JPH0680889A - Production of granular oil absorbing agent - Google Patents

Abstract

PURPOSE:To efficiently produce an oil absorbing agent absorbing a large amount of various kinds of oils, even an oil-water mixed system, swelling, having excellent oil retaining performances of absorbed oil and extremely improved oil absorption rate. CONSTITUTION:An aqueous solution of a metal salt of an organic acid and an aqueous solution of an inorganic polyvalent metal salt are subjected to double decomposition reaction in the presence of granules of an oil absorbing crosslinked polymer obtained by polymerizing a hydrophobic monomer having <=9 solubility parameter in the presence of a cross-linkable monomer so that a polyvalent metal salt of the organic acid is precipitated on the surface of the granules of the oil absorbing crosslinked polymer to give a granular oil absorbing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an oil absorbent. More specifically, a granular oil-absorbing agent that absorbs a large amount of oil and swells against a wide variety of oils even from an oil-water mixed system, has excellent oil-holding performance of the absorbed oil, and has a significantly improved oil-absorption rate Well about manufacturing methods.

[0002]

2. Description of the Related Art In recent years, the recovery of oil spilled into the sea and oil in waste water has become a major environmental issue. Further, there is a strong demand for a simple method for treating leaked oil such as small-scale waste oil discarded in homes and factories and machine oil in factories.

[0003] As one of the effective means for recovering these oil spills and oil components in waste water or treating waste oil and oil leaks, a method of adsorbing oil with an oil absorbent and then incineration or other post-treatment has been conventionally used. Has been. As such an oil absorbing material,
For example, a synthetic fiber oil absorbing material made of a hydrophobic fiber such as polypropylene fiber, polystyrene fiber, polyethylene fiber or a nonwoven fabric thereof has been used. However, the conventional synthetic fiber-based oil absorbent material is inferior in oil retention performance after oil absorption because the oil absorbing action is due to adsorption and holding of the oil in the voids existing in the oil absorbent material due to the capillary phenomenon, so that it is less than the low viscosity oil. Has substantially no oil retaining ability, and since the oil that was easily absorbed is re-released even with viscous oil with a slight external pressure, liquid sagging easily occurs and post-treatment becomes extremely complicated. Was. Also, when applied to the recovery of oil content of oil-water mixed system or thin film oil floating on the water surface, the recovery rate of oil is poor and a large amount of water is absorbed, so the oil absorbing material sinks in water and is difficult to recover. However, there is a problem in that combustion after recovery is inconvenient.

As means for solving these problems, some synthetic resin type oil absorbents of the type in which oil is absorbed and swelled in a certain polymer have been reported. For example,
A copolymer of t-butylstyrene / divinylbenzene (JP-A-45-27081), a cross-linked polymer of t-butyl methacrylate and / or neopentyl methacrylate (JP-A-50-15882), and menthyl methacrylate of Cross-linked polymer (JP-A-50-59486), polynorbornene rubber (for example, Nosolex AP manufactured by CdF), and cross-linked polymer of alkyl (meth) acrylate having 10 to 16 carbon atoms (JP-A-3-221).
582) and the like. These oil-absorbing agents have an oil-absorption function because they absorb oil into the molecule having a hydrophobic structure and swell, so that only oil is added to the oil content of oil-water mixed systems and thin-film oil floating on the water surface. Absorbs selectively,
Moreover, it has advantages such as excellent oil retaining ability for oil once absorbed.

However, these synthetic resin-based oil absorbents have the drawback that the time required for oil absorption is extremely long as compared with synthetic fiber oil absorbents, and in particular, they have a low oil absorption rate for highly viscous oils. There was a problem.

Therefore, in order to improve the oil absorption speed, measures have been taken to increase the surface area of these oil absorbents by processing these oil absorbents into fine particles. However, as the oil-absorbing agent becomes finer, the particles tend to agglomerate with each other, so that the actually expected sufficient oil-absorption rate has not been obtained. Therefore, these oil absorbing agents have a drawback that they are difficult to be applied to the field in which it is required to absorb the oil in a short time, such as when an oil spill accident occurs.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above problems of conventional oil absorbing materials (agents). That is, the object of the present invention is to absorb a large amount of oil to a wide variety of oils even from an oil-water mixed system and swell, and the oil absorption performance of the absorbed oil is excellent, and the oil absorption speed is remarkably improved. An object of the present invention is to provide a method for producing a granular oil-absorbing agent, which can easily produce the agent with good reproducibility.

