KR20030049208A - New Crosslinked Polymer Having a Good Oil Absorbancy and Method of Preparing the Same - Google Patents

Abstract

The oil-absorbing crosslinked polymer of the porous particles having excellent oil absorption properties according to the present invention is a monomer solution or a styrene-based monomer or an alkyl or alicyclic substituent prepared from a crystalline acrylamide monomer having a long chain hydrocarbon in the side chain. A lipophilic radical initiator and a crosslinking agent are dissolved in a mixed solution of one selected from vinyl monomers such as an acrylate monomer and an acrylamide monomer, and the solution has a hydrophilc-lipophilic balance (HLB) of between 8 and 18. It is prepared by stirring, dispersing in water containing phosphorus surfactant and heating the resulting emulsion or suspension for a period of time and polymerizing.

Description

New Crosslinked Polymer Having a Good Oil Absorbancy and Method of Preparing the Same}

Field of invention

The present invention provides a new oil-absorbing crosslinked polymer capable of selectively absorbing, swelling and gelling an aliphatic or aromatic organic solvent, oil such as crude oil, or the like spilled or mixed in water or seawater, and the preparation thereof. It is about a method. More specifically, the present invention relates to a novel oil-absorbing crosslinked polymer prepared from new acrylamide-based monomers in which a functional group having a very high oil absorption characteristic with the spilled organic solvent and oil is introduced into the side chain, and a method for preparing the same. will be.

Background of the Invention

As the use of organic solvents and petroleum increases rapidly due to the recent development of the industry, the pollution of rivers and the oceans as well as the destruction of the environmental ecosystem are serious due to the outflow of organic solvents and the marine accidents of oil tankers. Therefore, there is an urgent need to develop an oil-absorbing material capable of selectively absorbing and separating the organic solvent, oil, such as crude oil, etc., from the water for water quality improvement and environmental protection.

In general, organic solvents and oils are hydrophobic and have a weak surface tension, which spreads very quickly when spilled into hydrophilic water. Therefore, if organic solvents or oils are spilled into rivers or oceans, first put on an oil fence to prevent the spread of oil, and then absorb the oil with paper or synthetic nonwoven fabric that can simply absorb the oil by capillary action. Remove it. In addition, as disclosed in US Pat. No. 3,843,306, a method of spraying porous clay with a lot of pores on a solid surface and then adsorbing oil to sink the water is most used. However, these methods require a lot of effort and time, and can only be used if the spilled area is narrow.

If the above oil is spilled in a wide area, spray the surfactant into the oil spill area and stir it with a machine such as a water jet to make the water and oil into an emulsion and then decompose naturally. (日本 水産 學會 編, 1979, 石油 汚染 水産 生物, p128-145). However, this method is not only accompanied by secondary contamination by the oil emulsion formed but also has a fundamental disadvantage of not being able to recover the spilled oil.

U.S. Patent Nos. 3,668,118 and 3,812,973 disclose methods for adsorbing and separating spilled oils using synthetic nonwoven fabrics made by coating lipophilic compounds such as paraffin onto existing polyethylene (or polypropylene) fibers. have. However, according to this method, the oil spilled by the capillary phenomenon of the nonwoven fabric is absorbed by the nonwoven fabric, and the oil absorbed is swelled by weak interaction force with compounds such as paraffin coated on the nonwoven fabric. As a result, the oil absorption rate is very low and the external pressure is applied only to release the oil absorbed. In addition, it is difficult to apply a large amount of nonwoven fabric to the oil spill area in a short time and requires a lot of labor to use. Only available in

Therefore, in order to overcome the above-mentioned fundamental problems and remove organic solvents or oils that are widely spilled in a short time, development of new materials having high oil absorption capacity, high oil absorption speed, and excellent pressure holding power that does not release oil absorbed oil is required. Many studies have been conducted.

According to Japanese Patent Application Laid-Open No. 5-9243, a polymer obtained by reacting α-olefin and maleic anhydride in the presence of a radical initiator to synthesize a copolymer and then reacting with an alcohol or an amine compound at high temperature in the presence of a radical crosslinking agent Cross-linking reaction or UV irradiation in the presence of a photoinitiator to cause a cross-linking reaction to prepare a crosslinked polymer having excellent oil absorption properties. However, in the crosslinking reaction by heat or ultraviolet energy, crosslinking is randomly formed between radicals randomly generated in the main and side chains of the polymer. Therefore, it is almost impossible to design and manufacture new oil absorbing crosslinked polymers whose structure is controlled as well as the distance and length between crosslinks.

Accordingly, the present inventors have disclosed a new oil-absorbing crosslinked polymer in which the disadvantages mentioned in the above-described Japanese patent in Korean Patent Application No. 1999-32111 have been solved. That is, the styrene-maleic anhydride copolymer is reacted with functional alcohols having a controlled number of aliphatic hydrocarbons and then ethylene glycol diglycidyl ether or aliphatic diol having different molecular chain lengths. As a result of the crosslinking reaction, the structure of the crosslinked polymer was controlled and a new oil absorbent polymer having excellent oil absorption characteristics could be prepared.

