JPH06166725A - Oil absorbing agent - Google Patents

Abstract

PURPOSE:To obtain an oil absorbing agent useful for recovering an oil flowing out on the sea, having excellent oil absorbing rate, oil retaining performance and oil absorbing performance by subjecting a specific monomer component to aqueous suspension polymerization in the presence of a nonionic surfactant, etc. CONSTITUTION:A monomer component comprising a mixture of (A) one or more selected from (meth)acrylate of a 15-30C monohydric aliphatic alcohol, a 15-30C monofunctional fatty acid vinyl ester, a 15-30C aliphatic alkyl group- containing vinyl ether and a 15-30C aliphatic alkyl group-containing allyl ether and (B) a monomer containing one polymerizable unsaturated group in a molecule consisting essentially of a 2-6C alkyl group-containing methacrylate and (C) 0.001-10wt.% crosslinkable monomer containing two or more polymerizable unsaturated groups in the molecule based on the whole monomers is copolymerized in the presence of a nonionic surfactant and a slightly soluble inorganic salt by aqueous suspension polymerization to give the objective oil absorbing agent in a finely particulate state. The copolymerization ratio of the component A and the component B by weight is preferably 1/4-4/1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a swelling type oil absorbing agent having a high oil absorbing speed. More specifically, the present invention relates to a swelling-type oil absorbing agent that absorbs a wide variety of oils including edible oils and various organic solvents in a large amount and effectively and swells, and further significantly improves the oil absorption performance and oil absorption rate at room temperature.

[0002]

2. Description of the Related Art In recent years, the recovery of oil spilled into the sea and oil in wastewater has become a major environmental issue. Further, there has been a strong demand for a simple method for treating small-scale waste oil discarded at home or in factories, and leaked oil such as machine oil in factories. As one of the effective means for recovering these oil spills and oil in waste water or treating waste oil and leak oil, a method of incineration and other post-treatment after absorbing oil using an oil absorbent has been conventionally used. More used. As such an oil absorbing agent, for example,
Natural vegetable oil absorbing agents such as chaff, straw, pulp, peat, cotton; inorganic oil absorbing agents obtained by water repelling inorganic porous powder such as lime, silica, perlite; polypropylene fiber, polystyrene fiber, polyethylene fiber, etc. Synthetic fiber-based oil absorbents; foamed resin-based oil absorbents such as foamed polyurethane foam have been commercially available.

However, many of these conventional products cannot obtain a satisfactory oil absorption amount, and the oil absorption mechanism thereof absorbs and holds the oil in the voids or pores existing in the material. There was a flaw. That is, the conventional oil absorbing agent hardly changes in volume due to oil absorption, becomes extremely bulky, and is inconvenient for storage and handling. Poor retention after oil absorption, especially natural plant-based, synthetic fiber-based and foamed resin-based oil absorbents re-release the oil that was easily absorbed by slight external pressure, so post-processing is extremely complicated. is there. These oil absorbing agents are generally subjected to a water repellent treatment, but if they are used for a long time in an oil / water mixing system, water will penetrate into the voids and the oil absorbing ability will decrease. Although it is possible to absorb oil from an oil-water suspension state to some extent, there is a problem in that it cannot essentially absorb dissolved oil in water.

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,
Copolymer of t-butylstyrene / divinylbenzene (JP-A-45-27081), cross-linked polymer of t-butyl methacrylate and / or neopentyl methacrylate (JP-A-50-15882), menthyl methacrylate and / Or a cross-linked polymer of bornyl methacrylate (Japanese Patent Application Laid-Open No. 50-59486), polynorbornene rubber (for example, Nosolex A manufactured by CdF)
P), a cross-linked polymer of a (meth) acrylate of a monohydric aliphatic alcohol having 10 to 16 carbon atoms (JP-A-3-22158).
2) etc.

However, the t-butyl methacrylate and / or neopentyl methacrylate cross-linked polymer shows a certain amount of oil absorption with respect to an aromatic hydrocarbon low boiling point oil such as benzene, but it is an aliphatic hydrocarbon type. Satisfactory oil absorption was not obtained for oil. Further, although the t-butylstyrene / divinylbenzene copolymer, the cross-linked polymer of menthyl methacrylate, and the polynorbornene rubber show a certain amount of oil absorption for aromatic or aliphatic hydrocarbon oils having a low boiling point, It was inferior in oil absorption performance to polar oils such as fatty acid ester oils, fatty acids and higher alcohols, and highly viscous oils. Also, carbon number 1
Crosslinked polymers of (meth) acrylates of 0 to 16 monohydric aliphatic alcohols include low boiling point aromatic or aliphatic hydrocarbon oils, fatty acid ester oils, polar oils such as fatty acids and higher alcohols, and Although it shows a certain amount of oil absorption for high-viscosity oil, it is still unsatisfactory in terms of oil absorption speed for high-viscosity oil and high-viscosity solvent, and furthermore, it has the drawback of being extremely sticky and not easy to use. It was

Next, as a copolymer composition similar to the oil absorbing agent of the present invention, (meth) acrylate having 16 to 24 carbon atoms / (meth) acrylate having 2 to 12 carbon atoms / ethylenic group having polar group An unsaturated monomer copolymer crosslinked product (JP-A-2-110183) may be mentioned. However, the polymerization method of this polymer is a reaction in a solvent such as toluene, and the finished state is also a solvent solution. Moreover, its use is as a pressure sensitive adhesive and not as an oil absorbent. In addition, there is a drawback that the solvent must be evaporated at the time of use, and it cannot be used for the purpose of an oil absorbent.

