CN114920874A - Organic bentonite modified oil-absorbing resin and preparation method thereof - Google Patents
Organic bentonite modified oil-absorbing resin and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y02A20/204—Keeping clear the surface of open water from oil spills
Abstract
The invention belongs to the technical field of oil-absorbing resin, and discloses organic bentonite modified oil-absorbing resin and a preparation method thereof. The organic bentonite modified oil-absorbing resin comprises the following raw materials in parts by weight: 100 parts by weight of monomer; 0.6-2 parts by weight of a crosslinking agent; 0.2-2 parts by weight of an initiator; 0.3-1.3 parts by weight of a dispersant; 0.05-0.5 part by weight of an additive; the additive is organic bentonite, and is obtained by modifying the bentonite by adopting a cationic surface modifier; the monomer is one or two of cetyl methacrylate, methyl methacrylate and styrene. According to the invention, the oil-absorbing resin is modified by the organic bentonite, so that the modified oil-absorbing resin is spherical and has a regular size, and the oil-absorbing times of the oil-absorbing resin on organic matters such as carbon tetrachloride are obviously improved.
Description
Technical Field
The invention relates to the technical field of oil-absorbing resin, in particular to organic bentonite modified oil-absorbing resin and a preparation method thereof.
Background
The oil-absorbing resin material is a novel oil-removing material with better application prospect. The industrial production method of the oil-absorbing resin material mainly comprises emulsion polymerization, suspension polymerization, dispersion polymerization and the like. Currently, a variety of oil-absorbing resins have been prepared; however, the traditional oil-absorbing resin has the problems of single oil absorption, low oil absorption rate, incapability of being effectively recycled after oil absorption and the like in the practical application process.
Therefore, the biggest challenge in the current industrial production is how to prepare a high oil absorption resin, which not only can absorb various oils, but also is convenient for the recovery and reuse of the oil absorption resin.
The montmorillonite layers in the bentonite are mainly combined by intermolecular force, the acting force is weak, and the bentonite has weak negative charges, so the bentonite has good expansibility, dispersibility and cation exchangeability. At present, no report related to the bentonite modified oil-absorbing resin is found.
Disclosure of Invention
The inventor of the present application finds out through continuous research that: the bentonite is treated by adopting an organic modification method, exchangeable cations among montmorillonite layers are replaced by utilizing organic cations such as quaternary ammonium ions, so that the physicochemical property of bentonite minerals can be effectively changed, and the oleoresin is modified based on the modified bentonite, so that the surface energy of the resin can be reduced, the surface polarity of the resin can be changed, and the lipophilicity of the surface of the resin can be increased; and the addition of the organic bentonite not only influences the size and appearance of the resin, but also obviously improves the oil absorption multiple of the oil absorption resin on organic matters such as carbon tetrachloride and the like. Based on the above, the invention aims to provide an organic bentonite modified oil-absorbing resin and a preparation method thereof, so as to solve the problems in the prior art.
The above object can be achieved by the following technical solution:
according to one aspect of the invention, the organic bentonite modified oil absorption resin provided by the invention comprises the following raw materials in parts by weight: 100 parts by weight of monomers; 0.6-2 parts by weight of a crosslinking agent; 0.2-2 parts by weight of an initiator; 0.3 to 1.3 parts by weight of a dispersant; 0.05-0.5 part by weight of an additive; wherein the additive is organic bentonite, and is obtained by modifying the bentonite by adopting a cationic surface modifier; the monomer is one or two of cetyl methacrylate, methyl methacrylate and styrene.
Optionally, the cross-linking agent is one or two of divinylbenzene, ethylene glycol dimethacrylate and ethylene glycol diacrylate.
Optionally, the initiator is one or two of benzoyl peroxide, lauroyl peroxide and tert-butyl 2-ethyl acetate peroxide.
Optionally, the dispersant is polyvinyl alcohol.
Optionally, the cationic surface modifier is cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride, and the addition amount of the cationic surface modifier is 1% -10% of the mass of the sodium bentonite.