[0008]

[Means for Solving the Problems] The present inventors have prepared a crosslinked polymer by precipitating a water-insoluble polyvalent metal salt of an organic acid from a water by metathesis reaction in the presence of a specific oil-absorbing crosslinked polymer particles. It has been found that a complex oil-absorbing agent satisfying the above-mentioned object can be produced easily and with good reproducibility by combining an organic acid polyvalent metal salt, and the present invention has been completed.

That is, according to the present invention, the monomers (A) 96 to 9 having one polymerizable unsaturated group in the molecule whose main component is a monomer having a solubility parameter (SP value) of 9 or less.
9.999% by weight and 0.001 to 4 crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule
% By weight (however, the sum of monomers (A) and (B) is 10
(0% by weight) in the presence of granular particles of the oil-absorbing crosslinked polymer (I) obtained by polymerizing a monomer component composed of an organic acid metal salt aqueous solution and an inorganic polyvalent metal salt aqueous solution. A granular oil absorbent containing an oil-absorbing crosslinked polymer (I) and an organic acid polyvalent metal salt (II), characterized in that a water-insoluble organic acid polyvalent metal salt (II) is precipitated. The present invention relates to a manufacturing method of.

[0010]

The solubility parameter (SP value) is generally used as a measure of the polarity of a compound, and in the present invention, the value derived by substituting the Hoy cohesive energy constant into the Small calculation formula is applied. And the unit (cal /
expressed in cm ^{3) 1/2.}

The monomer constituting the main component of the monomer (A) used in the present invention is a monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule. If a monomer having a solubility parameter (SP value) of more than 9 is used as the main component of the monomer (A), only a crosslinked polymer having insufficient oil absorption performance can be obtained, which is not preferable.

Examples of the monomer having a solubility parameter (SP value) of 9 or less and having one polymerizable unsaturated group in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth). Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate,
Dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, octylphenyl (meth) acrylate, nonylphenyl (meth) acrylate, dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) Unsaturated carboxylic acid esters such as acrylate, isobornyl (meth) acrylate, dibutyl maleate, didodecyl maleate, dodecyl crotonate, didodecyl itaconate; (di) butyl (meth) acrylamide, (di) dodecyl (meth) acrylamide ,
(Meth) acrylamide having a hydrocarbon group such as (di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide; 1-hexene, 1-octene, isooctene, Α-Olefins such as 1-nonene, 1-decene, 1-dodecene; alicyclic vinyl compounds such as vinylcyclohexane; allyl ethers having a hydrocarbon group such as dodecyl allyl ether; vinyl caproate, vinyl laurate, palmitic acid Vinyl ester having a hydrocarbon group such as vinyl and vinyl stearate;
Vinyl ether having a hydrocarbon group such as butyl vinyl ether and dodecyl vinyl ether; aromatic vinyl compounds such as styrene, t-butyl styrene, octyl styrene and the like can be mentioned, and one or more of these monomers can be used. You can Among these, as a monomer that gives better oil absorption performance and oil retention performance,
It has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, and is alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide, alkylaryl (meth) acrylamide,
The monomer (A) containing as a main component at least one unsaturated compound (a) selected from the group consisting of fatty acid vinyl ester, alkylstyrene and α-olefin is particularly preferable.

Such solubility parameter (SP value)
Is 9 or less, the amount used in the monomer (A) is
The proportion is 50% by weight or more, more preferably 70% by weight or more, based on the total amount of the monomer (A). When the amount of the monomer having the solubility parameter (SP value) of 9 or less in the monomer (A) is less than 50% by weight, only a crosslinked polymer having poor oil absorption performance and oil retention performance can be obtained.

