CN108314762B - Polymer doped nano SiO2Oil-absorbing gel resin and preparation method and application thereof - Google Patents
Polymer doped nano SiO2Oil-absorbing gel resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a polymer doped nano SiO2The oil-absorbing gel resin is prepared by preparing styrene, functional monomer and coupling agent into mixed solution according to mass ratio, and then preparing nano SiO2Adding the mixed solution and stirring uniformly; dispersing and emulsifying by a compound emulsifier aqueous solution under high-speed shearing to form stable emulsion; initiating styrene by an initiator to carry out in-situ emulsion polymerization to prepare stable and monodisperse polystyrene-doped nano SiO2An emulsion; the emulsion is demulsified, separated, dried and crushed to obtain the polymer doped nano silicon dioxide gel resin. The prepared gel resin is used as a waste water treatment agent of aromatic hydrocarbon and derivatives thereof or aromatic hydrocarbon nitro compounds, or a waste water treatment agent of oil products containing aromatic hydrocarbon, has large oil absorption and is easy to realize oil-water separation.
Description
Technical Field
The invention relates to an oil absorption treeA preparation method of grease, in particular to polymer doped nano SiO2An oil-absorbing gel resin and a preparation method and application thereof.
Background
In the field of petrochemical industry, aromatic hydrocarbons such as benzene, toluene and xylene and derivatives or nitrates thereof, or oil products containing aromatic hydrocarbons and the like have extremely strong permeability, once leakage or discharge does not reach the standard, soil and water are seriously polluted, post-treatment is very difficult, pollutants are carcinogenic, teratogenic and mutagenic, and harm is caused to human beings and ecological environment.
Common oxidation method, biological degradation method and active carbon adsorption method have certain effect on treating the pollutants, but the treatment period is long, the chemical treatment agent can cause secondary pollution, and the removal of trace aromatic compounds is not ideal. However, the macroporous adsorption resin has low adsorption capacity, and needs to be pretreated before being used for preventing the resin from being dehydrated or frozen to be damaged, and the practical application has the disadvantages that the operation of resin column filling is blocked and the like.
Although nano SiO2Has wide application in the field of high molecular hybrid materials, but because of the nanometer SiO2The particle size is small, the specific surface area is large, the surface hydroxyl content is high, and the agglomeration is easy to happen. To improve agglomeration, it is generally necessary to work with nano-SiO2The surface treatment is carried out, and the surface treatment method mainly comprises two types: one kind adopts organic small molecules such as coupling agent, organic solvent and the like to carry out surface treatment on the polymer. Functionalization treatment of nano SiO by direct coupling agent2The method is commonly called dry method for processing the nano silicon dioxide, although the method is simple, the coupling agent is used for processing the nano SiO2Will result in nano SiO2Agglomerated and this process treats SiO2The surface is not uniform. Wet processing SiO after silane coupling agent is diluted by solvent2Commonly known as wet method, has the problem of environmental pollution caused by VOC emission due to solvent volatilization and can cause nano SiO2Difficult dispersion and large amount of agglomeration of nano SiO2The particles and the system are unstable dispersions. Another type of SiO coating by polymer2ParticlesAnd (6) surface treatment. The surface treatment of polymer coated particles realizes the nano SiO2And (3) coating and modifying the surface by using high polymers. The process firstly adopts coupling agent to couple nano SiO2Surface dry or wet treatment, and emulsion or suspension polymerization to obtain the final product with nano SiO particle microstructure2The core is core-shell particles coated by polymer. The application is mainly used as rigid particles for reinforcing and modifying polymers.
The problems of treatment unevenness, crosslinking agglomeration, solvent discharge or difficult recovery exist when the silica is treated by a coupling agent dry method or an organic solvent wet method; polystyrene coated nano SiO2The prepared is nano SiO2Polystyrene core-shell particles, wherein the surface of silicon dioxide is coated by polystyrene, and the surface of the particles presents the nonpolar characteristic of polystyrene. The hydrophobic particles are difficult to react with water, the absorption of trace aromatic hydrocarbon and other compounds in the wastewater is difficult to realize, and the separation of the hydrophobic particles from the water is difficult, which can cause the problem of secondary pollution of the water body.