According to another aspect of the present invention, the present invention provides a method for preparing an organobentonite-modified oil-absorbent resin, comprising:
step S10, modifying the sodium bentonite by cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride to prepare organic bentonite;
step S20, dissolving a dispersant to obtain a dispersant solution, adding a cross-linking agent, an initiator, a monomer and an additive into the dispersant solution, and carrying out suspension polymerization reaction for 4-8 h at 60-90 ℃; wherein the additive is the organic bentonite;
step S30, carrying out suction filtration on the solution while the solution is hot, washing with hot water, and drying at 80-110 ℃ for 22-26 h to obtain granular particles;
and step S40, washing the granular particles by adopting methylbenzene or acetone, and drying to obtain the modified oil absorption resin.
Optionally, in step S30, the temperature of the hot water is 60 ℃ to 80 ℃, and the amount of the hot water is 3 to 5 times of the solution amount.
Optionally, in step S40, the drying temperature is 80 ℃ to 110 ℃, and the drying time is 22h to 26 h. Alternatively, washing is performed with an equal amount of toluene or acetone.
Optionally, step S10, includes: preparing bentonite suspension from sodium bentonite and distilled water, and controlling the pH value to be 7-9; adding cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride into the bentonite suspension, heating to 60-80 ℃, rapidly stirring, reacting at constant temperature for 2.5-4 h, and drying at 80-110 ℃ for 22-26 h to obtain the organic bentonite.
Optionally, the concentration of sodium bentonite in the bentonite suspension is 4% to 10%.
Optionally, the preparation of the dispersant solution comprises: under the condition of constant-temperature water bath, the temperature is 62-68 ℃, the dispersant is added into deionized water, and the mixture is stirred for 2-3 hours to be completely dissolved, so that dispersant solution is obtained.
Optionally, the oil absorption of the organobentonite modified oil absorbent resin is higher than 11 g/g.
Has the advantages that: according to the invention, the oil-absorbing resin is modified based on the organic bentonite, and the addition amount is improved and optimized, so that the surface energy of the resin is reduced, and the surface polarity of the resin is changed, thereby increasing the lipophilicity of the surface of the resin; the addition of the organic bentonite not only influences the size and appearance of the resin, the size of the regular resin spheres changes the resin into a circular shape, but also obviously improves the oil absorption times of the oil-absorbing resin on organic matters such as carbon tetrachloride and the like. The reaction process is simple and quick; the organic bentonite modified oil-absorbing resin has the advantages of spherical shape, regular size, good oil-absorbing effect, high oil-absorbing rate of the finished product, capability of absorbing various oil products, reusability and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The raw materials of the organic bentonite modified oil-absorbing resin provided by the invention contain additives, the modified organic bentonite is used as an additive for increasing the lipophilicity of the surface of the oil-absorbing resin, and the addition amount is controlled to be the monomer dosage, so that the size and the appearance of the resin are optimized, and the oil absorption rate of the oil-absorbing resin is improved.
The invention provides a preparation method of an organic bentonite modified oil-absorbing resin, which is prepared by adding a cross-linking agent, an initiator, a monomer and an additive into a dispersing agent solution and carrying out suspension polymerization reaction by taking the modified organic bentonite as the additive for increasing the surface lipophilicity of the oil-absorbing resin. The prepared organic bentonite modified oil-absorbing resin can improve the oil absorption rate of the oil-absorbing resin.
The organic bentonite modified oil absorption resin provided in an embodiment of the invention comprises the following raw materials in parts by weight: 100 parts by weight of monomers; 0.6-2 parts by weight of a crosslinking agent; 0.2-2 parts by weight of an initiator; 0.3-1.3 parts by weight of a dispersant; 0.05-0.5 part by weight of an additive; the additive is organic bentonite, and is obtained by modifying sodium bentonite by adopting cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride; the monomer adopts one or two of cetyl methacrylate, methyl methacrylate and styrene. By adopting the additive and optimizing the mixture ratio of the additive and other raw materials, the oil absorption times of the oil-absorbing resin on organic matters such as carbon tetrachloride are obviously improved; and the organic bentonite modified oil-absorbing resin is spherical, has regular size and good oil-absorbing effect, and the finished product has high oil-absorbing rate, can absorb various oil products and can be repeatedly used.
The inventors of the present application have found that when no organobentonite is added to the system, the resulting resin hardly forms uniform and stable particles only by the action of the dispersant; if the dispersing agent and the organic bentonite exist in the system at the same time, the high polymer chain segment can generate uniform granular resin under the combined action of the dispersing agent and the organic bentonite, the resin is spherical, the sphere is in the most stable state, and the surface area can be increased; on the other hand, the resin with small and uniform size has larger specific surface area and faster oil absorption rate, thereby improving the oil absorption efficiency.