Therefore, in the present invention, 5 monomers having a solubility parameter (SP value) of 9 or less are included in the monomer (A).
It is necessary that the content of the solubility parameter (SP) is 50% by weight or less in the monomer (A), although the content of SP is 0% by weight or more.
A monomer having one polymerizable unsaturated group may be contained in a molecule whose value) exceeds 9. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride, fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. You can

Examples of the crosslinkable monomer (B) used for polymerizing the oil-absorbent crosslinked polymer (I) in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and polyethylene. Glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,
3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, N, N'-
Methylenebisacrylamide, N, N'-propylenebisacrylamide, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polyhydric alcohol (for example, glycerin, trimethylolpropane or tetra). Examples thereof include polyfunctional (meth) acrylate obtained by esterification of alkylene oxide adduct of (methylolmethane) and (meth) acrylic acid, divinylbenzene, etc., and one or two kinds of these crosslinkable monomers. The above can be used.

The ratio of the monomer (A) and the crosslinkable monomer (B) in the monomer component used for producing the oil-absorbent crosslinked polymer (I) is as follows. The amount of the monomer (A) is 96 to 99.9 based on the total amount of the crosslinkable monomer (B).
99% by weight, the crosslinkable monomer (B) is 0.001-
It is in the range of 4% by weight.

When the amount of the monomer (A) is less than 96% by weight or the amount of the crosslinkable monomer (B) exceeds 4% by weight, the crosslink density of the obtained crosslinked polymer becomes too high and a large amount of oil is obtained. It is not preferable because it cannot be absorbed. Further, the monomer (A) is 9
If it exceeds 9.999% by weight or the crosslinkable monomer (B) is less than 0.9.
If it is less than 001% by weight, the solubility of the resulting crosslinked polymer in oil is increased, and the crosslinked polymer is fluidized after oil absorption and the performance as an oil absorbing agent cannot be obtained, which is not preferable.

Oil-absorbing crosslinked polymer (I) in the present invention
Is, for example, the above-mentioned monomer component in an aqueous medium, polyvinyl alcohol, hydroxyethyl cellulose, a protective colloid agent such as gelatin or sodium alkylsulfonate,
It can be produced by dispersing in the presence of a surfactant such as sodium alkylbenzene sulfonate, polyoxyethylene alkyl ether, and fatty acid soap, and suspension-polymerizing with an oil-soluble radical polymerization initiator. If necessary, the monomer component may be dissolved in a water-insoluble organic solvent and then suspension-polymerized. By such suspension polymerization, an aqueous dispersion of the particulate matter of the crosslinked polymer (I) can be obtained and can be used as it is in the precipitation step of the organic acid polyvalent metal salt (II) described below. Examples of the oil-soluble radical polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide;
-Azo compounds such as azobisisobutyronitrile and 2,2'-azobisdimethylvaleronitrile can be used. The polymerization temperature can be appropriately selected within the range of 0 to 150 ° C. depending on the type of monomer component and the type of polymerization initiator.

In the present invention, as a method for producing the oil-absorptive crosslinked polymer (I), after the oil-absorptive crosslinked polymer (I) is polymerized by bulk polymerization, an operation such as pulverization is added to adjust the particle size to obtain granular particles. You can give a way to make things.
Bulk polymerization may be carried out, for example, by pouring a monomer component into a mold in the presence of the above-mentioned polymerization initiator and conducting the polymerization under the condition of 50 to 150 ° C.

In the present invention, the oil-absorbing crosslinked polymer (I)
Is preferably a granular material having an average particle size in the range of 0.5 to 500 μm by introducing a pre-suspension step using a homomixer during suspension polymerization or adjusting the stirring power during polymerization. When the average particle size of the particles of the oil-absorbent crosslinked polymer (I) is less than 0.5 μm, the surface area is reduced due to the Mamako phenomenon based on the aggregation of the particles, and an oil absorbent having an improved oil absorption rate can be obtained. It will be difficult. Further, if the average particle diameter of the granular particles of the oil-absorbent crosslinked polymer (I) exceeds 500 μm, the oil absorption rate also decreases as the surface area of the crosslinked polymer decreases, which is not preferable.