Chinese patent (application No. 201310000491.5) discloses a silica-loaded polyamine water treatment agent, a preparation method and application thereof, wherein polyamine is loaded on silica, which is beneficial to quickly capturing pollutants from water and can be conveniently separated from water. The patent utilizes porous silica particles with high surface area and macroscopic size to cooperatively load polyamine to prepare the water treatment agent, but the silica in the material only plays a role of adsorbing a carrier and mainly aims at hydrophilic aromatic dye.
Chinese patent (application No. 201310442823.5) discloses a method for preparing water-soluble polystyrene-silica core-shell composite particles, which uses a silicic acid hydrolysis method to prepare the polystyrene-silica core-shell composite particles, and avoids the use of tetraethyl orthosilicate TEOS when wrapping a silica shell, and the polystyrene-silica core-shell composite particles prepared by the application do not use silica as a doping element, and are applied to mechanical polishing solutions.
Therefore, it is necessary to develop a material having good dispersibility and large specific surface areaEnvironment-friendly polymer doped nano SiO with large oil absorption2The oil-absorbing gel resin can effectively treat aromatic hydrocarbon and derivatives or nitrates thereof, or waste water solution of oil products containing the aromatic hydrocarbon.
Disclosure of Invention
The invention aims to solve the technical problem of providing an environment-friendly polymer doped nano SiO with good dispersibility, large specific surface area and large oil absorption2The oil-absorbing gel resin can effectively treat aromatic hydrocarbon and derivatives or nitrates thereof, or waste water solution of oil products containing the aromatic hydrocarbon.
In order to solve the technical problems, the invention adopts the technical scheme that: the formula of the polymer doped nano SiO2 oil absorption gel resin comprises the following components in percentage by mass: 70-95% of styrene; 0.1-15% of nano silicon dioxide; 0.01-1.5% of functional monomer; 0.01-2.5% of a coupling agent; 0.1-2% of an initiator; 0.5-8% of a composite emulsifier; 0.1-1.0% of a pH regulator; and 0.1-0.5% of demulsifier.
The invention provides a selectable polymer doped nano SiO2The chemical structural formula of the oil absorption gel resin is as follows:
by adopting the technical scheme, through the composite doping of styrene, functional monomer and silicon dioxide, the styrene is adopted to dilute the coupling agent solution to treat the nano silicon dioxide for in-situ copolymerization, and because the surface functionality of the nano silicon dioxide treated by the coupling agent is more than 2, namely the nano silicon dioxide has a plurality of functional double bonds, the polymer doped with silicon dioxide micro-crosslinking can be prepared2A gel resin material; namely nano SiO2Similar to the cross-linking agent; wherein the nano SiO is functionalized by coupling agent only2Then nano SiO will be resulted2Agglomeration and uneven surface; if the silane coupling agent is diluted by a solvent, then the SiO is treated by a wet method2The problem of environmental pollution caused by VOC emission due to solvent volatilization exists; and the styrene/functional monomer/coupling agent mixed solution is adopted to react with the nano SiO2The particles are subjected to surface treatment, styrene/functional monomer/coupling agent and nano SiO2On one hand, the coupling agent diluted by the monomer can more uniformly process the nano SiO through the interaction2The surface does not need to remove monomers such as styrene and the like; on the other hand, the monomer mixed solution containing the coupling agent is used for nano SiO2Has swelling effect and inhibits SiO2Agglomeration is carried out, thereby solving the problem of nano SiO2The problem of difficult surface treatment; make SiO2The dispersion after surface treatment is good, the surface is uniform, and the problem of environmental pollution caused by VOC emission due to solvent volatilization does not exist; the polymer is doped with nano SiO2The gel resin material is doped with SiO2The surfaces of the gel resin material particles contain trace carboxyl functional groups and silanol groups, so that the gel resin material particles have certain hydrophilicity, the gel material is easy to combine with water and soil, and the nonpolar characteristic of a styrene coated nano material is overcome; all components in the formula are mutually synergistic, so that the prepared polymer is doped with nano SiO2The gel resin material is in a gel shape, the specific surface area is extremely large, nano particles swell after oil absorption, the oil absorption is large, silanol groups and carboxyl functional groups contained in surface silicon dioxide among particles form a gel block body due to hydrogen bond combination instead of the core-shell composite material directly formed by silicon dioxide and styrene, so that the gel material is favorable for separating from water, aromatic hydrocarbon and derivatives or nitrated compounds thereof or waste water solution of oil containing aromatic hydrocarbon can be effectively treated, and the invention provides a selectable structural formula according to various characterization results.