In an alternative embodiment, the preparation method of the organobentonite modified oil-absorbent resin comprises: adding a cross-linking agent, an initiator, a monomer and an organic bentonite additive into the dissolved dispersant solution for suspension polymerization reaction; filtering the solution while the solution is hot, washing the solution with hot water, and drying the solution to obtain granular particles; and (3) cleaning the granular particles by using toluene or acetone, and drying to obtain the modified oil-absorbing resin. The preparation method improves and optimizes the steps of the method and the like, so that the preparation process is simpler and quicker, the oil absorption times of the prepared organic bentonite modified oil absorption resin on organic matters such as carbon tetrachloride and the like are obviously increased, and the organic bentonite modified oil absorption resin is spherical, has regular size, good oil absorption effect and high oil absorption rate of a finished product, can absorb various oil products and can be repeatedly utilized.
In an alternative embodiment, a method for preparing an organobentonite-modified oil-absorbent resin comprises:
step S10, preparing organobentonite. The cationic surface modifier is used for modifying the sodium bentonite. The cationic surface modifier may be cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
Further, the sodium bentonite is modified by cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride to prepare the organic bentonite, and the specific method comprises the following steps:
and step S11, preparing bentonite suspension from sodium bentonite and distilled water, and controlling the pH value to be 7-9. Wherein the concentration of sodium bentonite in the bentonite suspension is 4-10%.
Step S12, weighing a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) or Cetyl Trimethyl Ammonium Chloride (CTAC), adding into the bentonite suspension, heating to 60-80 ℃, rapidly stirring, and reacting at constant temperature for 2.5-4 h; drying for 22-26 h at 80-110 ℃ to obtain the organic bentonite. Wherein the addition amount of the cetyl trimethyl ammonium bromide or the cetyl trimethyl ammonium chloride is 1 wt.% to 10 wt.% of the mass of the sodium bentonite.
By adopting the modification preparation method and carrying out improvement optimization control on all parameters, particularly controlling the concentration of sodium bentonite in the bentonite suspension and the addition amount of the surface modifier, the prepared organic bentonite can improve the modification performance of the organic bentonite to the oil-absorbing resin, so that the shape and the size of the oil-absorbing resin are more excellent, and the oil absorption rate of the oil-absorbing resin can be further improved.
The inventor finds that the internal structure of the bentonite contains tetrahedral and octahedral frameworks respectively composed of silicon elements and aluminum elements, but a small part of the two elements are replaced by the aluminum elements and the magnesium elements, so that negative charges exist among molecules, and the negative charges are neutralized by potassium ions and sodium ions to achieve charge balance; the specific surface area of the bentonite can reach hundreds of square meters per gram, and the great specific surface area determines that the bentonite also has outstanding adsorption capacity; therefore, based on the fact that the inorganic bentonite has strong hydrophilicity and electrons among inorganic bentonite layers are potassium ions or sodium ions, the organic modifier is intercalated among the bentonite layers through cation exchange reaction (organic matters are introduced among molecular layers to modify the bentonite layers), so that the organic bentonite with good lipophilicity is obtained, and the oil-absorbing resin has more excellent oil absorption rate by adopting the organic modifier as an additive.
In step S20, a suspension polymerization reaction is performed. Dissolving a dispersing agent; adding a cross-linking agent, an initiator, a monomer and an additive into the dispersant solution according to a ratio, and carrying out suspension polymerization reaction for 4-8 h at the temperature of 60-90 ℃.
Further, a dispersant solution was prepared: and (2) erecting a three-neck flask with a nitrogen protection device in a constant-temperature water bath kettle with a water bath temperature of 62-68 ℃, for example 65 ℃, adding a certain amount of dispersant and deionized water, and stirring for 2-3 h to completely dissolve the dispersant to obtain a dispersant solution.
The dispersing agent adopts polyvinyl alcohol, and the using amount of the polyvinyl alcohol is 0.3-1.3 wt% of the using amount of the monomer. The dispersant can be used for promoting the molding of resin particles, and the resin particles are not formed into resins with different shapes and sizes. The inventor of the application finds that when the concentration of the dispersing agent is small, particles are not completely generated, and the surface of a product has high viscosity and is not beneficial to use; when the concentration of the dispersant is large, the rigidity of the colloidal particles is increased, and the dispersant also hinders the oil-absorbing property of the resin.