The organic acid metal salt used in the present invention is water-soluble to form an aqueous solution, and is converted into a substantially water-insoluble organic acid polyvalent metal salt (II) by a metathesis reaction with an inorganic polyvalent metal salt. There is no particular limitation as long as it produces, for example, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid,
Palmitic acid, stearic acid, arachidic acid, behenic acid,
Linear saturated fatty acids such as lignoceric acid, serotic acid, montanic acid and melissic acid; linear unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid; branched fatty acids such as isostearic acid; ricinoleic acid, 12-hydroxystearic acid Examples of the fatty acid having a hydroxyl group such as; benzoic acid; naphthenic acid; sodium salts, potassium salts, lithium salts and the like of organic acids such as rosin acids such as abietic acid and dextropimaric acid; More than one species can be used. Among these organic acid metal salts, monovalent metal salts of fatty acids having 3 to 30 carbon atoms are preferable.

The inorganic polyvalent metal salt used in the present invention is a water-soluble organic acid polyvalent metal salt (II) which is water-soluble to form an aqueous solution and which undergoes a metathesis reaction with the organic acid metal salt. There is no particular limitation as long as it forms, and examples thereof include inorganic polyvalent metal salts such as calcium chloride, calcium sulfate, magnesium chloride, zinc chloride, and aluminum chloride, and one or more of these may be used. You can

According to the production method of the present invention, the organic acid metal salt aqueous solution and the inorganic polyvalent metal salt aqueous solution are mixed in the presence of the particulate oil-absorbing cross-linked polymer (I) to prepare two kinds of salts. Water-insoluble organic acid polyvalent metal salt (II)
Is precipitated from the aqueous solution. As a specific operation, for example, a granular material of the cross-linked polymer (I) obtained by the above polymerization is added to an aqueous solution of either the organic acid metal salt or the inorganic polyvalent metal salt, if necessary, with a surfactant. After dispersing using
The metathesis reaction may be performed by adding the other aqueous solution of either the organic acid metal salt or the inorganic polyvalent metal salt. After the reaction, the solid content is separated and washed if necessary, and then dried to give an oil-absorbing crosslinked polymer (I) and an organic acid polyvalent metal salt (I
It is possible to obtain a granular oil absorbent comprising I) and. The metathesis reaction proceeds at room temperature, but 40 to 100 ° C.
It is preferable to react within the range.

Furthermore, as an effective means in the production method of the present invention, an organic acid metal salt such as sodium stearate or sodium laurate is used as a dispersant when polymerizing the oil-absorbing crosslinked polymer (I) by suspension polymerization. It is also possible to employ a method in which an aqueous dispersion of the granular polymer (I) obtained by suspension polymerization is directly mixed with an aqueous solution of an inorganic polyvalent metal salt to carry out a metathesis reaction.

Organic acid polyvalent metal salt (II) in the present invention
Is a water-insoluble or sparingly water-soluble compound precipitated from an aqueous solution by a metathesis reaction of the organic acid metal salt and the inorganic polyvalent metal salt, and a combination of the organic acid metal salt and the inorganic polyvalent metal salt described above. It consists of various compounds. For example, aluminum stearate, calcium stearate, calcium laurate, zinc caprylate and the like can be mentioned.

The mixing ratio of the oil-absorptive crosslinked polymer (I) and the organic acid polyvalent metal salt (II) in the present invention is not particularly limited, but the oil-absorptive crosslinked polymer (I) is 30 to 99.9 parts by weight. It is preferable that the polyvalent metal salt of organic acid (II) is 0.1 to 70 parts by weight. Organic acid polyvalent metal salt (I
If the amount of I) is less than 0.1 parts by weight, the particles of the oil-absorbing crosslinked polymer (I) aggregate with each other, and the oil absorption rate of the obtained oil absorbing agent decreases, which is not preferable. Further, it is not preferable to use a large amount of the organic acid polyvalent metal salt (II) in an amount exceeding 70 parts by weight because the oil absorption amount of the oil absorbing agent and the oil retaining performance are deteriorated.

The oil absorbing agent thus obtained can be used in various forms. For example, a granular oil-absorbing agent may be used as it is by adding or sprinkling it to an oil-water mixed system such as an oil-water suspension or an aqueous solution in which oil is dissolved, or oil, or after being filled in an open container such as a cylindrical tube. Good. Further, the oil absorbing agent of the present invention may be granulated with a binder if necessary, attached to or contained in a fiber, or filled in a cloth bag or a porous package for use.