Further, as a method similar to the method for producing an oil absorbent of the present invention, a method for producing a fine particle polymer in which a water-soluble inorganic salt is added during aqueous suspension polymerization in the presence of a surfactant (Japanese Patent Laid-Open No. HEI-2) -75603) can be mentioned. However, when a vinyl-based monomer having an alkyl group having 15 or more carbon atoms is polymerized by this method, there is a drawback that the resulting polymer is extremely sticky and difficult to handle.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above problems of conventional oil absorbents. That is, the object of the present invention is excellent in oil absorption capacity, oil absorption speed and oil retention performance after oil absorption for highly viscous oil or highly viscous solvent, without stickiness of the resin, and further, the oil absorption performance is significantly reduced even at low temperature. It is to provide a swellable oil-absorbing agent that does not.

[0009]

As a result of earnest research, the present inventors have found that a crosslinked polymer of a specific monomer component is suspended in an aqueous solution in the presence of a nonionic surfactant and a sparingly soluble inorganic salt. It has been found that dispersion polymerization is extremely effective in achieving the above object. Further, they have found that the oil absorbing rate of this oil absorbing agent is extremely higher than that of the conventional oil absorbing agent, and have completed the present invention. The object of the present invention is, in the presence of a nonionic surfactant and a sparingly soluble inorganic salt, a (meth) acrylate of a monovalent aliphatic alcohol having 15 to 30 carbon atoms, a vinyl ester of a monovalent fatty acid having 15 to 30 carbon atoms. , Carbon number 15
To vinyl ether having 30 to 30 aliphatic alkyl groups, at least one (A) selected from allyl ethers having 15 to 30 aliphatic alkyl groups, and 2 to 2 carbon atoms.
A monomer mixture having one polymerizable unsaturated group in the molecule, the main component of which is a methacrylate (B) having an alkyl group of 6, and a crosslinkability having at least two polymerizable unsaturated groups in the molecule. The present invention relates to a particulate oil-absorbing agent obtained by copolymerizing a monomer component containing the monomer (D) in an amount of 0.001 to 10% by weight of all monomers by aqueous suspension polymerization.

The number of carbon atoms of the aliphatic alkyl group of the monomer (A) used in the present invention is in the range of 15-30. If the number of carbon atoms is less than 15, the produced crosslinked polymer becomes too sticky and difficult to handle, or only a crosslinked polymer having insufficient oil absorption performance can be obtained. Further, if the carbon number is more than 30, the crystallinity of the side chains becomes remarkably high, so that only a crosslinked polymer having a remarkably low oil absorption performance at room temperature can be obtained.

The following are examples of the monomer (A) used in the present invention. Examples of the (meth) acrylate of an aliphatic monohydric alcohol having 15 to 30 carbon atoms include pentadecyl (meth) acrylate and hexadecyl.
(Meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate,
Hen Eicosyl (meth) acrylate, Docosyl (meth)
Acrylate, tricosyl (meth) acrylate, tetracosyl (meth) acrylate, pentacosyl (meth) acrylate, hexacosyl (meth) acrylate, heptacosyl (meth) acrylate, octacosyl (meth)
Acrylate, nonacosyl (meth) acrylate, triacontyl (meth) acrylate, etc., having 15 carbon atoms
Examples of the vinyl ester of monohydric fatty acid of 30 to 30 include vinyl hexadecanoate, vinyl heptadecanoate, vinyl octadecanoate, vinyl nonadecanoate, vinyl eicosate, vinyl heneicosate, vinyl docosanoate, vinyl tricosanoate, vinyl tetracosanoate, Vinyl pentacosanoate, vinyl hexacosanoate, vinyl heptacosanoate, vinyl octacosanoate, vinyl nonacosanoate, vinyl triacontanate, etc., having 15 to 3 carbon atoms.
Examples of vinyl ethers having 0 aliphatic alkyl groups include pentadecyl vinyl ether, hexadecyl vinyl ether, heptadecyl vinyl ether, octadecyl vinyl ether, nonadecyl vinyl ether,
Eicosyl vinyl ether, hene eicosyl vinyl ether, docosyl vinyl ether, tricosyl vinyl ether, tetracosyl vinyl ether, pentacosyl vinyl ether, hexacosyl vinyl ether, heptacosyl vinyl ether, octacosyl vinyl ether, nonacosyl vinyl ether, triacontyl vinyl ether Examples of the allyl ether having an aliphatic alkyl group having 15 to 30 carbon atoms include pentadecyl allyl ether, hexadecyl allyl ether, heptadecyl allyl ether, octadecyl allyl ether, nonadecyl allyl ether, eicosyl allyl. Ether, heneicosyl allyl ether, docosyl allyl ether, tricosyl allyl ether, tetracosyl allyl ether, pentacosh Allyl ether, hexa cosyl allyl ether, hepta cosyl allyl ether, octa cosyl allyl ether, Roh Naco sill allyl ether, a triacontyl allyl ether, may be used alone or two or more thereof.