The monomer adopts one or two of cetyl methacrylate, methyl methacrylate and styrene. In the invention, a monomer containing unsaturated bonds is adopted, and preferably, an acrylate is adopted, wherein the acrylate contains not only the unsaturated bonds, but also branched chains, and the branched chains mainly play a role in forming a three-dimensional network structure of the resin, and have formed three-dimensional meshes, so that the resin can bind oil stain molecules in the gaps through intermolecular force.
The cross-linking agent is one or two of divinylbenzene, ethylene glycol dimethacrylate and ethylene glycol diacrylate (also called vinyl diacrylate or ethylene glycol diacrylate), and the dosage of the cross-linking agent is 0.6 wt.% to 2 wt.%, for example 0.8 wt.%, 1.0 wt.%, 0.5 wt.%, 1.8 wt.% and the like of the dosage of the monomers. The cross-linking agent is used as a substance capable of combining a plurality of long-chain-segment molecules together, and promotes the interaction among the intermolecular force, ions and covalent bonds, so that a plurality of monomers form a criss-cross network structure. The cross-linking degree is controlled by controlling the dosage of the cross-linking agent, so that the material has the optimal mechanical property.
The initiator is one or two of benzoyl peroxide, lauroyl peroxide and tert-butyl 2-ethyl acetate peroxide, and the dosage of the initiator is 0.2-2 wt% of the dosage of the monomer. In the polymerization reaction, the initiator is the key point of the synthesis reaction, and is decomposed into free radicals along with the rise of the temperature, the high-activity free radicals attack the monomer, so that double bonds are opened to generate polymerization, and the generated high polymer forms a uniform shape under the action of the dispersing agent. The molecular weight and the crosslinking degree of the resin are controlled by controlling the using amount of the initiator. The inventor finds that the dosage is too low, the reaction speed is slow, the crosslinking degree is small, and an effective three-dimensional network structure cannot be formed, so that the oil absorption rate of the oil-absorbing resin is reduced; the dosage is too high, the three-dimensional network structure is too compact, the crosslinking degree is increased, the swelling capacity of the resin is reduced, and the oil absorption rate is also reduced; in the above amount range, the oil-absorbing resin can have excellent oil absorption.
The additive is the organic bentonite prepared in step S10, and the dosage of the additive is 0.05 wt.% to 0.5 wt.%, for example, 0.1 wt.%, 0.15 wt.%, 0.2 wt.%, 0.25 wt.%, 0.3 wt.%, 0.35 wt.%, 0.4 wt.%, 0.45 wt.% of the dosage of the monomer, so that the oil-absorbing resin has excellent morphology and size, and the oil absorption of the oil-absorbing resin is improved. More preferably, the amount of the organobentonite is 0.15 wt.% to 0.5 wt.% of the amount of the monomer, so that the oil absorption rate of the oil-absorbing resin can be further improved by making the morphology and size of the oil-absorbing resin more excellent.
According to the preparation method, each parameter of the suspension polymerization reaction is optimized, reasonable raw materials are selected, the ratio of the raw materials is optimized, the prepared organic bentonite is used as an additive, the lipophilicity of the surface of the oil-absorbing resin is increased, the size appearance of the resin is optimized, namely the resin is spherical, the size regularity is high, and the oil absorption rate of the oil-absorbing resin is greatly improved.
In step S30, hot water washing is performed with suction filtration and drying is performed. And (2) carrying out suction filtration on the solution obtained by suspension polymerization while the solution is hot, fully washing the solution by using hot water, wherein the temperature of the hot water is 60-80 ℃, the using amount of the hot water is 3-5 times of the solution amount, and drying the solution for 22-26 h, for example, 24h at 80-110 ℃ after full washing to obtain milky white or yellowish granular particles. The hot water at the temperature is adopted for washing, so that the dispersing agent and other substances adhered to the surface of the resin can be removed, the pores are prevented from being blocked, and the specific surface area is reduced. By the mode, full cleaning can be realized, and high-performance oil absorption resin can be generated.
