomer may be styrene, an alkyl styrene bonded to an alkyl dibenzene ring having 1 to 6 carbon atoms, or a halogenated styrene in which a halogen such as fluorine, chlorine, bromine or iodine is substituted one or more times in the benzene ring , Or a mixture of two or more selected from these. More specific examples of such aromatic vinyl monomers include monomers selected from the group consisting of? -Methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, p-ethylstyrene, Or more.

The alkyl (meth) acrylate monomer having 8 to 20 carbon atoms in the second monomer may be any (meth) acrylate compound having a long chain alkyl group. Specific examples thereof include dodecyl (meth) acrylate, (Meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate and octadecyl (meth) acrylate.

Such a second monomer can be cross-linked with the first monomer to control the non-polarity and hydrophobicity of the crosslinked polymer of one embodiment and form a suitable crosslinked structure, thereby further diversifying the types of oils and organic solvents that can be adsorbed. In addition, the crosslinked polymer of one embodiment can be processed and provided in an appropriate form such as fine particles applicable to the adsorbent. When a crosslinked polymer is prepared using only the first monomer without using the second monomer, it is difficult to form the crosslinked polymer or crosslinked gel itself, and thus it may be used as an actually adsorbing crosslinked polymer or may be difficult to be applied to an adsorbent.

In the crosslinked polymer of one embodiment described above, the molar ratio of the first monomer to the second monomer (or the molar ratio of the repeating units derived from each monomer) is about 1.5: 8.5 to 6.5: 3.5, or about 2: 6: 4. When the molar ratio of the first monomer is excessively large, it is difficult to form the crosslinked polymer and the crosslinked gel itself, as in the case of producing a crosslinked polymer using only the first monomer, and thus it may be used as an adsorptive crosslinked polymer or may be difficult to apply to an adsorbent . On the other hand, when the molar ratio of the second monomer is excessively large, it may exhibit adsorption only to a part of various organic solvents and / or oil components, and may exhibit poor adsorption to the rest.

On the other hand, in the adsorptive crosslinked polymer of one embodiment described above, the multifunctional (meth) acrylate crosslinking agent used for introducing the crosslinked structure may be a bifunctional (meth) acrylate crosslinking agent having two or more functional groups or Any multifunctional (meth) acrylate-based compound can be used. Specific examples thereof include (di- or tetra) ethylene glycol di (meth) acrylate [(di, tri, or tetra) ethyleneglycol di (meth) acrylate] or 1,14-tetradecanediol dimethacrylate (C _2-18 alkanediol di (meth) acrylate) having 2 to 18 carbon atoms such as 1,14-tetradecanediol dimethacrylate; Di (meth) acrylate-based compounds having a bisphenol A group such as bisphenol A dimethacrylate; Pentaerythritol triacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethyl propane ethoxy triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol (Meth) acrylate-based compounds having three to six functional (meth) acrylate groups such as hydroxypentaacrylate, dipentaerythritol hexaacrylate, and the like, and two or more selected from these may be used together Of course it is.

Further, a multifunctional acrylamide-based crosslinking agent may be used for introduction of the crosslinking structure, and any multifunctional acrylamide-based compound having two or more functional acrylamide groups may be used without limitation as the crosslinking agent. Specific examples thereof include N, N'-Ethylene Bisacrylamide, N, N'-Hexametylenebisacrylamide, N, N'-methylenebis Acrylamide (N, N'-methylenebisacrylamide), N, N'-cystaminebisacrylamide, or N, N'-diallylacrylamide And two or more selected from these may be used together.

Of these various crosslinking agents, the bisphenol A dimethacrylate and the like can be appropriately used from the viewpoint of introduction of an appropriate crosslinking structure and the like. This is because the bisphenol A group phenol, which forms an intermediate part of the crosslinking agent molecule, can have high compatibility with the aromatic hydrocarbon functional groups of the monomers, and the isopropyl group of the bisphenol A group has high compatibility with the linear or branched hydrocarbon functional groups of the monomers . Also, since the bisphenol A group is relatively bulky and provides a long and large space between methacrylate groups at both terminal ends of the crosslinking agent, it can be effectively used for polymerization-crosslinking reaction with monomers having bulky side chains.