Further, the oil absorbent may be used in combination with conventionally known oil absorbents and fillers such as chaff, straw, pulp, cotton, porous lime, porous silica, porous pearlite, polypropylene fiber and the like. You can also

[0029]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight unless otherwise specified.

[0030]

Example 1 A 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube, and a reflux condenser was charged with polyoxyethylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., trade name: Sophthanol 150, which is also used in the following examples. 3 parts (commercially used) were dissolved in 300 parts of water and charged, and the inside of the flask was replaced with nitrogen while stirring and heated to 40 ° C. under a nitrogen stream. Then, 99.794 parts of nonylphenyl acrylate (SP value: 8.3) as the monomer (A), 0.206 parts of 1,6-hexanediol diacrylate as the crosslinkable monomer (B), and a polymerization initiator. Was added to the flask all at once, and the mixture was vigorously stirred under the condition of 750 rpm.

Then, the temperature inside the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out the polymerization reaction. Then, the temperature inside the flask was further raised to 90 ° C. and maintained for 2 hours to complete the polymerization. By doing so, an aqueous dispersion containing the oil-absorptive cross-linked polymer (1) having an average particle diameter of 30 μm (resin content 25% by weight)
Got

After adding 60 parts of an aqueous dispersion containing the oil-absorptive crosslinked polymer (1) obtained by the previous polymerization to an aqueous solution prepared by dissolving 5 parts of sodium stearate in 150 parts of water, the temperature was raised to 70 ° C. The mixture was stirred at 300 rpm for 10 minutes. Then, an aqueous solution prepared by dissolving 1 part of calcium chloride in 20 parts of water was gradually added, and stirring was continued at 70 ° C. for 15 minutes to complete the metathesis reaction. The reaction product solution thus obtained is dried in an oil bath at 105 ° C. with stirring to obtain a granular oil absorbent (1) containing 15 parts of the oil-absorbing crosslinked polymer (1) and 5 parts of calcium stearate. Obtained.

[0033]

Example 2 Hexadecyl methacrylate (SP value: 7.8) 49.93 as the monomer (A) in Example 1.
0 part and N-octyl methacrylamide (SP value:
8.6) 49.930 parts, divinylbenzene O.V. as the crosslinkable monomer (B). By the same method as in Example 1 except that 140 parts were used instead and the number of revolutions was changed to 200 rpm, an aqueous dispersion containing the oil-absorbing crosslinked polymer (2) having an average particle diameter of 300 μm (resin content 25 wt. %) Was obtained.

To an aqueous solution of 5 parts of sodium stearate dissolved in 150 parts of water was added 180 parts of an aqueous dispersion containing the oil-absorptive crosslinked polymer (2) obtained by the previous polymerization, and the temperature was raised to 70 ° C. The mixture was stirred at 300 rpm for 10 minutes.
Then, an aqueous solution prepared by dissolving 1 part of calcium chloride in 20 parts of water was gradually added, and stirring was continued at 70 ° C. for 15 minutes to complete the metathesis reaction. The obtained reaction product liquid is dried in an oil bath at 105 ° C. with stirring to obtain a granular oil absorbent (2) containing 45 parts of the oil-absorbing crosslinked polymer (2) and 5 parts of calcium stearate. Obtained.

[0035]

Example 3 Dodecyl acrylate (SP value: 7.9) 57.7 as a monomer (A) in an aqueous solution prepared by dissolving 3 parts of the polyoxyethylene alkyl ether in 300 parts of water.
72 parts and N, N-dioctyl acrylamide (SP
Value: 8.2) 38.515 parts, polypropylene glycol dimethacrylate (molecular weight 4000) as the crosslinkable monomer (B) 3.713 parts, and as the polymerization initiator 2,2
′ -Azobisisobutyronitrile O. A solution consisting of 5 parts was added and mixed with a homomixer at 10,000 rpm for 10 minutes to obtain an aqueous dispersion of a monomer.