The amount of these monomers (A) used is 16 to 80 relative to the total amount of the monomer having one polymerizable unsaturated group.
Weight% is preferable, and a ratio of 25 to 50% by weight is more preferable. When the amount of the monomer (A) used is less than 16% by weight based on the total amount of the monomer having one polymerizable unsaturated group, only a crosslinked polymer having insufficient oil absorption performance can be obtained. . Further, when the amount of the monomer (A) used is more than 80% by weight based on the total amount of the monomer having one polymerizable unsaturated group, the crystallinity of the side chains becomes extremely high, so that the room temperature is increased. Only a cross-linked polymer having extremely low oil absorption performance can be obtained.

The monomer (B) used in the present invention is a lipophilic monomer used to inhibit the crystallinity of the side chain of the monomer (A) and has a carbon number of 2 to 6. Range of alkyl methacrylate. When the carbon number is less than 2, only a crosslinked polymer having insufficient oil absorption performance can be obtained. When the carbon number is more than 6, the effect of inhibiting the crystallinity of the side chain of the monomer (A) is remarkably impaired, and only a crosslinked polymer having a remarkably low oil absorption performance at room temperature can be obtained.

The monomer (B) used in the present invention is as follows. As the methacrylate having an alkyl group having 2 to 6 carbon atoms, for example, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate,
Isobutyl methacrylate, tert-butyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, 1-methylbutyl methacrylate, 1,2-dimethylpropyl methacrylate, 2-ethylpropyl methacrylate, 1-ethylpropyl methacrylate, 2,2- Dimethylpropyl methacrylate, 1,1-dimethylpropyl methacrylate, cyclohexyl methacrylate, 1-methylpentyl methacrylate, 2-methylpentyl methacrylate, 3-methylpentyl methacrylate, 4-methylpentyl methacrylate, 1-ethylbutyl methacrylate, 2-ethylbutyl methacrylate , 3-ethylbutyl methacrylate, etc., and one or more of these can be used.

The amount of these monomers (B) used is 16 to 80 relative to the total amount of the monomer having one polymerizable unsaturated group.
Weight% is preferable, and a ratio of 35 to 75% by weight is more preferable. When the amount of the monomer (B) used is less than 16% by weight based on the total amount of the monomer having one polymerizable unsaturated group, the crystallinity of the side chain of the monomer (A) may be reduced. Only the cross-linked polymer having a significantly low oil absorption performance at room temperature can be obtained because the inhibiting effect is significantly impaired. Further, when the amount of the monomer (B) used is more than 80% by weight based on the total amount of the monomer having one polymerizable unsaturated group, only a crosslinked polymer having insufficient oil absorption performance is obtained. Disappear. In addition, the total amount of the monomers (A) and (B) must be 80% by weight or more of the total amount of the monomers. The total amount of monomers (A) and (B) is
If the total amount of the monomers is less than 80% by weight, only a crosslinked polymer having insufficient oil absorption performance can be obtained.

Further, in the present invention, a monomer (C) having one polymerizable unsaturated group other than (A) and (B) may be copolymerized, but the amount thereof used is the whole unit amount. 20 for body
Must be less than wt%. When the amount used is 20% by weight or more, only a crosslinked polymer having insufficient oil absorption performance can be obtained. Examples of such a monomer include (meth) acrylic acid, acrylonitrile, maleic anhydride,
Fumaric acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene (meth) acrylate, methyl (meth) acrylate, vinyl ethyl ether, vinyl propyl ether,
Vinyl acetate etc. can be mentioned.

Examples of the crosslinkable monomer (D) used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 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 ( Alkylene glycol di (meth) acrylates such as (meth) acrylates;
N, N'-alkylenebisacrylamide such as N, N'-methylenebisacrylamide, N, N'-propylenebisacrylamide; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Polyol tri (meth) acrylate such as acrylate; Divinyl compound such as divinylbenzene and divinyl ether; Polyol tetra (meth) acrylate such as tetramethylolmethane tetra (meth) acrylate; N, N'-diacetyl-N, N'-divinyl -1,4-bisaminomethylcyclohexane, N, N'-1,6-hexylenebis (N
-Vinylacetamide), N, N'-1,4-butylenebis (N-vinylacetamide), N, N'-1,10
-N, such as decylene bis (N-vinylacetamide),
N'-alkylenebis (N-vinylcarboxylic acid amide); N, N 'such as p-xylylenebis (N-vinylacetamide), m-xylylenebis (N-vinylacetamide), m-xylylenebis (N-vinylformylamide) -Xylylene bis (N-vinylcarboxylic acid amide); polyallyl compounds such as trimethylolpropane diallyl ether, pentaerythritol triallyl ether, triallyl phosphate, tetraallyloxyethane, sucrose allyl ether, and the like. One type or two or more types of crosslinkable monomers can be used.