Such a crosslinking agent may be used in a proportion of from about 0.01 to 5 moles, or from about 0.1 to 2 moles, or from about 0.3 to 0.7 moles, per 100 moles of the first and second monomers described above, The crosslinking polymer may be used in an amount of about 0.01 to 5 moles, or about 0.1 to 2 moles, or about 0.3 to 0.7 moles, based on 100 moles of the repeating units derived from the first and second monomers, As shown in FIG. If the content of the crosslinking agent (or the crosslinking structure derived therefrom) is too low, the physical strength of the crosslinking polymer (crosslinked gel) is low and it is difficult to maintain the state of the adsorbed swelling gel and the content of various organic solvents and / It may be difficult to apply to an adsorbent. On the contrary, if the content of the crosslinking agent is excessively high, the adsorption property may be lowered for at least a part of the organic solvent and / or the oil component.

In addition, since the physical properties of the prepared adsorbing crosslinked polymer depend not only on the concentration of the crosslinking agent used but also on the chain length of the crosslinking agent, it is necessary to appropriately increase or decrease the concentration of the crosslinking agent when different chain lengths of the crosslinking agent are used have. However, the kind and content of the cross-linking agent can be selected by a person skilled in the art in consideration of the specific kind and the content of the first and second monomers, and a further explanation thereof will be omitted.

On the other hand, the adsorptive crosslinking polymer of one embodiment described above can be obtained by crosslinking the above-mentioned first and second monomers in the presence of a polyfunctional (meth) acrylate or polyfunctional acrylamide crosslinking agent and a polymerization initiator by a free radical polymerization process .

Therefore, as the polymerization initiator, any radical polymerization initiator known to be routinely usable for the free radical polymerization reaction may be used. Examples of such polymerization initiators include peroxide-based polymerization initiators and azo-based polymerization initiators. More specific examples thereof include benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t- Based peroxides selected from the group consisting of butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, and t- Azobisisobutyronitrile, 2,2'-azobis (2-methylpropionitrile), and 1,1'-azobis (2-methylpropionitrile) (Cyclohexanecarbonitrile)], or a mixture of two or more selected from the group consisting of an azo type thermal initiator selected from the group consisting of 1,1'-azobis (cyclohexanecarbonitrile)

Such a polymerization initiator is preferably used in an amount sufficient to achieve a proper degree of crosslinking or degree of polymerization of the crosslinked polymer in one embodiment and to prevent the unreacted polymerization initiator from remaining in the crosslinked polymer as much as possible, About 0.1 to 5 mol%, or about 0.2 to 2 mol%.

In addition, the adsorptive crosslinking polymer of one embodiment described above can be produced by solution polymerization of a monomer composition containing the first and second monomers in the presence of a polymerization initiator and a crosslinking agent. Examples of the solvent usable in such a solution polymerization include at least one selected from the group consisting of cyclohexane, n-pentane, n-hexane, tetrahydrofuran, toluene, and benzene, Any organic solvent which can dissolve the polymerization initiator appropriately and which is known to be usable as a medium in the free radical polymerization reaction can be used.

Unlike suspension polymerization or emulsion polymerization, the solution polymerization does not require other additives such as a surfactant and a dispersant, has a small effective reaction volume, and has a simple reaction system. Thus, through such solution polymerization, the crosslinked polymer of one embodiment can be obtained more easily and effectively.

The adsorptive crosslinked polymer mainly consists of a main chain and a side chain which imparts an adsorption function and a crosslinked structure connecting the main chains of the polymer. The physical properties of the crosslinked polymer are the same as those of the main chain, side chain and crosslinked structure It can be greatly affected by the chemical structure. For example, the chemical structure including the crosslinked structure may greatly affect adsorption property, adsorption rate and stability (pressure holding force) of the crosslinked gel after swelling after adsorption, which are main physical properties of the adsorbing crosslinked polymer. However, the cross-linking polymer of one embodiment can be suitably controlled in chemical structure such as the cross-linking structure and side chain structure by optimizing the kind and structure of the first and second monomers, the content ratio thereof, and the kind and structure of the cross- . As a result, as described above, excellent adsorption and removal performance can be exhibited for various organic solvents and / or oil components contained in wastewater.