In addition, styrene-based monomers such as styrene and pt-butylstyrene or t-butylmethacrylate, 1,5-dimethyl-6-bicyclo [3,2,1] Acrylate-based monomers such as octyl methacrylate (1,5-dimethyl-6-bicyclo [3,2,1] octyl-methacrylate), methyl acrylate and aryl methacrylate are selected from the radical initiator and Polymerization in the presence of an emulsifier produced new oil absorbent crosslinked polymers. These inventions have been studied by Dow Chemical of the United States, Mitsui Petrochemical of Japan, Catalytic Chemistry, etc., and Japanese Patent Offices 45-27081, Japanese Patent Publications 50-15882, 50-59486 and 50-94092. Respectively. In addition, an acrylate-based low-crosslink density polymer having a long hydrocarbon group in the side chain has been developed and published by Japan's catalytic chemistry (Nov. 1990, pages 43-49).

The well-known emulsion or suspension polymerization technique has the advantage that it is very easy to prepare an oil-absorbing polymer having a uniform particle size in view of the polymerization process, but it is an interface that is a dispersant used during polymerization. Depending on the type and concentration of the active agent, the particle shape (size, appearance, surface structure, etc.) is very different. In addition, since the physical properties of the oil absorbent polymer mainly depend on the molecular structure of the monomer, the selection of these vinyl monomers and the composition of the monomers constituting the oil absorbent polymer are important.

Therefore, the present inventors have conducted a lot of research to overcome the problems shown in the known manufacturing techniques mentioned above, the high oil absorption ratio to the solvent, the speed of oil absorption is high, the pressure holding ability to the external pressure is excellent and the particles Has developed new oil-absorbing crosslinked polymers with homogeneous and porous structure and their preparation method.

It is an object of the present invention to provide a novel oil-absorbing crosslinked polymer capable of selectively absorbing, swelling and gelling an aliphatic or aromatic organic solvent and oils such as crude oil from water, and a method for producing the same.

It is another object of the present invention to provide a novel oil-absorbing crosslinked polymer prepared from new acrylamide-based monomers in which a functional group having a very high oil absorption property with the spilled organic solvent and oil is introduced into the side chain, and a method for preparing the same. It is for.

Still another object of the present invention is to provide a new oil-absorbing crosslinked polymer having a high oil absorption capacity, a high oil absorption rate, and excellent pressure holding power that does not release oil absorbed, and is uniform and porous.

Both the above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

1 is an electron micrograph of the oil absorbent crosslinked polymer prepared in Example 3. FIG.

2a and 2b are electron micrographs of the oil-absorbing crosslinked polymer prepared in Example 4.

3 is an electron micrograph of the oil absorbent crosslinked polymer prepared in Example 7.

4 is an electron micrograph of the oil absorbent crosslinked polymer prepared in Example 8.

5 is an electron micrograph of the oil absorbent crosslinked polymer prepared in Comparative Example.

The oil-absorbing crosslinked polymer of the present invention is vinyl, such as a monomer solution prepared from crystalline acrylamide monomer having a long chain hydrocarbon in the side chain, or a styrene monomer or an acrylate monomer having an alkyl or cyclic substituent. A lipophilic radical initiator and a crosslinking agent are dissolved in a monomer mixture prepared from one of the monomers and the acrylamide monomer, and the solution is immersed in water containing a surfactant having a hydrophilc-lipophilic balance (HLB) of 8-18. It is prepared by stirring, dispersing and heating the resulting emulsion or suspension for a period of time and polymerizing.

Hereinafter, a method for preparing the oil absorbent crosslinked polymer according to the present invention will be described in detail.

A new class of crystalline acrylamide monomers having long chain hydrocarbons in the side chain for use in the present invention is represented by the following formula (I):

Wherein R is-(CH ₂ ) n-CH ₃ , R 'is-(CH ₂ ) m-CH ₃ , n is 1-17, m is 1-10.

In Formula (I), R group is a long-chain alkyl group substituted at the ortho, meta, or para position of the benzene ring, and is a branched linear hydrocarbon or a constitutional isomer thereof. It is a branched hydrocarbon.

Specific examples of the crystalline acrylamide monomer having a long chain hydrocarbon represented by the formula (I) in the side chain include p-dodecylphenyl-N-acrylamide (DPAA) and p-tetradecylphenylacrylamide ( p-tetradecylphenyl-N-acrylamide (TPAA) or p-hexadecylphenylacrylamide (HPAA).