Then, an aqueous dispersion of the above monomer was charged into a 500 ml flask equipped with a thermometer, a stirrer, a gas introduction tube and a reflux condenser, and the inside of the flask was replaced with nitrogen while vigorously stirring under the conditions of 400 rpm. did. Subsequently, the temperature inside the flask was raised to 70 ° C. under a nitrogen stream, the polymerization temperature was maintained for 2 hours to carry out the polymerization reaction, and then the temperature was further raised to 90 ° C. to complete the polymerization, and the oil absorption with an average particle diameter of 5 μm was obtained. An aqueous dispersion (resin pure content: 25% by weight) containing the crosslinkable polymer (3) was obtained.

After adding 30 parts of an aqueous dispersion containing the oil-absorptive cross-linked polymer (3) obtained by the previous polymerization to an aqueous solution prepared by dissolving 5 parts of sodium caprylate in 150 parts of water, the temperature was raised to 70 ° C. The mixture was stirred at 300 rpm for 10 minutes. Then, an aqueous solution prepared by dissolving 2 parts of zinc chloride in 40 parts of water was gradually added, and stirring was continued at 70 ° C. for 15 minutes to complete the metathesis reaction. The reaction product solution thus obtained is dried in an oil bath at 105 ° C. while being stirred, whereby a granular oil absorbing agent containing 7.5 parts of the oil-absorbing crosslinked polymer (3) and 5 parts of zinc caprylate ( 3) was obtained.

[0038]

Example 4 99.823 parts of dodecyl acrylate (SP value: 7.9) as the monomer (A) in Example 1,
As the crosslinkable monomer (B), ethylene glycol diacrylate O. By the same method as in Example 1 except that 177 parts was used instead, an aqueous dispersion containing the oil-absorbing crosslinked polymer (4) having an average particle diameter of 30 μm (resin pure content: 25% by weight) was obtained.

After adding 60 parts of an aqueous dispersion containing the oil-absorptive crosslinked polymer (4) obtained by the above polymerization to an aqueous solution prepared by dissolving 5 parts of sodium stearate in 150 parts of water, the temperature was raised to 70 ° C. The mixture was stirred at 300 rpm for 10 minutes. Then, an aqueous solution prepared by dissolving 1 part of calcium chloride in 20 parts of water was gradually added, and stirring was continued at 70 ° C. for 15 minutes to complete the metathesis reaction. The obtained reaction product liquid is dried in an oil bath at 105 ° C. with stirring to obtain a granular oil absorbent (4) containing 15 parts of the oil-absorbing crosslinked polymer (4) and 5 parts of calcium stearate. Got

[0040]

Example 5 In Example 1, t- was used as the monomer (A).
54.881 parts of butylstyrene (SP value: 7.9) and 44.903 parts of 1-decene (SP value: 7.0), 0.216 parts of divinylbenzene as the crosslinkable monomer (B) were used instead. A water dispersion containing the oil-absorbing crosslinked polymer (5) (resin content of 25% by weight) was obtained by the same method as in Example 1 except for the above. Then, the solid content was separated from the aqueous dispersion by filtration, dried and pulverized with a colloid mill to obtain granular oil-absorbing crosslinked polymer (5) having an average particle size of 5 μm.

To an aqueous solution prepared by dissolving 5 parts of sodium stearate in 150 parts of water was added 15 parts of the oil-absorptive crosslinked polymer (5) obtained by the previous polymerization, and the temperature was raised to 70 ° C., and then 300 rpm. It stirred for 10 minutes on condition of. Then, an aqueous solution prepared by dissolving 1 part of calcium chloride in 20 parts of water was gradually added, and stirring was continued at 70 ° C. for 15 minutes to complete the metathesis reaction. The obtained reaction product liquid was dried in an oil bath at 105 ° C. with stirring to give 15 parts of an oil-absorbing crosslinked polymer (5) and 5 parts of calcium stearate.
A granular oil absorbing agent (5) containing 10 parts was obtained.

[0042]

Example 6 Nonylphenyl acrylate (SP value: 8.3) 74.79 as the monomer (A) in Example 1.
3 parts and hydroxyethyl acrylate (SP value: 1
0.3) The same method as in Example 1 except that 24.931 parts was used instead and the amount of 1,6-hexanediol diacrylate as the crosslinkable monomer (B) was changed to 0.276 parts. Thus, an aqueous dispersion (resin content of 25% by weight) containing the oil-absorbent crosslinked polymer (6) having an average particle diameter of 30 μm was obtained.