And step S40, cleaning. And (3) washing the granular resin prepared in the step S30 with toluene or acetone, and drying for 22-26 h, for example 24h, at the temperature of 80-110 ℃ after washing to obtain the modified oil-absorbing resin. Wherein, the dosage of the toluene or the acetone can be 0.8 to 1.2 times of the resin, and the toluene or the acetone with the same dosage is preferably adopted for cleaning. By adopting the toluene or acetone re-cleaning mode, redundant grease and organic matters on the surface and in the gaps of the resin balls can be washed away, so that the oil absorption capacity of the resin is further improved.
In the embodiment of the invention, sodium bentonite is modified by Cetyl Trimethyl Ammonium Bromide (CTAB) or Cetyl Trimethyl Ammonium Chloride (CTAC) to obtain organobentonite with more excellent performance; the modified bentonite is used as an additive for increasing the surface lipophilicity of the oil-absorbing resin, so that the size appearance of the resin is optimized, and the oil absorption rate of the oil-absorbing resin is improved; meanwhile, the types and the proportions of the raw materials are further optimized, so that the modified oil-absorbing resin has the advantages of being excellent in performance, low in preparation cost, simple and rapid in reaction process, round in shape, regular in size, high in oil absorption rate of a finished product and the like, and the obtained organic bentonite modified oil-absorbing resin has high oil absorption rate on various organic matters such as benzene, carbon tetrachloride and the like, specifically the oil absorption rate on carbon tetrachloride is higher than 11g/g, so that the oil-absorbing effect is excellent, and the oil-absorbing resin can be recycled.
The technical scheme of the invention is further described by combining the specific embodiment as follows: among them, the organobentonite preparation in examples 1 to 5 and comparative examples 1 to 3: preparing bentonite suspension, adding a cationic surface modifier, heating to 70 ℃, rapidly stirring, reacting at constant temperature for 3h, and drying at 80 ℃ for 24h to obtain the bentonite suspension.
Example 1
Organobentonite was prepared with 5 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration in bentonite suspension 6%).
Adding a crosslinking agent divinylbenzene (content of 1.4 wt.%), an initiator benzoyl peroxide (content of 1.2 wt.%), a monomer (cetyl methacrylate), and organobentonite (0.2 wt.%) to a dispersing agent polyvinyl alcohol solution (content of 0.8 wt.%);
reacting at 80 ℃ for 6h, carrying out suction filtration on the solution while the solution is hot, fully washing the solution by adopting hot water at 70 ℃ of 4 times of the solution amount, drying the solution at 80 ℃ for 24h, washing the solution again by using equivalent acetone, and drying the solution for 24h to obtain the high-efficiency oil-absorbing resin modified by the organic bentonite, which is a composite material.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 15 g/g.
Example 2
Organobentonite was prepared with 10 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration 10%).
Adding divinylbenzene (content: 1.4 wt.%), benzoyl peroxide (content: 1.2 wt.%), monomer (cetyl methacrylate), and organobentonite (content: 0.2 wt.%) into polyvinyl alcohol solution (content: 1.2 wt.%) as cross-linking agent,
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ of 4 times of the solution amount, drying the solution for 24 hours at 80 ℃, washing the solution by using equivalent toluene, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 12 g/g.
Example 3
Organobentonite was prepared with 5 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration 10%).
To the dispersing agent polyvinyl alcohol solution (content: 0.8 wt.%) were added the cross-linking agent divinylbenzene (content: 1.4 wt.%), the initiator benzoyl peroxide (content: 1.2 wt.%), the monomer cetyl methacrylate (and organobentonite (0.3 wt.%),
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ with 4 times of solution amount, drying the solution for 24 hours at 80 ℃, washing the solution by using toluene with 1.2 times of solution amount, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 15.5 g/g.
Example 4
Organobentonite was prepared with 10 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration 6%).
Adding divinylbenzene (content: 1.2 wt.%), benzoyl peroxide (content: 1.2 wt.%), monomer (cetyl methacrylate), and organobentonite (content: 0.25 wt.%) into polyvinyl alcohol solution (content: 0.8 wt.%) as cross-linking agent,
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ of 4 times of the solution amount, drying the solution for 24 hours at 80 ℃, washing the solution by using acetone of 1.2 times, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 13 g/g.
Example 5
Organobentonite was prepared with 5 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration of 6%).
Adding divinylbenzene (content: 1.4 wt.%), benzoyl peroxide (content: 0.8 wt.%), monomer (cetyl methacrylate), and organobentonite (content: 0.2 wt.%) into polyvinyl alcohol solution (content: 0.8 wt.%) as cross-linking agent,
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ which is 4 times the amount of the solution, drying the solution at 80 ℃ for 24 hours, washing the solution by using equivalent acetone, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 11.5 g/g.