In the present invention, the crystalline acrylamide monomer having the long chain hydrocarbon represented by the formula (I) in the side chain may be used alone, and groups such as styrene, methyl, ethyl, t-butyl, or hydroxy are substituted in the para position. It may be used by mixing with the existing vinyl monomers selected from the styrene monomers. In addition, n-alkyl methacrylate having a long hydrocarbon such as lauryl, dodecyl, stearyl in addition to the styrene monomer; Methacrylates having alicyclic groups such as cyclohexyl methacrylate or ethylene glycol dicyclopentenyl ether methacrylate (EGDEM); Vinyl acetate; Acrylonitrile; Alternatively, conventional vinyl monomers of various structures such as n-pentene may be used.

However, in consideration of the physical properties of the prepared oil absorbent polymer, it is preferable to use a mixture of new acrylamide-based and styrene-based monomers or a mixture solution composed of new acrylamide-based and methacrylate-based monomers.

When the crystalline acrylamide is used alone or when the composition ratio of acrylamide to vinyl monomer in the monomer mixture exceeds 10%, cyclohexane, n-pentane, n-hexane, benzene, toluene, Dissolve in organic solvents such as xylene and use. At this time, the weight ratio of the monomer to the organic solvent is preferably adjusted to 20 to 80%.

In the polymerization reaction of the present invention, the water used as the continuous phase for the solution of the above-described monomers, which are discontinuous phases, was used in an amount of 1.0 to 5.0 times the weight of the monomer, depending on the controllability of the heat of polymerization released during the polymerization reaction. The amount is determined.

Polymerization initiators usable in the present invention are pyrolytic radical initiators such as azobisisobutyronitrile (AIBN), benzoylperoxide (BPO), 2,2'-azobis- (2,4-dimethylvaloronitrile ) (2,2'-azobis- (2,4-dimethyl valeronitrile)). The initiator is preferably used in an amount of 0.001 to 2.0% by weight of the monomer.

Physical properties of the oil absorbent polymer are greatly affected by the chemical structure of the polymer. In general, an oil absorbent polymer is composed of a main chain and a side chain possessing an oil absorption function, and a crosslink which connects the polymer main chains with each other. Among them, crosslinking has a great influence on the three properties of oil absorbent polymers: oil absorption capacity, oil absorption rate, and stability (pressure holding force) of swollen polymer gel after oil absorption. That is, their physical properties vary greatly depending on the distance between the crosslink and the crosslink and the length of the crosslink between the main chains depending on the structure and length of the chain of the crosslinker used. In other words, if the distance between the crosslinks and the length of the crosslinking agent is too long, the chemical attraction between the oil absorbed organic solvent or crude oil and the oil absorbent polymers is so weak that both properties are inferior. On the other hand, if these distances and lengths are too short, the space for the oil absorbing material can be narrowed to decrease the physical properties (usually the oil absorption capacity and the oil absorption rate or the oil absorption capacity and the pressure holding force are inversely proportional to each other, and the oil absorption speed and the pressure holding force are Proportional to each other).

Therefore, the inventors of the present invention are very important to control the oil absorption properties of the side chain that can impart the main chain and oil absorption properties of the polymer when preparing the oil absorbent polymer, as well as the molecular structure and length of the chain of the crosslinking agent described above. The study was conducted as judged. As a result, it was possible to prepare the oil absorbent polymer having the desired oil absorption properties by optimizing the selection and concentration conditions of the crosslinking agent as well as the synthesis of a new monomer.

The crosslinking agent usable in the present invention is a divinyl monomer having two or more vinyl groups in which the structure and the chain length of the crosslinking agent are different from each other and which can be crosslinked by a radical initiator, and examples thereof include divinyl benzene and ethylene glycol di ( Meta) acrylate, 1,4-butane diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, methylene, ethylene or propylene bisacrylamide, glycerol tri (meth) acrylate, trimethanol Propane tri (meth) acrylate and the like.

In addition to the crosslinking agent, it is also possible to use a bisphenol A-bisalkylenediacrylate (BADA) crosslinking agent represented by the following formula (II) in which the length of the chain synthesized for the first time in the present invention is controlled, in which case The properties of the absorbent polymers can be easily controlled:

In the formula, n is 2 to 12.

In the present invention, the crosslinking agent is preferably used at a concentration of 0.05 to 5.0% by weight of the monomer. If it is 0.05% or less, the pressure holding force is too weak to maintain the shape of the swelled swelling gel. On the other hand, if it is more than 5.0%, the oil absorption capacity for a particular solvent and oil is too low. In addition, since the physical properties of the prepared oil absorbent polymer depend not only on the concentration of the crosslinking agent used but also on the chain length of the crosslinking agent, when the chain length of the crosslinking agent is used, the concentration of the crosslinking agent should be increased.