Therefore, the adsorptive crosslinked polymer of this embodiment can be very advantageously used to selectively adsorb and remove these contaminants from various wastewaters containing relatively low concentrations of various organic solvents and / or oil components.

Examples of the organic solvent and / or the oil component in which the adsorbing crosslinking polymer of this embodiment can exhibit excellent adsorption and removal performance include any organic solvent having a carbon number of 1 or more and a boiling point of about 10 ° C or higher and / And fossil fuel-derived oil components. More specific examples thereof include organic solvents having a dielectric constant of 2 to 10 such as n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, benzene, nitrobenzene, chlorobenzene, toluene, Examples of the solvent include dichloromethane, chloroform, chloroform, tetrahydrofuran (THF), dichloromethane (DCM), anisole, diethyl ether, trichloroethyelen or triethylamine And oil components such as crude oil, gasoline, light oil, heavy oil, kerosene, diesel oil, Bunker C oil, or mixtures thereof.

As such, since the adsorbent crosslinked polymer exhibits excellent adsorption and removal performance against various organic solvents and / or oil components, the adsorbent crosslinked polymer selectively and effectively adsorbs these contaminants from various wastewaters containing various organic solvents and / or oil components And an adsorbent for removing it.

As a representative example, the adsorptive crosslinked polymer and the adsorbent containing the adsorptive crosslinking polymer of the one embodiment can be very preferably used for selectively adsorbing and removing contaminants such as dichloromethane and triethylamine from the wastewater generated during the PC resin production process. The crosslinked polymer of the embodiment exhibits excellent adsorbability to most of contaminants such as dichloromethane and triethylamine and thus is produced in the PC resin manufacturing process in a very low process without requiring a complicated process or a processing device It is possible to effectively treat waste water.

In addition, the adsorptive crosslinked polymer can be obtained by pulverizing it to provide fine powder or particles. Further, the crosslinked polymer can be molded by various methods such as injection or extrusion to form a film, a sheet or a molded product, a fiber, Or in the form of a nonwoven fabric or the like. Therefore, it can be included in the adsorbent in an optimized form in consideration of the use purpose and the like. However, when the adsorptive crosslinked polymer and the adsorbent are used for selectively adsorbing and removing these contaminants from wastewater containing various organic solvents and / or oil components such as wastewaters such as PC resin manufacturing processes, It is appropriate to use it in powdered or granular state. Such powders or particles may have, for example, a particle size of about 1 to 1000 mu m.

In addition, the adsorbent crosslinked polymer and the adsorbent containing the adsorbent crosslinked polymer may be dried under reduced pressure, for example, at room temperature or higher, or at a temperature of about 50 ° C or higher, or about 100 ° C or higher, It can be heated and dried at a temperature of 200 ° C under normal pressure to exhibit excellent adsorption performance against the organic solvent and / or oil component again. Therefore, it can be reused after drying, and can be more preferably used for the step of removing the organic solvent and / or the oil component from the wastewater, and the efficiency and economical efficiency of the wastewater treatment process can be greatly improved.

The adsorptive crosslinked polymer according to the present invention can exhibit excellent adsorption performance against various organic solvent components and / or oil components contained in wastewater. Therefore, the use of the adsorptive crosslinked polymer makes it possible to more effectively and selectively adsorb and remove them from the wastewater containing various organic solvents and / or oil components, even though the conventional complicated apparatus or process is not applied, I can do it.

In addition, the adsorbing crosslinked polymer may exhibit excellent adsorption to an organic solvent, etc. after a simple process such as drying, and as a result, it can be reused many times.

Therefore, the adsorptive crosslinked polymer and the adsorbent containing the adsorbent crosslinked polymer can be very suitably used for adsorbing and removing various organic solvents and oil components from wastewater generated in the PC resin manufacturing process, etc., and simplify and efficient the wastewater treatment process, And the like.