Comparative example 1
Organobentonite was prepared with 5 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration of 6%).
Adding divinylbenzene (0.6 wt.%), benzoyl peroxide (0.2 wt.%), monomer (cetyl methacrylate), and organobentonite (0.2 wt.%) into polyvinyl alcohol solution (0.2 wt.%) as disperser,
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ which is 4 times the amount of the solution, drying the solution at 80 ℃ for 24 hours, washing the solution by using equivalent acetone, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 5 g/g.
Comparative example 2
Organobentonite was prepared with 2 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration 6%).
To the dispersing agent polyvinyl alcohol solution (content 0.2 wt.%) were added the cross-linking agent divinylbenzene (content 0.6 wt.%), the initiator benzoyl peroxide (content 0.2 wt.%) monomer (cetyl methacrylate), and organobentonite (0.4 wt.%),
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ which is 4 times the amount of the solution, drying the solution at 80 ℃ for 24 hours, washing the solution by using equivalent acetone, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 4.5 g/g.
Comparative example 3
Organobentonite was prepared with 2 wt.% cetyltrimethylammonium bromide as surface modifier (bentonite concentration 6%).
Adding divinylbenzene (0.6 wt.%), benzoyl peroxide (0.2 wt.%), monomer (cetyl methacrylate), and organobentonite (0.02 wt.%) into polyvinyl alcohol solution (0.2 wt.%) as disperser,
reacting for 6 hours at 80 ℃; and (3) carrying out suction filtration on the solution while the solution is hot, washing the solution by adopting hot water at 70 ℃ of 4 times of the solution amount, drying the solution for 24 hours at 80 ℃, washing the solution by using equivalent acetone, and drying the solution again to obtain the high-efficiency oil-absorbing resin.
The oil absorption rate of the obtained oil absorption resin composite material to carbon tetrachloride can reach 3.8 g/g.
As can be seen from the examples and comparative examples, a decrease or increase in the amount of either component has a greater effect on the final oil absorption of the oleoresin. When the dosage of the cross-linking agent and/or the initiator is too low, an effective three-dimensional network structure cannot be formed, and the oil absorption rate of the oil-absorbing resin is greatly reduced. In the case of the same other components, the oil absorption rate of the additive decreases after the additive is used to a certain value.
Compared with the prior art, the embodiments of the invention also have the following advantages and beneficial effects:
1) compared with the existing oil-absorbing resin obtained by suspension polymerization, the invention adopts the organic bentonite to modify the oil-absorbing resin, and researches and optimizes the addition amount of the organic bentonite, thereby achieving the effects of regulating the size of the resin ball, enabling the resin ball to be round and enhancing the oil-absorbing capacity of the resin.
2) Proper dispersing agent, initiator, cross-linking agent and monomer are adopted, so that the preparation price is lower; meanwhile, the dispersant, the initiator, the cross-linking agent and the proportion of the monomer to the organic bentonite are optimized, so that the modified oil-absorbing resin has more excellent performance.
3) And acetone and the like are adopted to re-clean the resin, so that redundant grease and organic matters on the surface and in the gaps of the resin balls are thoroughly eluted, and the oil absorption capacity of the resin is improved.
4) Compared with the existing high oil absorption resin, the organic bentonite modified oil absorption resin has better oil absorption effect, can absorb various organic matters such as carbon tetrachloride and the like, and can be repeatedly used.
5) Compared with other one-time oil removal substances in the prior art, such as pure organic bentonite, the organic bentonite provided by the invention has the advantages that the oil absorption resin is improved and can be recycled repeatedly, and the oil absorption effect is greater than that of the one-time oil removal substances.
6) Some water-absorbent resins in the prior art can not be compared with the oil-water separation method, the water-absorbent resins and the oil-water separation method belong to two different fine categories, and the oil-water separation method can not realize oil-water separation of the water-absorbent resins.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to practitioners skilled in this art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. The organic bentonite modified oil-absorbing resin is characterized by comprising the following raw materials in parts by weight:
wherein the additive is organic bentonite, and is obtained by modifying sodium bentonite by adopting a cationic surface modifier;
the monomer is one or two of cetyl methacrylate, methyl methacrylate and styrene.