In general, the suspension polymerization or emulsion polymerization method can easily remove excess heat of polymerization generated by polymerization by dispersing or emulsifying the lipophilic monomer in water and then causing a polymerization reaction, and having a uniform particle size after polymerization. There is an advantage to obtain a polymer of. At this time, the particle size and shape of the polymer produced varies depending on the type and concentration of the surfactant used in the O / W (oil in water) type polymerization in which the lipophilic monomer is dispersed in water. When using a hydrophilic surfactant (or emulsifier) having an HLB value of 14 to 18, which shows a correlation between the hydrophilicity and lipophilicity of a nonionic surfactant, polymer particles of 10 to 0.1 mu m are obtained. This polymerization is called emulsion polymerization. On the other hand, using nonionic surfactants (or dispersants) with HLB values between 8 and 13, or mixtures of anionic and nonionic systems, polymer particles between tens to hundreds of microns in size can be obtained. Is called suspension polymerization. In addition to the nonionic surfactants, mixtures of two or more selected from anionic and cationic surfactants or nonionic, anionic or cationic surfactants may be used as emulsifiers or dispersants.

Therefore, the inventors of the present invention have applied the characteristics of the polymerization method using the emulsifier or dispersant to produce an oil absorbent polymer having uniform and porous particles.

Surfactants usable in the polymerization reaction of the present invention include sorbitan monolaurate, polyoxyethylene sorbitan fatty acid esters (monolaurate, monostearate, monooleate), polyoxyethylene fatty acid esters (monolaurate, mono Stearate, monooleate), polyethylene glycol alkyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitol oleate, sodium dodecylbenzenesulfonate or mixtures thereof, polyvinyl alcohol or hydroxypropyl methyl cellulose, etc. Surfactants composed of nonionic mixtures or mixtures of anionic and nonionic compounds having an HLB value of between 8 and 18, either alone or selected from among surfactants, are used. At this time, the surfactant is preferably used in an amount of 0.05 to 3.0% by weight relative to the concentration of the monomer used.

On the other hand, the size and stability of the emulsion (emulsion) or suspension formed in the O / W type of polymerization, such as the present invention depends in particular on the type and concentration of the above-described surfactant. If this stability is destroyed by the heat of polymerization released during the polymerization reaction, the polymer particles are entangled with each other to produce a powder of uniform particles. Therefore, in order to obtain the shape (size, shape, surface structure, etc.) of uniform new oil-absorbing polymer particles, which is another feature of the present invention, selection of the type and concentration of the surfactant is important. In addition, the size and stability of the emulsion or suspension formed is closely related to the stirring speed of the surfactant polymerization. That is, in order to smoothly discharge the heat of polymerization generated during the polymerization reaction, the reactants should be stirred at a sufficient speed. In general, as the stirring speed increases under the same concentration of surfactant conditions, the size of the suspension decreases. As a result, the particle size of the prepared oil absorbent polymer is also reduced.

The polymerization temperature depends on the type of radical initiator used, but is preferably controlled between 40 and 90 ° C. in consideration of the heat of polymerization control, the stability of the surfactant and the ease of the polymerization process. The polymerization time is preferably between 5 and 10 hours in consideration of the polymerization conversion rate and the reaction process.

Water-soluble polycarboxylic acid, inorganic oxide (phosphorous oxide) in the polymerization solution after the completion of the polymerization in addition to the above components in order to improve the dispersibility of water-absorbent polymer according to the present invention and the oil absorption rate for the oil spilled ), Silica (trade name: AEROSIL), powder particles or fibers such as ethyl or hydroxypropyl cellulose, or cellulose acetate can be added to granulate the oil absorbent polymer of uniform particles. At this time, the additive is preferably used in an amount of 0.01 to 1.0% based on the weight of the monomer.

Through the optimization of the reaction conditions as described above, it was possible to prepare oil-absorbing crosslinked polymers having a new molecular structure not seen in the known art so far. The oil-absorbing crosslinked polymer synthesized by the present invention has excellent pressure holding power that does not discharge the absorbed solvent even under external pressure by selectively absorbing, swelling, and gelling the spilled organic solvent and oil from water. As a result, although there is a difference depending on the type of the organic solvent measured, it has an oil absorption capacity of 3 to 40 times per weight of the oil absorbent crosslinked polymer. The oil absorption rate showed the maximum oil absorption capacity between about 5 to 30 minutes after dispersing the oil absorbent crosslinked polymer of the porous powder particles. At this time, the oil absorption rate was very dependent on the shape, such as particle size, shape, degree of porosity and granulated shape of the prepared oil-absorbing crosslinked polymer.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1 Synthesis of Acrylamide Monomer (Formula I)