The total amount of monomers having one polymerizable unsaturated group containing the monomers (A) and (B) as the main components used in the production of the oil absorbent of the present invention is Against 90-99.
It is in the range of 999% by weight, preferably 95-99.9.
It is 9% by weight. That is, the amount of the crosslinkable polymer (D) is in the range of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on all the monomers. Monomer
When the total amount of the monomers having (A) and (B) as a main component and having one polymerizable unsaturated group is less than 90% by weight or the amount of the crosslinkable monomer (D) exceeds 10% by weight. However, the crosslinking density of the obtained crosslinked polymer is too high to absorb a large amount of oil, which is not preferable. In addition, the total amount of monomers having one polymerizable unsaturated group containing the monomers (A) and (B) as main components exceeds 99.999% by weight, and the amount of the crosslinkable monomer (D) is 0. If it is less than 0.001% by weight, the solubility of the obtained crosslinked polymer in oil is increased, and the crosslinked polymer is eluted after oil absorption and the original function of the oil absorbent cannot be exhibited, which is not preferable.

The method for producing the oil absorbing agent of the present invention is aqueous suspension polymerization. Aqueous suspension polymerization is one in which suspension polymerization is carried out in an aqueous medium, but as this aqueous medium, water is indispensable, and a water-soluble organic solvent is dissolved within a range that does not impair the stability of the suspension system. Water may be used. Further, as the dispersant, a nonionic surfactant having a high HLB and a sparingly soluble phosphate are used. As the nonionic surfactant having a high HLB, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether and the like are used.
The amount of the surfactant used is 0.2 to all monomers.
It is preferable to contain 10% by weight. If the amount of the surfactant used is less than 0.2% by weight based on all the monomers, the dispersion state of the suspension dispersion liquid may be broken during the polymerization. Also,
The amount of this surfactant used is 10% by weight based on all monomers.
If it is contained in a larger amount, foaming during polymerization becomes severe, which is not preferable.

The poorly soluble inorganic salt used in the present invention not only plays the role of a dispersant, but also has the role of increasing the oil absorption rate of the produced crosslinkable polymer (oil absorbing agent). The amount used is 0.2 to all monomers.
It is preferably 20% by weight. If the amount of the hardly soluble inorganic salt used is less than 0.2% by weight based on the total amount of the monomers, the oil absorption rate may be reduced. If the amount of the poorly soluble inorganic salt exceeds 20% by weight, the amount of the poorly soluble inorganic salt with respect to the oil absorbing agent becomes too large, which is not practical.
The sparingly soluble inorganic salt used in producing the oil absorbent of the present invention includes, for example, calcium carbonate, tribasic calcium phosphate, tribasic magnesium phosphate, dibasic magnesium phosphate, dibasic calcium phosphate, and barium dibasic phosphate. . Of these, dibasic magnesium phosphate and tribasic magnesium phosphate are particularly preferable, and the oil absorption rate of the produced crosslinkable polymer (oil absorbing agent) can be remarkably increased.

At the same time, a water-soluble polymer protective colloid can be used together as a dispersant. Examples of the water-soluble polymer protective colloid include polyvinyl alcohol, water-soluble cellulose derivatives such as alkyl cellulose, hydroxyalkyl cellulose and carboxyalkyl cellulose, gelatin, sodium polyacrylate and the like. The polymerization initiator used in the present invention is not particularly limited, but examples thereof include benzoyl peroxide, dichlorobenzoyl peroxide, cumyl peroxide, and ter peroxide.
t-Butyl, 2,5-di (peroxybenzoate) hexyne-3, 1,3-bis (tertiary butyl peroxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5 -Di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and organic peroxides such as tert-butyl perbenzoate, methyl ethyl ketone peroxide, and methylcyclohexanone peroxide , Azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethylazodiisobutyrate, and the like, and one or more of these can be used.
The amount used is determined depending on the type of the monomer used and the like, but is preferably about 0.1 to 4.0% by weight based on all the monomers.

The polymerization method for obtaining the oil absorbent of the present invention is as follows:
Although it is an aqueous suspension dispersion polymerization as described above, the temperature during the polymerization is preferably in the range of 40 to 150 ° C. After completion of the polymerization, the obtained aqueous suspension of fine particle resin is filtered, washed with water for 2 to 3 times and then dried to obtain the desired oil absorbing agent. The oil absorbing agent of the present invention is not limited to aromatic hydrocarbons and aliphatic hydrocarbon oils, but also a large amount of oil for a wide variety of oils such as aliphatic ester oils, higher fatty acids, higher alcohols and ethers. Oil is absorbed more rapidly than conventional swelling oil absorbents, and the effect of oil absorption performance due to temperature changes is smaller than that of conventional oil absorbents, and high oil absorption performance can be maintained even at low temperatures.