2. The organobentonite-modified oil-absorbing resin of claim 1, wherein the cross-linking agent is one or two of divinylbenzene, ethylene glycol dimethacrylate and ethylene glycol diacrylate; the initiator is one or two of benzoyl peroxide, lauroyl peroxide and tert-butyl 2-ethyl acetate peroxide; the dispersing agent is polyvinyl alcohol.
3. The organobentonite-modified oil-absorbing resin of claim 1, wherein the cationic surface-modifying agent is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride; the addition amount of the cationic surface modifier is 1-10% of the mass of the sodium bentonite.
4. A method for preparing the organobentonite-modified oil-absorbing resin according to any one of claims 1 to 3, comprising:
step S10, modifying the sodium bentonite by adopting hexadecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium chloride to prepare the organic bentonite;
step S20, dissolving a dispersant to obtain a dispersant solution, adding a cross-linking agent, an initiator, a monomer and an additive into the dispersant solution, and carrying out suspension polymerization reaction for 4-8 h at 60-90 ℃; wherein the additive is the organic bentonite;
step S30, carrying out suction filtration on the solution while the solution is hot, washing the solution with hot water, and drying the solution at the temperature of between 80 and 110 ℃ for 22 to 26 hours to obtain granular particles;
and step S40, washing the granular particles by toluene or acetone, and drying to obtain the modified oil-absorbing resin.
5. The method according to claim 4, wherein the hot water is used at a temperature of 60 to 80 ℃ in an amount of 3 to 5 times the amount of the solution in step S30.
6. The preparation method according to claim 4, wherein in the step S40, the drying temperature is 80-110 ℃, and the drying time is 22-26 h.
7. The method according to claim 4, wherein the step S10 includes:
preparing bentonite suspension from sodium bentonite and distilled water, and controlling the pH value to be 7-9;
adding cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride into the bentonite suspension, heating to 60-80 ℃, rapidly stirring, reacting at constant temperature for 2.5-4 h, and drying at 80-110 ℃ for 22-26 h to obtain the organic bentonite.
8. The method according to claim 7, wherein the concentration of sodium bentonite in the bentonite suspension is 4% to 10%.
9. The method according to claim 4, wherein the preparation of the dispersant solution comprises: under the condition of constant-temperature water bath, the temperature is 62-68 ℃, the dispersant is added into deionized water, and the mixture is stirred for 2-3 hours to be completely dissolved, so that dispersant solution is obtained.
10. The method for preparing the oil-absorbing resin as claimed in claim 4, wherein the oil absorption of the organobentonite-modified oil-absorbing resin is higher than 11 g/g.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005075852A (en) * | 2003-08-28 | 2005-03-24 | Dainippon Ink & Chem Inc | Method for producing highly absorbing resin |
| CN101215355A (en) * | 2008-01-09 | 2008-07-09 | 苏州大学 | High oil absorption resin and synthetic method thereof |
| CN102633945A (en) * | 2012-05-03 | 2012-08-15 | 山东大学 | Manufacturing method of compound type super absorbent resin |
| CN105001517A (en) * | 2015-07-13 | 2015-10-28 | 安徽成方新材料科技有限公司 | Rapid oil absorption composite material and preparation method thereof |
| CN105001516A (en) * | 2015-07-13 | 2015-10-28 | 安徽成方新材料科技有限公司 | Recyclable oil absorbing composite material and preparation method therefor |
-
2022
- 2022-06-21 CN CN202210702535.8A patent/CN114920874A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005075852A (en) * | 2003-08-28 | 2005-03-24 | Dainippon Ink & Chem Inc | Method for producing highly absorbing resin |
| CN101215355A (en) * | 2008-01-09 | 2008-07-09 | 苏州大学 | High oil absorption resin and synthetic method thereof |
| CN102633945A (en) * | 2012-05-03 | 2012-08-15 | 山东大学 | Manufacturing method of compound type super absorbent resin |
| CN105001517A (en) * | 2015-07-13 | 2015-10-28 | 安徽成方新材料科技有限公司 | Rapid oil absorption composite material and preparation method thereof |
| CN105001516A (en) * | 2015-07-13 | 2015-10-28 | 安徽成方新材料科技有限公司 | Recyclable oil absorbing composite material and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 陈晓磊等: "有机膨润土改性高吸油树脂复合材料的合成及性质", 《高等学校化学学报》 * |
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