p-dodecylphenylacrylamide (DPAA) synthesis

5 g of p-Dodecylaniline and 2.72 ml of triethylamine (TEA) used as a hydrogen chloride (HCl) remover are dissolved in 75 ml of tetrahydrofuran (THF) solvent and dissolved in 100 ml of nitrogen. Put into a ml 2-neck round flask. To this solution, 1.59 ml of acryloyl chloride diluted with 25 ml of THF was dropped for 10 minutes through a 0 ° C. dropping funnel, followed by reaction for 6 hours. Thereafter, the mixture was further reacted at room temperature for 9 hours, and the resulting solution was filtered through a filter paper to remove salt precipitate, followed by removal of THF solvent. The resulting material was dissolved in 250 ml of dichloromethane, 100 ml of 5% aqueous NaHCO ₃ solution was added to a separatory funnel and shaken. The aqueous layer was separated to remove unreacted acryloyl chloride. 0.2 g of anhydrous magnesium sulfate (magnesium sulfate) was added to the separated organic solution layer and stirred for 2 hours to remove the trace amount of dissolved water. The dichloromethane solvent was then evaporated to give a solid mixture. 100 ml of hexane solvent was added thereto, stirred for 2 hours, and filtered through a filter paper to remove p-dodecylaniline remaining without reaction with the hexane solvent. After filtration and drying, a new white p-dodecylphenyl-N-acrylamide (DPAA) solid was obtained. The yield was 89% (5.35 g). The synthesized DPAA (Tm: 101 ° C.) was purified by recrystallization twice with ethanol and then used for the synthesis of oil-absorbing crosslinked polymer.

p-tetradecylphenylacrylamide (TPAA) synthesis

p-tetradecylphenyl-N-acrylamide (TPAA) was synthesized in the same manner as the DPAA synthesis except that p-tetradecylaniline was used instead of p-dodecylaniline. . The yield of synthesized TPAA (Tm: 104 ° C.) was 80%.

p-hexadecylphenylacrylamide (HPAA) synthesis

p-hexadecylphenyl-N-acrylamide (HPAA) was synthesized in the same manner as the DPAA synthesis, except that p-hexadedylananiline was used instead of p-dodecylaniline. . The yield of synthesized HPAA (Tm: 108 ° C) was 94%.

Example 2: Bisphenol A-bisalkylenediacrylate (BADA) Synthesis

0.4 g of potassium iodide and 6.5 mL of 6-chloro-1-hexanol were added to 50 mL of ethanol under a nitrogen atmosphere at room temperature, and stirred in a two-necked round flask. 5.0 g of bisphenol A and 1.92 g of sodium hydride were slowly added to the solution through a dropping funnel, followed by reaction for 96 hours. After the reaction, the salt precipitate was filtered through a filter paper and ethanol was removed by a 45 ^° C. rotary evaporator. The viscous liquid obtained here was dissolved in chloroform and filtered through a filter paper. The solution was subjected to column chromatography using a solution of ethyl acetate and hexane of 3: 1, and purified by bis (1-hydroxyhexane-oxyphenyl) bis (1-hydroxyhexane-oxyphenyl). propane). Yield 63% (5.9 g).

2.717 g (6.3 mmol) of bis (1-hydroxyhexane-oxyphenyl) propane synthesized above and 30 ml of THF were added to a 2-necked round flask and stirred under a nitrogen atmosphere of 0 ° C. A mixed solution of 1.285 ml of acryloyl chloride dissolved in 10 ml of THF was slowly added to the solvent through a dropping funnel, followed by reaction for 48 hours with stirring. At this time, 0.64 mL of TEA was used as the HCl remover. After the reaction, the THF was removed by a rotary evaporator, dissolved in dichloromethane, and 100 ml of a 5% aqueous NaHCO ₃ solution was added to a separatory funnel, shaken, and the aqueous layer was separated to remove unreacted acryloyl chloride. After this process three times, MgSO ₄ was added to the dichloromethane solvent layer to remove water by stirring and the solvent was evaporated. The resulting liquid was dissolved in a small amount of chloroform and subjected to column chromatography using a solution of 1: 3 ratio of ethyl acetate and hexane. Got. Yield 85% (2.865 g).

Instead of 6-chloro-1-hexanol, 12-chloro-1-dodecanol, 10-chloro-1-decanol, 8-chloro-1-octanol, 7-chloro-1-heptanol, 5-chloro A new crosslinker BADA having a controlled chain length was synthesized in the same manner as above except that -1-pentanol, 4-chloro-1-butanol or 2-chloroethanol was used. Yields vary between about 70-85%, depending on the length of alkylene bound to bisphenol A (n = 12, 10, 8, 7, 6, 5, 4, or 2).

Example 3

5 g of a new acrylamide monomer DPAA, 0.2 g of an initiator AIBN, and 0.05 g of a new crosslinking agent BADA (n = 6) were put together in a flask, and dissolved in 5 g of 50-55 ° C. benzene under a nitrogen atmosphere to prepare a monomer solution. A solution prepared by dissolving 0.05 g of polyoxyethylene monolaurate having a HLB value of 13.1, which is a nonionic surfactant, in 40 ml of distilled water was placed in a 100 ml jacket flask, followed by stirring at 250 rpm per minute. Continuously added at a rate of 2 mL / min and polymerized for 9 hours at 70 ℃. After the polymerization was terminated, the prepared polymerization solution was precipitated in a sufficient amount of methanol and filtered to recover the polymer powder. This was dried in a vacuum oven to obtain a powder of DPAA homopolymer, a new oil absorbent crosslinked polymer having a particle size of between about 75 and 200 μm.