1 and 2 show electron micrographs of the fine particles obtained by using the crosslinked gel of Comparative Example 1 and Example 1 in Test Example 2. FIG.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

[Comparative Example 1] Preparation of crosslinked gel of Polystyrene

13 mg (0.1 mmol) of divinyl benzene, which is a crosslinking agent, and 96.9 mg (0.4 mmol) of benzoyl peroxide, which is a radical initiator, were added to 20 mL of glass ampoule and subjected to freeze-pump-thawing To remove the oxygen present in the solution, the ampoule was sealed and the radical polymerization reaction was carried out at 70 DEG C for 24 hours. The cross-linked gel after polymerization was impregnated with 400 mL of chloroform and swelled for 8 hours to dissolve the initiator, the unreacted monomer and the cross-linking agent in chloroform to wash the cross-linked gel, followed by vacuum filtration and drying to remove chloroform, 2.01 g of polystyrene crosslinked gel was prepared.

[Comparative Example 2] Preparation of poly (dodecyl acrylate) crosslinked gel

Except for using 2.4 g (10 mmol) of dodecyl acrylate instead of monomer styrene, 18.3 mg (0.05 mmol) of 1,14-tetradecanediol dimethacrylate instead of divinyl benzene as crosslinking agent and 48.4 mg (0.2 mmol) of benzoyl peroxide, Poly (dodecyl acrylate) crosslinked gel was prepared in the same manner as in Comparative Example 1. The yield thereof was 86%, and 2.08 g of the crosslinked gel was obtained.

[Comparative Example 3] Preparation of poly (styrene-dodecyl acrylate) crosslinked gel

Except that 0.62 g (6 mmol) of monomer styrene was used, and 1.44 g (6 mmol) of dodecyl acrylate and 58.1 mg (0.24 mmol) of benzoyl peroxide were used in the same manner as in Example 1, -dodecyl acrylate crosslinked gel. The yield thereof was 88%, and 1.84 g of the crosslinked gel was obtained.

[Comparative Example 4] Preparation of cross-linked gel of poly (p-dodecylphenyl acrylamide) [poly (DOPAM)]

Bisphenol A dimethacrylate (12.8 mg, 0.035 mmol) as a crosslinking agent and 33.9 mg (0.14 mmol) of benzoyl peroxide as a radical initiator were dissolved in benzene (5.04 mL) obtained in Example 1 of Patent Registration No. 1163659 in an amount of 2.21 g Was placed in a 20 mL glass ampoule and oxygen present in the solution was removed by a freeze-pump-thawing method. The ampoule was sealed and the radical polymerization was carried out at 70 ° C for 24 hours. In order to wash the resultant product after the polymerization in the same manner as in the above-mentioned comparison 1, the result of the polymerization was impregnated into 400 mL of chloroform. As a result, the polymerization product was dissolved without swelling. That is, it was confirmed that the result of the polymerization of Comparative Example 4 was insufficient in crosslinking, and thus the crosslinked gel could not be formed.

[Example 1] Poly (styrene-DOPAM) crosslinked gel

A solution obtained by dissolving 1.58 g (5 mmol) of the monomer DOPAM obtained in Example 1 of Patent Registration No. 1163659 in 3.6 mL of benzene and 0.52 g (5 mmol) of another monomer styrene, 18.2 mg (0.05 mmol) of bisphenol A dimethacrylate as a crosslinking agent, 48.4 mg (0.2 mmol) of benzoyl peroxide, an initiator, was placed in a 20 mL glass ampoule and the oxygen present in the solution was removed by freeze-pump-thawing method. The ampoule was sealed and heated at 70 ° C. for 24 hours with radical Polymerization reaction was carried out. The crosslinked gel after polymerization was impregnated with 400 mL of chloroform and swelled for 8 hours to dissolve the initiator and the unreacted monomer and the crosslinking agent in chloroform to wash the crosslinked gel. The crosslinked gel was then filtered under reduced pressure and dried to remove chloroform. Finally, 81% 1.71 g of poly (styrene-DOPAM) crosslinked gel having a molar ratio of styrene to DOPAM of 5: 5 was prepared. Such a poly (styrene-DOPAM) crosslinked gel was confirmed to have a chemical structure represented by the following chemical formula 3, including a crosslinked structure derived from a repeating unit derived from each monomer and a crosslinking agent:

(3)

In the above formula (3), the molar ratio of x: y: z = 50: 50: 0.5.