Therefore, the oil absorbent of the present invention is effective under low temperature conditions for recovering oil spilled over the sea, floating oil, and oil in wastewater, and also an emulsion breaker, an oil leakage treatment agent, and a microwave oven heating. It can be applied to a very wide range of applications such as covers, edible waste oil treatment agents, machine waste oil treatment agents, household or industrial oil wiping agents, scientific wipes, oil leak sensors, oil seal agents, and various oil retaining agents. Further, since the oil absorbent of the present invention absorbs and retains a wide range of oils, it can be used as a sustained-release base material for various fragrances, insect repellents, insecticides, bactericides, fish collecting agents, etc. It can greatly contribute to the development.

[0024]

EXAMPLES Next, the oil absorbent of the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 A 1 liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser was charged with polyoxyethylene nonylphenyl ether 4.5 as a nonionic surfactant.
Part, magnesium diphosphate 7.5 as a sparingly soluble inorganic salt
And 1.5 parts of hydroxyethyl cellulose as a water-soluble polymer protective colloid were dissolved in 510 parts of water and charged. The flask was purged with nitrogen while stirring and heated to 70 ° C. under a nitrogen stream. Then, 60 parts of octadecyl acrylate as the monomer (A) and te as the monomer (B).
90 parts of rt-butyl methacrylate, crosslinkable monomer (D)
As a solution, a solution of 0.1 part of divinylbenzene and 0.8 part of benzoyl peroxide as a polymerization initiator was added at once to the flask, and the mixture was vigorously stirred at 700 rpm. Three
After the lapse of time, the temperature inside the flask was raised to 80 ° C.
The polymerization reaction was carried out while maintaining the time, and then the temperature inside the flask was further raised to 95 ° C. and maintained for 3 hours to complete the polymerization. After the completion of the polymerization, the granular crosslinked polymer was filtered off, washed with water several times, and dried to obtain a white powder having a particle size of 100 to 1000 μm [the oil absorbent (1) in the example].

Example 2 Polyoxyethylene nonylphenyl ether 4.5 as a nonionic surfactant was placed in a 1 liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser.
Parts, magnesium triphosphate 7.5 as a sparingly soluble inorganic salt
And 2.0 parts of hydroxyethyl cellulose as a water-soluble polymer protective colloid were dissolved in 510 parts of water and charged. The flask was purged with nitrogen while stirring and heated to 70 ° C. under a nitrogen stream. Then, 50 parts of octadecyl methacrylate as a monomer (A), 100 parts of isobutyl methacrylate as a monomer (B), and a crosslinkable monomer (D)
As trimethylolpropane trimethacrylate 0.
09 parts and lauroyl peroxide 0.6 as a polymerization initiator
Solution consisting of 3 parts at once at 700 rpm
The mixture was vigorously stirred under the conditions of. After 3 hours, the temperature inside the flask was raised to 80 ° C., the temperature was maintained at the same temperature for 2 hours to carry out the polymerization reaction, and then the temperature inside the flask was further raised to 95 ° C. and maintained for 3 hours to complete the polymerization. . After completion of the polymerization, the granular crosslinked polymer was filtered off, washed with water several times, and dried to obtain a particle size of 1
White powder of 100 to 1000 μm [Example oil absorbent (2)]
Got

Example 3 A 1 liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser was charged with 4.5 parts of polyoxyethylene nonyl ether as a nonionic surfactant, and as a sparingly soluble inorganic salt. 7.5 parts of magnesium diphosphate and 2.0 parts of carboxymethyl cellulose as a water-soluble polymer protective colloid were dissolved in 510 parts of water and charged.
Heated to ° C. Thereafter, 55 parts of vinyl octacosanoate as the monomer (A), 100 parts of neopentyl methacrylate as the monomer (B), 0.1 part of ethylene glycol dimethacrylate as the crosslinkable monomer (D) and a polymerization initiator A solution consisting of 0.6 part of azobisisobutyronitrile was added to the flask all at once and vigorously stirred at 700 rpm. After 3 hours, the temperature inside the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out a polymerization reaction. Then, the temperature inside the flask was further raised to 100 ° C. and maintained for 3 hours to complete the polymerization. . After completion of the polymerization, the granular crosslinked polymer was filtered off, washed with water several times, and then dried to obtain a particle size of 100 to 10
A white powder of 00 μm [the oil absorbent of the example (3)] was obtained.