The further improvement of the invention is that the nano-silica is gas-phase nano-silica or precipitation nano-silica, preferably gas-phase nano-silica. The fumed nano-silica is white amorphous flocculent semitransparent solid colloidal nanoparticles (the particle diameter is less than 100nm) in a normal state, is nontoxic and has a large specific surface area (100-400 m)2(iv)/g); the nano silicon dioxide prepared by the vapor phase method is all nano silicon dioxide, the purity of the product can reach 99 percent, and the particle size can reach 10-20 nm; the precipitation method of nano-silica is divided into the traditional precipitation method of nano-silica and the special precipitation method of nano-silica, the former refers to the use of sulfuric acid, hydrochloric acid and CO2The nano silicon dioxide produced by taking water glass as a basic raw material refers to the nano silicon dioxide produced by adopting a special method such as a supergravity technology, a sol-gel method, a chemical crystal method, a secondary crystallization method or a reversed-phase micelle microemulsion method; thus, fumed nanosilica is preferred.
The invention is further improved in that the functional monomer is one or a combination of at least two of alpha-methacrylic acid, itaconic acid, acrylic acid and maleic anhydride, and is preferably acrylic acid. The polarity of the monomer directly influences the affinity of the oil-absorbing gel resin to oil products, and plays a determining role in determining the oil absorption rate of the oil-absorbing gel resin; when the solubility parameters of the resin and the oil product are similar, the resin achieves the maximum oil absorption rate, for the acrylate resin, generally, the longer the carbon chain of the monomer, the better the absorption performance on the nonpolar oil product, secondly, the spatial structure of the monomer determines the number and the size of the internal micropores of the resin, and the number of the internal micropores of the resin is greatly influenced on the oil product selectivity, and generally, the number of the micropores in the resin can be effectively increased by selecting the multi-branched monomer. A large number of experiments prove that acrylic acid is selected as a functional monomer to be doped with styrene and silicon dioxide under the combined action to form polymer doped nano SiO2The oil absorption rate of the gel resin material can reach the maximum, and the nano SiO2The dispersibility of (A) is best; meanwhile, the carboxyl-containing functional monomer is easily dissolved in water, such as acrylic acid, and is easy to generate sodium carboxylate to generate self-emulsification under the condition that the pH is more than 9, so that the emulsion is stable, and the carboxyl-containing monomer is bonded on the surface of the polymer colloidal particle through polymerization reaction.
The invention further improves that the coupling agent is a titanate coupling agent or a silane coupling agent, and as a preferable scheme of the invention, the coupling agent is a silane coupling agent which is one or a combination of at least two of vinyltrimethoxysilane A-171, vinyltris (methoxyethoxy) silane A-172, vinylethoxysilane A-151, vinyltriisopropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane; as the most preferred embodiment of the present invention, the coupling agent is gamma-methacryloxypropyltrimethoxysilane.