[Example 2] Preparation of poly (dodecyl acrylate-DOPAM) crosslinked gel

A solution obtained by dissolving 1.26 g (4 mmol) of the monomer DOPAM obtained in Example 1 of Patent Registration No. 1163659 in 2.88 mL of benzene, 0.96 g (4 mmol) of another monomer dodecyl acrylate, 14.6 mg (0.05 mmol) of bisphenol A dimethacrylate as a crosslinking agent, (Dodecyl acrylate-DOPAM) crosslinked gel was prepared in the same manner as in Example 1, except that 48.4 mg (0.2 mmol) of benzoyl peroxide was used as a radical initiator. Its yield was 77%, and 1.72 g of the crosslinked gel was obtained. Such a poly (dodecyl acrylate-DOPAM) crosslinked gel was confirmed to have a chemical structure represented by the following chemical formula 4, including a crosslinked structure derived from a repeating unit derived from each monomer and a crosslinking agent:

[Chemical Formula 4]

In the formula (4), x: y: z = 50: 50: 0.5.

[Test Example 1] Evaluation of adsorptivity of crosslinked gel to various organic solvent components

The crosslinking gels of the remaining Comparative Examples 1 to 3 and Examples 1 and 2 were evaluated for adsorption performance against various organic solvent components by the following method, except that Comparative Example 4, which could not be made into a crosslinked gel, was carried out. The target organic solvent components were n-hexane, benzene, triethylamine (TEA) and dichloromethane (DCM).

0.1 g of each crosslinked gel and 50 cc of the target organic solvent were placed in a beaker and allowed to stand for 2 hours. Each swollen crosslinked gel adsorbed on each target organic solvent component was placed on a metal mesh (100 mesh), and the excess organic solvent not adsorbed was removed by filtration, and the weight of the swollen resin was measured. From these measurement results, the adsorption capacity (times) of the sample was calculated according to the following equation.

Adsorption capacity = (weight of crosslinked gel after adsorption - weight of crosslinked gel before adsorption) / weight of crosslinked gel before adsorption)

The results of the calculation of adsorption capacity are summarized in Table 1 below:

Evaluation of adsorption properties on various organic solvent components n-hexane (g) Benzene (g) TEA (g) DCM (g) Comparative Example 1 0.39 12.05 1.06 18.83 Comparative Example 2 4.57 6.22 5.56 7.78 Comparative Example 3 2.38 6.76 4.11 11.55 Example 1 1.42 7.46 4.37 15.40 Example 2 2.70 7.82 4.23 13.73

Referring to Table 1, Comparative Examples 1 and 2, which consist of only repeating units of one structure, exhibit poor adsorptivity for some organic solvent components. In the case of Comparative Example 3 having the repeating units of Comparative Examples 1 and 2 at the same time, the adsorbability of Comparative Examples 1 and 2 was exhibited in a complex and complementary form, but the adsorption properties of Comparative Examples 1 and 2 were lower than those of Examples 1 and 2 Adsorption. This is because DOPAM, which is one of the repeating units of Examples 1 and 2, has both an aromatic ring and a chained aliphatic structure and thus has a high interaction with various hydrophobic and nonpolar organic components. In addition, due to the large molecular volume of DOPAM, It seems that the cohesion between the organic solvent and the organic solvent becomes low and the organic solvent adsorbs and creates a lot of empty space.

In particular, Examples 1 and 2 show excellent adsorptivity for both TEA and DCM, which are mainly contained in wastewater during the PC resin production process, and can be used to remove these organic solvent components together. In contrast, Comparative Examples 1 and 2 exhibited poor adsorptivity to TEA or DCM, respectively, and Comparative Example 3 was found to exhibit low adsorptivity for both solvents in comparison with the Examples. Thus, the crosslinked gel of the examples may be suitably used to treat wastewater in a more simplified process during the PC resin production process.