Example 4 A 1 liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser was charged with 4.5 parts of polyoxyethylene nonyl ether as a nonionic surfactant, and as a sparingly soluble inorganic salt. 7.5 parts of magnesium triphosphate and 2.0 parts of sodium polyacrylate as a water-soluble polymer protective colloid were used, and these were dissolved in 510 parts of water and charged. Heated to 40 ° C. Then, 75 parts of octadecyl vinyl ether as the monomer (A), 75 parts of cyclohexyl methacrylate as the monomer (B), and N, N'- as the crosslinkable monomer (D).
A solution consisting of 0.5 parts of diacetyl-N, N'-divinyl-1,4-bisaminomethylcyclohexane and 1.2 parts of azobisdivaleronitrile as a polymerization initiator was added at once to the flask, and the conditions were 700 rpm. Stir vigorously. After 3 hours, the temperature inside the flask was raised to 70 ° C. and maintained at the same temperature for 2 hours to carry out a polymerization reaction, and then the temperature inside the flask was further raised to 90 ° C. and maintained for 3 hours to complete the polymerization. . After the completion of the polymerization, the granular crosslinked polymer was separated by filtration, washed with water several times, and dried to obtain a white powder having a particle size of 100 to 1000 μm [Example oil absorbent (4)].

Example 5 Polyoxyethylene nonylphenyl ether 4.5 as a nonionic surfactant was placed in a 1 liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser.
And 7.5 parts of dibasic magnesium phosphate as a sparingly soluble inorganic salt were dissolved in 510 parts of water and charged. The flask was purged with nitrogen while stirring and heated to 70 ° C. under a nitrogen stream. Thereafter, 75 parts of hexacosyl methacrylate as the monomer (A), 75 parts of isopropyl methacrylate as the monomer (B), 0.5 part of trimethylolpropane diallyl ether as the crosslinkable monomer (D), and a polymerization initiator. As a solution, 1.2 parts of di-tert-butyl peroxide was added at once to the flask, and the mixture was vigorously stirred at 700 rpm. After 3 hours, the temperature inside the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out a polymerization reaction. Then, the temperature inside the flask was further raised to 100 ° C. and maintained for 3 hours to complete the polymerization. . After completion of the polymerization, the granular crosslinked polymer was filtered off, washed with water several times, and then dried to obtain a particle size of 100 to 10
A white powder of 00 μm [the oil absorbing agent of the example (5)] was obtained.

Example 6 A 1-liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser was charged with 4.5 parts of polyoxyethylene nonyl ether as a nonionic surfactant, and as a sparingly soluble inorganic salt. 7.5 parts of magnesium triphosphate and 2.0 parts of sodium polyacrylate as a water-soluble polymer protective colloid were used, and these were dissolved in 510 parts of water and charged. Heated to 40 ° C. Then, 54 parts of octadecyl vinyl ether as the monomer (A), 75 parts of cyclohexyl methacrylate as the monomer (B), 21 parts of acrylonitrile as the monomer (C), and N, N 'as the crosslinkable monomer (D). A solution consisting of 7.5 parts of diacetyl-N, N'-divinyl-1,4-bisaminomethylcyclohexane and 1.2 parts of azobisdivaleronitrile as a polymerization initiator was added at once to the flask, and the conditions of 700 rpm were applied. Stir vigorously at. Three
After the lapse of time, the temperature inside the flask was raised to 70 ° C.
The polymerization reaction was carried out while maintaining the time, and then the temperature inside the flask was further raised to 90 ° C. and maintained for 3 hours to complete the polymerization. After the completion of the polymerization, the granular crosslinked polymer was filtered off, washed with water several times, and dried to obtain a white powder having a particle size of 100 to 1000 μm [Example oil absorbent (6)].

Example 7 A 1-liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser was charged with polyoxyethylene nonylphenyl ether 4.5 as a nonionic surfactant.
Parts, 7.5 parts of dibasic magnesium phosphate as a sparingly soluble inorganic salt were dissolved in 510 parts of water and charged. The flask was purged with nitrogen while stirring and heated to 70 ° C. under a nitrogen stream. Then, 48 parts of hexacosyl methacrylate as the monomer (A), 75 parts of isopropyl methacrylate as the monomer (B), 27 parts of hydroxypropyl methacrylate as the monomer (C), and a crosslinkable monomer (D) As a solution, 0.5 parts of trimethylolpropane diallyl ether and 1.2 parts of di-tert-butyl peroxide as a polymerization initiator were added at once to the flask, and vigorously stirred at 700 rpm. After 3 hours, the temperature inside the flask was raised to 80 ° C. and maintained at the same temperature for 2 hours to carry out a polymerization reaction. Then, the temperature inside the flask was further raised to 100 ° C. and maintained for 3 hours to complete the polymerization. . After completion of the polymerization, the granular crosslinked polymer was filtered off, washed with water several times, and then dried to obtain a particle size of 100 to 10
A white powder having a diameter of 00 μm [Example oil absorbing agent (7)] was obtained.