To an aqueous solution prepared by dissolving 0.8 part of calcium chloride in 120 parts of water was added 60 parts of an aqueous dispersion containing the oil-absorptive crosslinked polymer (6) obtained by the above polymerization, and the temperature was raised to 70 ° C. After that, the mixture was stirred for 10 minutes under the condition of 300 rpm. Then, an aqueous solution in which 5 parts of sodium behenate was dissolved in 150 parts of water was gradually added, and stirring was continued at 70 ° C. for 15 minutes to complete the metathesis reaction. The obtained reaction product liquid is dried in an oil bath at 105 ° C. while being stirred to give a granular oil absorbent (6) containing 15 parts of the oil-absorbing crosslinked polymer (6) and 5 parts of calcium behenate. Got

[0044]

Example 7 In Example 1, 2 parts of sodium stearate was used instead of 3 parts of polyoxyethylene alkyl ether.
Using 5 parts, vinyl laurate (S) as the monomer (A)
P value: 7.9) 99.811 parts, trimethylolpropane triacrylate O.V. as the crosslinkable monomer (B). 18
By the same method as in Example 1 except that 7 parts were used instead, an aqueous dispersion (pure resin content: 25% by weight) containing the oil-absorbing crosslinked polymer (7) having an average particle diameter of 30 μm was obtained.

Then, an aqueous solution prepared by dissolving 5 parts of calcium chloride in 100 parts of water was gradually added to 60 parts of an aqueous dispersion containing the oil-absorptive cross-linked polymer (7) obtained by the above polymerization, to obtain 70 parts.
Stirring was continued for 15 minutes at 0 ° C. to complete the metathesis reaction. The obtained reaction product liquid is dried in an oil bath at 105 ° C. with stirring to give an oil-absorbing crosslinked polymer (7) 1
A granular oil absorbent (7) containing 5 parts and 5 parts of calcium stearate was obtained.

[0046]

Comparative Example 1 An average particle diameter of 30 μm was obtained in the same manner as in Example 4 except that the amount of dodecyl acrylate was changed to 94.637 parts and the amount of ethylene glycol diacrylate was changed to 5.363 parts. An aqueous dispersion containing the comparative polymer (1) was obtained.

Then, a comparative oil absorbent (1) containing 15 parts of the comparative polymer (1) and 5 parts of calcium stearate was obtained in the same manner as in Example 4.

[0048]

Comparative Example 2 Dodecyl acrylate 9 in Example 4
Instead of the monomer (A) consisting of 9.823 parts, 39.854 parts of dodecyl acrylate and methacrylic acid (SP
Value: 10.1) 59.780 parts were used, and Comparative Polymer (2) having an average particle size of 30 μm was prepared in the same manner as in Example 4 except that the amount of ethylene glycol diacrylate was changed to 0.366 parts. An aqueous dispersion containing it was obtained.

Then, a comparative oil absorbent (2) containing 15 parts of the comparative polymer (2) and 5 parts of calcium stearate was obtained in the same manner as in Example 4.

[0050]

Comparative Example 3 An aqueous dispersion containing the comparative polymer (3) having an average particle size of 30 μm was obtained by the same method as in Example 4 except that the crosslinkable monomer (B) was not used. It was

Then, a comparative oil absorbent (3) containing 15 parts of the comparative polymer (3) and 5 parts of calcium stearate was obtained by the same method as in Example 4.

[0052]

Comparative Example 4 The aqueous dispersion of the crosslinked polymer (4) obtained in Example 4 was put in a glass petri dish and dried at 100 ° C. for 24 hours to obtain a sheet-shaped comparative oil absorbent (4).

[0053]

[Example 8] Oil absorbing agent (1) obtained in Examples 1-7
(7) and the comparative oil absorbent obtained in Comparative Examples 1 to 4 (1)
Each of 5 g of (4) to (4) was immersed in kerosene at 20 ° C. for 24 hours, and then collected by filtration on a 508 mesh nylon filter cloth. Next, the kerosene that was not absorbed and retained by the oil absorbing agent was wiped off, the weight of the oil absorbing agent was measured, and the saturated absorption amount of kerosene was calculated according to the following formula. The results are shown in Table 1.