[Test Example 2] Evaluation of particle formability of crosslinked gel

The cross-linked gels of Comparative Examples 1 to 3 and Examples 1 and 2 were pulverized with Freezer Mill (SPEX 6850) except for Comparative Example 4, which could not be made into a crosslinked gel, and the formability into particles was confirmed. The cross-linked gels of Comparative Examples 2 and 3 were in the form of jelly-like jelly having high elasticity, and were not easy to crush and crush into particles through physical impact such as milling. This seems to be due to the properties of dodcyl acrylate repeating units. Since the Tg of the uncrosslinked poly (doecyl acrylate) is low at -3 ° C and the Tm is as low as 1.5 ° C and is not a solid at room temperature, Comparative Examples 2 and 3, in which the proportion of the repeating units of dodecyl acrylate is high, It has a lump shape, but it is not a solid solid and has flexibility and elasticity. Therefore, even if a physical impact is applied, it has been confirmed that processing into fine particles is not suitable because it absorbs the impact very well and does not break well.

On the other hand, Comparative Example 1, Example 1 and Example 2 each have a particle diameter of 20 to 100 占 퐉 (Comparative Example 1), a particle diameter of 10 to 100 占 퐉 (Example 1), and a particle diameter of 20 to 150 占 퐉 It can be molded into the form of fine particles having The electron micrographs of the fine particles of Comparative Example 1 and Example 1 are shown in FIGS. 1 and 2, respectively.

[Test Example 3] Efficiency of wastewater treatment in the process of PC resin production of crosslinked gel

Using the crosslinked gel of Comparative Example 1 and Example 1, the wastewater treatment efficiency generated during the PC resin production process was evaluated by the following method.

First, an aqueous solution containing 0.2% by weight of TEA and 1% by weight of DCM was prepared so as to resemble the wastewater of the plant generated in the actual PC resin production process. To 2 g of this aqueous solution was added 0.2 g of crosslinked gel particles of Comparative Example 1 and Example 1 (prepared in Test Example 2), and the aqueous solution was stirred at 3000 rpm for 2 minutes using a voltex mixer.

Using a syringe filter, the crosslinked gel in the aqueous solution was removed and the concentration of TEA and DCM in the filtered wastewater was analyzed by GC. Experiments using each crosslinking gel were carried out twice to confirm reproducibility. The results of this analysis are summarized in Table 2 below:

GC peak area Percent removed (%) TEA DCM TEA DCM Aqueous solution before treatment (wastewater) 1171.21 817.33 - - The aqueous solution (wastewater) treated in Comparative Example 1 1102.74 407.25 5.85 50.17 1159.87 412.02 0.97 49.59 The aqueous solution (wastewater) treated in Example 1 504.55 282.21 56.92 65.47 546.50 279.64 53.34 65.79

Referring to Table 2, it was confirmed that the crosslinked gel of Example 1 exhibited excellent adsorption to both TEA and DCM mainly contained in wastewater in the PC resin production process and could be used to remove these organic solvent components together. In contrast, in Comparative Example 1, the TEA adsorption and removal performance was low, and it was confirmed that when the wastewater was treated using the same, a separate process and apparatus for TEA removal were required.

In addition, Example 1 was found to exhibit superior adsorption and removal performance over both Comparative Example 1 and TEA in a single aqueous solution (wastewater).

[Test Example 4] Evaluation of reusability of crosslinked gel

In Test Example 3, the crosslinked gel of Example 1 used primarily for the treatment of an aqueous solution (wastewater) was recovered and dried at room temperature in a vacuum oven for 2 hours or at a convection oven for 6 hours at 70 ° C. The dried crosslinked gel was again treated with an aqueous solution (wastewater) in the same manner as in Test Example 3, and the treatment results are summarized in the following Table 3:

GC peak area Percent removed (%) TEA DCM TEA DCM Aqueous solution before treatment (wastewater) 910.5 670.6 - - Reuse The aqueous solution (wastewater) treated in Example 1 Convection oven drying 436.6 203.8 52.05 69.61 Vacuum oven drying 426.6 175.8 53.15 73.78

Referring to Table 3, it was confirmed that the crosslinked gel of Example 1 can be reused because once it has been used for adsorption, it can exhibit excellent adsorptivity again after being subjected to a drying process or the like.