The oil absorption ability to the solvent of the oil-absorbing crosslinked polymer prepared by the above method was measured by the following method. 0.1 g of oil-absorbing crosslinked polymer was placed in a beaker, and 100 ㏄ of the selected organic solvent was added thereto. The resultant was absorbed and swollen for 30 minutes. Oil absorption capacity (fold) was calculated. The results are shown in Table 1.

The oil absorption rate was measured by the following method. A 50 ml porous glass filter funnel was connected to a 50 ml burette with a silicone tube, and the middle of the tube could be opened and closed with a lock. 0 ml of the glass filter of the funnel and the scale of the burette were leveled, and the organic solvent to be measured was filled to 0 ml. After that, the locking device was closed, and evenly sprayed 1.0 g of the synthesized oil absorbent crosslinked polymer was evenly spread on the surface of the glass filter. Then, the locking device was opened, and a decrease in the scale of the burette over time was measured to calculate the oil absorption rate (ml / min).

Oil absorption time means the time to reach the maximum oil absorption capacity when using the above-mentioned oil absorption rate measuring apparatus. The results are shown in Table 1.

The particle size, shape, surface structure, etc. of the synthesized new oil absorbent crosslinked polymer were confirmed through a scanning electron microscope (SEM) photograph, and are shown in FIG. 1.

Example 4

When preparing a monomer solution, a new oil-absorbing crosslinked polymer, DPAA / styrene copolymer, was prepared in the same manner as in Example 3 except that the composition ratio of DPAA and the existing styrene monomer was adjusted to 2: 8 (weight ratio). Scanning electron micrographs of the oil absorbing crosslinked polymers obtained at this time are shown in FIGS. 2A and 2B. The oil absorbent crosslinked polymer was spherical porous particles having a particle size of about 600 μm (FIG. 2A), and the size of the surface pores was about 50 μm (FIG. 2B).

On the other hand, the composition ratio of the styrene monomer to the weight of DPAA in addition to the above composition ratio was optionally adjusted in the same manner as in Example 3 to prepare a new oil-absorbing crosslinked polymer of various compositions DPAA / styrene copolymer. At this time, the particle size, size distribution, surface appearance, etc. of the oil-absorbing crosslinked polymer were different depending on the composition ratio of the monomers used, but a porous powder having a uniform size of about 100 to 600 μm was obtained.

Example 5

A new oil absorbent crosslinked polymer, TPAA / Styrene copolymer, was prepared in the same manner as in Example 3 except that the composition ratio of TPAA and styrene monomers was adjusted to 2: 8 (weight ratio). At this time, the powder of the oil absorbent crosslinked polymer obtained spherical porous particles having a size of about 500 to 600 µm.

Example 6

A new oil-absorbing crosslinked polymer, HPAA / styrene copolymer, was prepared in the same manner as in Example 3 except that the composition ratio of HPAA and styrene monomers was adjusted to 2: 8 (weight ratio) when the monomer solution was prepared. At this time, the oil-absorbing crosslinked polymer powder obtained spherical porous particles having a size of about 400 to 550 μm.

Example 7

1.0 g of a new monomer DPAA, 4.0 g of t-butyl styrene (TBS) and 0.1 g of a surfactant having a HLB value of 13.2 consisting of a mixture of anionic and nonionic (trade name: Atlox 4851 B) Except for the same as in Example 3 to prepare a new oil-absorbing crosslinked polymer DPAA / TBS copolymer. The powder obtained was uniform spherical particles having a size between about 240 and 300 μm. Scanning electron micrographs of the prepared oil absorbing crosslinked polymer are shown in FIG. 3.

Example 8

2.0 g of a new monomer DPAA, 3.0 g of ethylene glycol dicyclopentenyl ether methacrylate (EGDEM), 0.025 g of divinylbenzene crosslinker, 0.1 g of sodium dodecylbenzenesulfonate anionic surfactant, After the polymerization was completed, the same procedure as in Example 3 was carried out except that 0.1 g of silica powder (trade name: AEROSIL-200) was used for granulation of the oil absorbent polymer, and a new oil absorbent crosslinked polymer, DPAA / EGDEM copolymer. Was prepared. A powder obtained by granulating fine spherical particles between about 0.5 to 1.0 μm was obtained, and a scanning electron micrograph is shown in FIG. 4.

Comparative Example

Surfactant with an HLB value of 13.2 consisting of 2.0 g of existing monomer pt-butylstyrene (TBS), 3.0 g of EGDEM, 0.05 g of a new crosslinking agent, BADA (n = 6), and a mixture of nonionics A new oil-absorbing crosslinked polymer, TBS / EGDEM copolymer, was prepared in the same manner as in Example 3 except that 0.1 g of Atlox 4851 B) was used and no benzene solvent was used to prepare the monomer solution. The powder obtained was a relatively large spherical particle between about 350-500 μm and a scanning electron micrograph is shown in FIG. 5.