Comparative Example 1 4.0 parts of completely saponified polyvinyl alcohol and 0.16 part of partially saponified polyvinyl alcohol were placed in 600 ml of water in a 1 liter flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a reflux condenser. Part of the flask was charged, and the inside of the flask was replaced with nitrogen while stirring, and the flask was heated to 40 ° C. under a nitrogen stream.
Then, a solution containing 150 parts of dodecyl acrylate, 0.3 part of ethylene glycol diacrylate, and 0.5 part of azobisdimethylvaleronitrile as a polymerization initiator was added to the flask all at once, and the mixture was vigorously stirred at 700 rpm. After 3 hours, the temperature inside the flask was raised to 70 ° C. and maintained at the same temperature for 2 hours to carry out the polymerization reaction, and then the temperature inside the flask was further raised to 80 ° C. and maintained for 3 hours to complete the polymerization. . After the completion of the polymerization, the granular crosslinked polymer was separated by filtration, washed with water several times, and dried to give a comparative oil absorbent (1).
Got

Comparative Example 2 Instead of 150 parts of dodecyl acrylate in Comparative Example 1, 67.3 parts of dodecyl acrylate and 82.7 of styrene were used.
Comparative Example oil absorbent (2) was obtained by the same method as Comparative Example 1 except that 0.5 part of ethylene glycol diacrylate was used.

Comparative Example 3 150 parts of 2-ethylhexyl acrylate was used in place of 150 parts of dodecyl acrylate in Comparative Example 1,
Comparative Example 1 except that 0.35 part of divinylbenzene was used instead of 0.5 part of ethylene glycol diacrylate.
A comparative oil absorbent (3) was obtained in the same manner as in (1).

Comparative Example 4 The oil absorbent of Comparative Example 1 was prepared in the same manner as in Comparative Example 1 except that 150 parts of octadecyl acrylate was used in place of 150 parts of dodecyl acrylate and 0.35 part of ethylene glycol diacrylate was used. (4) was obtained.

Comparative Example 5 In Comparative Example 1, 150 parts of t-butylstyrene was used instead of 150 parts of dodecyl acrylate, and N, N'-diacetyl-N, N'-divinyl was used instead of 0.5 part of ethylene glycol diacrylate. Comparative Example 1 except that 0.1 part of -1,4-bisaminomethylcyclohexane was used.
A comparative oil absorbent (5) was obtained in the same manner as in (1).

Example 8 <Measurement of oil absorption ratio> Example oil absorbents (1) to (7) obtained in Examples 1 to 7 and comparative oil absorbents (1) to (5) obtained in Comparative Examples 1 to 5 For each of (5), the oil absorption capacity was measured by the following method. (Measurement method) 1 g of the oil absorbing agent sample was immersed in various oils and solvents shown in Table 1 under the condition of 25 ° C., and after 24 hours, it was collected by filtration on a wire mesh. Then, the sample was left on a wire net for 20 minutes to allow the oil or solvent not retained by the sample to flow down sufficiently, and then the weight (αg) of the swollen sample was measured, and the oil absorption capacity was calculated according to the following formula. Oil absorption capacity (g / g) = (weight of swollen sample-weight of sample before immersion)
/ Sample weight before immersion = (α-1) / 1 The evaluation results are shown in Table 1.

[0038]

[Table 1]

As is clear from Table 1, the swellable oil absorbing agents of the present invention and Comparative Example 1 can absorb a large amount of oil with respect to a wide variety of oils.

Example 9 <Measurement of saturated oil absorption time> Example oil absorbents (1) to (7) obtained in Examples 1 to 7 and comparative oil absorbents (Comparative Example 1 and Comparative Example 2) For each of 1) to (2),
The time until the oil absorption ratio reached saturation (time until saturation swelling) was measured by the following method. (Measurement method) 1 g of the oil absorbing agent sample was immersed in carbon tetrachloride, toluene, kerosene and rapeseed oil under the condition of 25 ° C, and the oil absorption ratio of each oil and solvent was measured at regular intervals. The method for measuring the oil absorption ratio at regular intervals is the same as that used in the above <Measurement of oil absorption ratio> except for the immersion time. The evaluation results are shown in Table 2.

[0041]

[Table 2]

As shown in Table 1, it was the oil absorbents of the present invention and Comparative Example 1 that were able to absorb a large amount of oil against a wide variety of oils. Comparing the saturated oil absorption times (oil absorption speeds), the oil absorbent of the present invention is obviously shorter in saturated oil absorption time (larger oil absorption speed) than the oil absorbents of Comparative Examples 1 and 2. That is, for a wide range of oils, it is possible to absorb a large amount of oil in a short time.
Only the oil absorbent of the present invention.

Example 10 <Stickiness Test> Oil absorbing agents (1) to (7) obtained in Examples 1 to 7 and oil absorbing agents (1) to Comparative Examples obtained in Comparative Example 1 and Comparative Example 2 For each of (2), the presence or absence of stickiness was evaluated by the following method. (Evaluation method) 1 g of the oil absorbing agent sample is placed on a silicone release paper under the condition of 25 ° C., and a high quality paper is placed on the silicone release paper, 1 kg /
After applying a pressure of m ² for 10 seconds, it was evaluated by examining whether or not the oil absorbent sample adhered to the woodfree paper. The evaluation results are shown in Table 3.