Claims (15)

In the presence of a polyfunctional (meth) acrylate-based or polyfunctional acrylamide-based crosslinking agent,
A first acrylamide-based monomer represented by the following general formula (1)
A monomer composition comprising at least one second monomer selected from the group consisting of an aromatic vinyl monomer and an alkyl (meth) acrylate monomer having from 8 to 20 carbon atoms is a cross-linked copolymerized adsorptive crosslinked polymer,
Wherein the molar ratio of the first monomer to the second monomer is from 2: 8 to 6: 4,
An adsorbable crosslinking polymer used for selectively adsorbing an oil component or an organic solvent component containing dichloromethane and triethylamine from wastewater containing an oil component or an organic solvent component at a concentration of less than 5 wt%
[Chemical Formula 1]

R is hydrogen or methyl,
R 'is X or

ego,
X is -ZR ", and < RTI ID =
Y is alkylene having 1 to 10 carbon atoms,
Z is arylene having 6 to 20 carbon atoms,
R "is a linear or branched hydrocarbon having 10 to 20 carbon atoms.
The thermoplastic resin composition according to Claim 1, which comprises a repeating unit derived from the first monomer and a repeating unit derived from the second monomer, the repeating unit derived from the first monomer and having a crosslinking structure derived from the polyfunctional (meth) Crosslinked Polymer:
(2)

In the above formula (2), n is an integer of 15 to 1800, and R and R 'are as defined in formula (1).
The polymerizable composition according to Claim 2, which is characterized in that it has adsorptivity (relative to 100 moles of the repeating units derived from the first and second monomers) of 0.01 to 5 moles of the crosslinking structure derived from the polyfunctional (meth) Crosslinked polymer.
2. A compound according to claim 1, wherein Z is ortho-phenylene,

), Meta-phenylene,

), Para-phenylene,

), Naphthalene (naphthalene,

), Azobenzene (azobenzene,

), Anthracene,

), Phenanthrene (phenanthrene,

), Tetracene (tetracene,

), Pyrene (pyrene,

) And benzopyrene,

). ≪ / RTI >
The adsorbing crosslinked polymer according to claim 1, wherein the aromatic vinyl-based monomer comprises at least one member selected from the group consisting of styrene, alkylstyrene, and halogenated styrene.
The composition according to claim 1, wherein the alkyl (meth) acrylate monomer having 8 to 20 carbon atoms is selected from the group consisting of dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate and octadecyl Wherein the adsorptive crosslinking polymer comprises at least one member selected from the group consisting of an alkyl group,
2. The composition of claim 1 wherein the polyfunctional (meth) acrylate based crosslinking agent is selected from the group consisting of (di- or tetra) ethylene glycol di (meth) acrylate [(di, tri, or tetra) ethyleneglycol di 1,4-tetradecanediol dimethacrylate, bisphenol A dimethacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, At least one member selected from the group consisting of trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, and dipentaerythritol hexaacrylate, / RTI >
The method of claim 1, wherein the polyfunctional acrylamide crosslinking agent is selected from the group consisting of N, N'-Ethylene Bisacrylamide, N, N'-Hexametylenebisacrylamide, , N, N'-methylenebisacrylamide, N, N'-cystaminebisacrylamide, and N, N'-diallylacrylamide (N , N-diallylacrylamide). ≪ / RTI >
The crosslinkable adsorbent crosslinked polymer according to claim 1, wherein the monomer composition comprising the first and second monomers is crosslinked in the presence of a polyfunctional (meth) acrylate crosslinking agent or a polyfunctional acrylamide crosslinking agent and a polymerization initiator.
The method of claim 9, wherein the polymerization initiator is selected from the group consisting of benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide butyl peroxyisobutyrate, azobisisobutyronitrile, 2,2'-azobis (2-methylpropionitrile), and 1,1'-azobisisobutyronitrile '-Azobis (cyclohexanecarbonitrile). The adsorptive crosslinkable polymer is one or more peroxide-based or azo-based compounds selected from the group consisting of' -azobis (cyclohexanecarbonitrile).
delete delete An adsorbent comprising the adsorptive crosslinkable polymer according to any one of claims 1 to 10.
14. The adsorbent according to claim 13, wherein the adsorbent comprises particles of the adsorbing crosslinked polymer having a particle diameter of 1 to 1000 mu m.
14. The adsorbent of claim 13, wherein the adsorbent is reusable after drying.

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