Example Comparative Example One 2 3 4 5 6 Oil absorption capacity (g / g polymer) chloroform 18 30 28 27 24 20 10 toluene 16 28 26 27 21 18 7 Kerosene 8 4 6 8 5 6 6 n-octene 11 5 8 9 4 5 5 Oil absorption time (minutes) 15 10 11 10 25 8 30

According to the present invention, an aliphatic or aromatic organic solvent and oils such as crude oil can be selectively absorbed and swollen from water, and gelated, and functional groups having an oil absorption characteristic having a very high mutual attraction with the spilled organic solvent and oil are introduced into the side chain. As a result, the oil absorption capacity is high, the oil absorption speed is high, and the particles having excellent pressure holding power that do not release the oil absorbed are uniform and porous.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (27)

One monomer selected from a monomer solution prepared from a crystalline acrylamide monomer having a long chain hydrocarbon in the side chain, or a vinyl monomer such as a styrene monomer or an acrylate monomer having an alkyl or cyclic substituent, and acryl. Dissolving a lipophilic radical initiator and a crosslinking agent in a monomer mixed solution prepared from an amide monomer; The solution is stirred and dispersed in water containing a surfactant having a hydrophilc-lipophilic balance (HLB) of between 8 and 18; And Heating and polymerizing the resulting emulsion or suspension for a period of time; A process for producing oil-absorbing crosslinked polymers, comprising the steps of: The method of claim 1, wherein the crystalline acrylamide monomer having the long-chain hydrocarbon in the side chain is represented by the following formula (I): Wherein R is-(CH ₂ ) n-CH ₃ , R 'is-(CH ₂ ) m-CH ₃ , n is 1-17, m is 1-10. The R and R 'groups in the formula (I) are long-chain alkyl groups substituted at ortho, meta or para positions of the benzene ring. A process for preparing oil-absorbing crosslinked polymers, characterized in that they are branched hydrocarbons which are their constitutional isomers. The crystalline acrylamide monomer according to claim 2, wherein the crystalline acrylamide monomer having the long-chain hydrocarbon represented by the formula (I) in the side chain is p-dodecylphenyl-N-acrylamide (DPAA) or p-tetradecylphenyl A method for producing an oil absorbent crosslinked polymer, characterized in that it is selected from the group consisting of acrylamide (p-tetradecylphenyl-N-acrylamide: TPAA) or p-hexadecylphenyl-N-acrylamide (HPAA). The method of claim 1, wherein the vinyl monomer is styrene; Styrene monomers in which a group such as methyl, ethyl, t-butyl, or hydroxy is substituted in the para position; N-alkyl methacrylates with long hydrocarbons such as lauryl, dodecyl, stearyl; Methacrylates having alicyclic groups such as cyclohexyl methacrylate or ethylene glycol dicyclopentenyl ether methacrylate (EGDEM); Vinyl acetate; Acrylonitrile; Or n-pentene is selected from the group consisting of oil-absorbing crosslinked polymer. The cyclohexane, n-pentane, n-hexane, benzene according to claim 1, wherein a single solution of the crystalline acrylamide monomer is used or the composition ratio of acrylamide to vinyl monomer in the monomer mixture is more than 10%. And dissolved in an organic solvent such as toluene, xylene and used, wherein the weight ratio of monomer to organic solvent is 20 to 80%. The method of claim 1, wherein water used as a continuous phase for the monomer solution, which is a discontinuous phase, is used in an amount of 1.0 to 5.0 times the weight of the monomer. The radical initiator of claim 1, wherein the radical initiator is azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), 2,2'-azobis- (2,4-dimethylvaleronitrile) (2,2 ' -azobis- (2,4-dimethyl valeronitrile)), wherein the initiator is used in an amount of 0.001 to 2.0% by weight of the monomer. The method according to claim 1, wherein the crosslinking agent is bisphenol A-bisalkylenediacrylate (BADA) represented by the following formula (II): N is from 2 to 12. According to claim 1, wherein the cross-linking agent is a divinyl benzene, ethylene glycol di (meth) acrylate, 2 or more vinyl groups having different structures and chain lengths of the cross-linking agent and the cross-linking reaction is possible by a radical initiator , 4-butane diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, methylene, ethylene or propylene bisacrylamide, glycerol tri (meth) acrylate or trimethanol propane tri (meth) acrylic A method for producing an oil absorbent crosslinked polymer, characterized in that it is selected from the group consisting of a rate. The method according to claim 1, wherein the crosslinking agent is used at a concentration of 0.05 to 5.0% by weight of the monomer. The method of claim 1, wherein the surfactant is sorbitan monolaurate, polyoxyethylene sorbitan fatty acid ester (monolaurate, monostearate, monooleate), polyoxyethylene fatty acid ester (monolaurate, monostearate) , Monooleate), polyethylene glycol alkyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitol oleate, sodium dodecylbenzenesulfonate or mixtures thereof, polyvinyl alcohol or hydroxypropyl methyl