[0044]

[Table 3]

Example 11 <Measurement of Oil Leakage Amount by Change in Pressure> The oil absorbents (1) to (7) of Examples obtained in Examples 1 to 7 and the commercially available oil absorbent of PP fiber were measured by the following method. The amount of oil leakage due to pressure change was measured. (Measurement method) After absorbing the toluene to the oil absorbing agent sample to make it saturated, 50 g of the saturated sample was filled in a cylinder (φ = 20 mm) equipped with a wire mesh at one end and pressurized by a piston, and leakage at that time It was determined by measuring the amount of oil and removing it from the saturated oil absorption. The evaluation results are shown in FIG. In addition, the oil absorbing agents (2) to (7) of the example also had the same results as the oil absorbing agent (1) of the example.

Example 12 <Floating oil recovery test> 30 liters of water (water surface area: 1000 cm ² ) was placed in a 36-liter water tank, and 15 g of B heavy oil was added to the water surface. On this water surface, Examples 1-5
5 g of each of the oil absorbing agents (1) to (7) obtained in Example
Sandwiched between polypropylene (PP) non-woven fabric of 10 cm x 10 cm and PP of 10 cm x 10 cm
The non-woven fabrics were floated for 4 hours and then pulled up, and the floating oil recovery ability was evaluated according to the following criteria from the appearance of the B heavy oil remaining on the water surface. The results are shown in Table 4.

[0047]

[Table 4]

[0048]

INDUSTRIAL APPLICABILITY According to the present invention, not only aromatic hydrocarbons and aliphatic hydrocarbon oils, but also a wide variety of oils such as aliphatic ester oils, higher fatty acids, higher alcohols and ethers are used at room temperature. It is possible to provide a swellable oil-absorbing agent which is capable of absorbing a large amount of oil in a short period of time and which is difficult to release the oil once absorbed. Further, the oil absorbent of the present invention is effective even under low temperature conditions such as oil spill recovery at sea, floating oil recovery, oil recovery in wastewater, and the like, emulsion breaker, oil leakage treatment agent, microwave heating cover, edible Waste oil treatment agent, machine waste oil treatment agent,
To absorb and retain a very wide range of oils such as household or industrial oil wipes, scientific wipes, oil leak sensors, oil sealants, and various oil retention agents, various fragrances, insect repellents, insecticides, bactericides, fish collectors. It can also be used as a sustained-release base such as an agent.

[Brief description of drawings]

FIG. 1 is a diagram showing an amount of re-leakage of an oil absorbing material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C09K 3/32 ZAB 8318-4H

Claims (3)

[Claims] 1. A (meth) acrylate of a monohydric aliphatic alcohol having 15 to 30 carbon atoms, a vinyl ester of a monovalent fatty acid having 15 to 30 carbon atoms, in the presence of a nonionic surfactant and a sparingly soluble inorganic salt. At least one (A) selected from vinyl ether having an aliphatic alkyl group having 15 to 30 carbon atoms, allyl ether having an aliphatic alkyl group having 15 to 30 carbon atoms, and methacrylate having an alkyl group having 2 to 6 carbon atoms. A monomer mixture containing (B) as a main component and having one polymerizable unsaturated group in the molecule, and a crosslinkable monomer (D) having at least two polymerizable unsaturated groups in the molecule
A fine oil absorbing agent obtained by copolymerizing a monomer component containing 0.001 to 10% by weight of all monomers by aqueous suspension polymerization. 2. A (meth) acrylate of a C15 to C30 monohydric aliphatic alcohol, a vinyl ester of a C15 to C30 monovalent fatty acid in the presence of a nonionic surfactant and a sparingly soluble inorganic salt, At least one (A) selected from vinyl ether having an aliphatic alkyl group having 15 to 30 carbon atoms, allyl ether having an aliphatic alkyl group having 15 to 30 carbon atoms, and methacrylate having an alkyl group having 2 to 6 carbon atoms. Including a total of 80% by weight or more of (B),
A monomer mixture containing less than 20% by weight of a monomer (C) having one polymerizable unsaturated group in the molecule other than (A) and (B), and at least two polymerizable compounds in the molecule. The crosslinkable monomer (D) having an unsaturated group is 0.001-1 of all monomers.
An oil absorbing agent in the form of fine particles obtained by copolymerizing a monomer component containing 0% by weight by an aqueous suspension polymerization method. 3. A (meth) acrylate of a monohydric aliphatic alcohol having 15 to 30 carbon atoms, a vinyl ester of a monohydric fatty acid having 15 to 30 carbon atoms, a vinyl ether having an aliphatic alkyl group having 15 to 30 carbon atoms, and carbon. The copolymerization ratio of at least one kind (A) selected from an allyl ether having an aliphatic alkyl group having a number of 15 to 30 and the methacrylate (B) having an alkyl group having a carbon number of 2 to 6 is 1: 4 to 4: 1.
(Weight ratio), The oil absorbent according to claim 1 or 2.