Saturated absorption amount (g) = weight of oil absorbent after immersion in kerosene-weight of oil absorbent before immersion in kerosene

[0055]

[Example 9] Oil absorbing agent (1) obtained in Examples 1 to 7
(7) and the comparative oil absorbent obtained in Comparative Examples 1 to 4 (1)
5 g of each of (4) to (4) were weighed into a cylindrical glass test tube having an inner diameter of 20 mm. Then, under the condition of 20 ° C., the kerosene equivalent to half the saturated absorption amount of kerosene obtained in Example 8 was charged into each test tube at a time, and the time until no fluidized kerosene was observed (oil absorption time) Was measured. The results are shown in Table 1.

[0056]

[Table 1]

[0057]

According to the production method of the present invention, it is easy to uniformly and reproducibly coat the surface of a specific oil-absorbing crosslinked polymer with fine powder of an organic acid metal salt, and the resulting granular oil-absorbing agent is obtained. Has a high surface water repellency, so that it can selectively absorb only oil from an oil-water mixed system, has excellent oil retention performance of oil once absorbed, and has a sufficient oil passage to secure oil absorption speed. It will be extremely fast. Furthermore, the oil absorbent obtained by the present invention has a particle size of 1 compared to the conventional oil absorbents.
Even if the particle size is smaller than 00 μm, aggregation of particles is unlikely to occur during oil absorption, so that the high oil absorption capacity originally possessed by the oil-absorptive crosslinked polymer can be efficiently and quickly exhibited.

Therefore, the oil absorbing agent obtained by the present invention is used for the recovery of oil spilled at sea, the recovery of floating oil, the recovery of oil in waste water, the emulsion breaker, the oil leakage treatment agent, the edible waste oil treatment agent, the machine waste oil treatment agent, and the household waste oil treatment agent. Or industrial oil wipes, chemical wipes, oil leak sensors, oil sealants,
It can be applied to a very wide range of applications such as various oil retention agents,
It can also be used as a sustained-release base material for various fragrances, insecticides, fish collecting agents and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 33/00 LHZ 7921-4J C09K 3/32 8318-4H (72) Inventor Toshio Tamura Kawasaki, Kanagawa Prefecture 14-1, Chidori-cho, Kawasaki-ku, Yokohama, Japan

Claims (4)

[Claims] 1. A monomer (A) having one polymerizable unsaturated group in a molecule containing a monomer having a solubility parameter (SP value) of 9 or less as a main component in an amount of 96 to 99.999% by weight, and 0.001 to 4% by weight of a crosslinkable monomer (B) having at least two polymerizable unsaturated groups in the molecule (however, the total amount of the monomers (A) and (B) is 100% by weight). The organic acid metal salt aqueous solution and the inorganic polyvalent metal salt aqueous solution are mixed in the presence of the particulate matter of the oil-absorbing crosslinked polymer (I) obtained by polymerizing the monomer component consisting of An acid-absorbing cross-linked polymer (I) and an organic acid polyvalent metal salt (I) characterized by precipitating an acid polyvalent metal salt (II)
I) A method for producing a granular oil-absorbing agent containing: 2. The monomer (A) has at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms and is alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide. , Alkylaryl (meth) acrylamide, fatty acid vinyl ester,
The method for producing a granular oil absorbent according to claim 1, which comprises at least one unsaturated compound (a) selected from the group consisting of alkylstyrene and α-olefin as a main component. 3. The oil-absorbing crosslinked polymer (I) has an average particle size of 0.
The method for producing a granular oil absorbent according to claim 1, wherein the granular oil absorbent is in the range of 5 to 500 µm. 4. The ratio of the oil-absorbing crosslinked polymer (I) and the organic acid polyvalent metal salt (II) in the oil-absorbing agent is such that the oil-absorbing crosslinked polymer (I).
Is 30 to 99.9 parts by weight, and the organic acid polyvalent metal salt (II) is in the range of 0.1 to 70 parts by weight.