cellulose A method for producing an oil-absorbing crosslinked polymer, characterized in that it is a single or two or more surfactants selected from the group consisting of a nonionic mixture having a HLB value of 8 to 18 or a mixture of anionic and nonionic. The method according to claim 1, wherein the surfactant is used in an amount of 0.05 to 3.0% by weight relative to the concentration of the monomer used. The method according to claim 1, wherein the polymerization temperature is between 40 and 90 ° C. The method according to claim 1, wherein the polymerization time is 5 to 10 hours. The method according to claim 1, wherein after completion of the polymerization reaction, powdered particles or fibers such as water-soluble polycarboxylic acid, inorganic oxide (phosphorous oxide), silica, ethyl or hydroxypropyl cellulose, or cellulose acetate, etc. The method for producing an oil-absorbing crosslinked polymer is further added. The method of claim 16, wherein the additive is used in an amount of 0.01 to 1.0% by weight based on the weight of the monomer. Crystalline acrylamide having a long chain hydrocarbon represented by the following formula (I) in the side chain: Wherein R is-(CH ₂ ) n-CH ₃ , R 'is-(CH ₂ ) m-CH ₃ , n is 1-17, m is 1-10. 19. The compound according to claim 18, wherein in the formula (I), R and R 'groups are long-chain alkyl groups substituted at ortho, meta or para positions of the benzene ring. Crystalline acrylamide having a long-chain hydrocarbon in the side chain, characterized in that the branched hydrocarbon (branched hydrocarbon) that is their constitutional isomer. Bisphenol A-bisalkylenediacrylate (BADA) represented by following formula (II): N is from 2 to 12. One monomer selected from a monomer solution prepared from a crystalline acrylamide monomer having a long chain hydrocarbon in the side chain or a vinyl monomer such as a styrene monomer or an acrylate monomer having an alkyl or cyclic substituent, and an acryl A lipophilic radical initiator and a crosslinking agent are dissolved in a monomer mixed solution prepared from an amide monomer, and the solution is stirred, dispersed in water containing a surfactant having a hydrophilc-lipophilic balance (HLB) value of 8 to 18, and the resulting solution. Oil-absorbing crosslinked polymer of porous particles having excellent oil absorption properties, characterized in that the emulsion or suspension is prepared by heating and polymerizing for a predetermined time. 22. The oil-absorbing crosslinked polymer of the porous particles having excellent oil absorption properties according to claim 21, wherein the crystalline acrylamide monomer having the long-chain hydrocarbon in the side chain is represented by the following formula (I): Wherein R is-(CH ₂ ) n-CH ₃ , R 'is-(CH ₂ ) m-CH ₃ , n is 1-17, m is 1-10. 23. The compound of claim 22, wherein in the formula (I), R and R 'groups are long-chain alkyl groups substituted at the ortho, meta or para position of the benzene ring. Oil-absorbing crosslinked polymer of porous particles having excellent oil absorption properties, characterized in that the branched hydrocarbon (branched hydrocarbon) which is their constitutional isomer. The crystalline acrylamide monomer according to claim 22, wherein the crystalline acrylamide monomer having the long chain hydrocarbon represented by the formula (I) in the side chain is p-dodecylphenyl-N-acrylamide (DPAA), p-tetradecylphenyl Absorption of porous particles having excellent oil absorption properties, characterized in that it is selected from the group consisting of acrylamide (p-tetradecylphenyl-N-acrylamide: TPAA) or p-hexadecylphenyl-N-acrylamide (HPAA). Oily crosslinked polymer. The method of claim 21, wherein the vinyl monomer is styrene; Styrene monomers in which a group such as methyl, ethyl, t-butyl, or hydroxy is substituted in the para position; N-alkylmethacrylates with long hydrocarbons such as lauryl, dodecyl, stearyl; Methacrylates having alicyclic groups such as cyclohexyl methacrylate or ethylene glycol dicyclopentenyl ether methacrylate (EGDEM); Vinyl acetate; Acrylonitrile; Or n-pentene oil-absorbing crosslinked polymer of porous particles having excellent oil absorption properties, characterized in that selected from the group consisting of. 22. The oil absorbent crosslinked polymer of claim 21, wherein the crosslinking agent is bisphenol A-bisalkylenediacrylate (BADA) represented by the following Formula (II): N is from 2 to 12. The method of claim 21 wherein the surfactant is sorbitan monolaurate, polyoxyethylene sorbitan fatty acid esters (monolaurate, monostearate, monooleate), polyoxyethylene fatty acid esters (monolaurate, monostearate) , Monooleate), polyethylene glycol alkyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitol oleate, sodium dodecylbenzenesulfonate or mixtures thereof, polyvinyl alcohol or hydroxypropyl methyl cellulose Oil absorption properties of porous particles having excellent oil absorption properties, characterized in that they are selected from the group consisting of one or two or more surfactants and a nonionic mixture having a HLB value of 8 to 18 or a mixture of anionic and nonionic. Crosslinked polymer.