The invention further improves that the initiator is one or the combination of at least two of potassium persulfate, ammonium persulfate and dibenzoyl peroxide, and as a preferable scheme of the invention, the initiator is potassium persulfate and/or ammonium persulfate. In the free radical polymerization, the dosage of the initiator has important influence on the molecular weight and the crosslinking degree, the oil absorption rate of the oil-absorbing gel resin has a peak value and then gradually decreases with the increase of the concentration of the initiator, the crosslinking degree increases and the molecular weight decreases due to the excessive dosage of the initiator, so the oil absorption rate decreases, but the reaction speed is slower when the dosage of the initiator is too small, the crosslinking degree is too small, and the oil absorption rate also decreases. In the prior art, oil-soluble initiators such as dibenzoyl peroxide are mostly selected; in the application, potassium sulfate and/or ammonium persulfate are preferably selected, and a large number of experiments show that the oil absorption rate can reach a peak value by selecting potassium sulfate and/or ammonium persulfate as an initiator in the polymer oil absorption resin material doped with silicon dioxide.
The invention further improves that the compound emulsifier is as follows: the emulsifier is a compound consisting of a nonionic emulsifier and an anionic emulsifier, wherein the mass ratio of the nonionic emulsifier to the anionic emulsifier is 0.01-4: 1.
The invention is further improved in that the anionic emulsifier is one or the combination of at least two of sodium oleate, potassium oleate, disproportionated rosin sodium, sodium laurate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and acrylamide isopropyl sulfonate; the non-ionic emulsifier is one or the combination of at least two of nonylphenol polyoxyethylene ether (OP-10), polyoxyethylene monolaurate (PEG), polyoxyalkene sorbitan monooleate (T-80) or fatty alcohol polyoxyethylene ether (AEO-22).
The invention further improves that the PH regulator is one or the combination of at least two of sodium carbonate, sodium bicarbonate, ammonia water, potassium hydroxide and sodium hydroxide; in a preferred embodiment of the present invention, the pH adjuster is sodium carbonate or/and sodium bicarbonate.
The invention is further improved in that the demulsifier is one or a combination of at least two of aluminum potassium sulfate, aluminum trichloride, magnesium sulfate, calcium chloride, magnesium chloride, dilute hydrochloric acid and dilute sulfuric acid, and as a preferable scheme of the invention, the demulsifier is aluminum potassium sulfate.
The invention also aims to solve the technical problem of providing the environment-friendly polymer doped nano SiO which has good dispersity, large specific surface area and large oil absorption2A method of oil-absorbing gel resin; and can solve the problems of the coupling agent processing silica or macromolecule coating silica in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: the polymer is doped with nano SiO2The preparation method of the oil absorption gel resin adopts in-situ emulsion polymerization to prepare the polymer doped nano silicon dioxide oil absorption gel resin, and specifically comprises the following steps:
(1) dissolving the composite emulsifier in deionized water to prepare an emulsifier aqueous solution for later use; dissolving an initiator in deionized water to prepare an initiator aqueous solution for later use;
(2) adding styrene (St), a functional monomer and a coupling agent into a reaction kettle according to a mass ratio, uniformly stirring to prepare a monomer mixed solution, and then adding nano SiO2Adding the mixture into the monomer mixed solution and stirring the mixture evenly to prepare the nano SiO2A mixture of the monomer mixed solution, wherein the stirring time is 30-40 min;
(3) adding the emulsifier aqueous solution prepared in the step (1) into the nano SiO prepared in the step (2)2Stirring the mixture of the monomer mixed solution at a high speed by a stirrer, wherein the high-speed stirring speed is more than 500 r/min; after dispersion and emulsification, adding a pH value regulator to regulate the pH value to 9-10 to obtain milky emulsion with stable appearance;
(4) taking 2/3 emulsion out of the reaction kettle in the step (3) and adding the emulsion into a funnel or a storage tank, adding the 1/3 initiator aqueous solution prepared in the step (1) into the reaction kettle, and keeping the rest 2/3 initiator aqueous solution and the emulsion in the funnel or the storage tank for later use;
(5) controlling the stirring speed in the reaction kettle to be 120-180 r/min, heating to 65-80 ℃, and controlling the temperature in the kettle to be 65When the emulsion in the reaction kettle turns blue at the temperature of 80 ℃ below zero, the residual initiator aqueous solution and the emulsion in the funnel or the storage tank are synchronously dripped, the dripping speed is controlled to be synchronously dripped within 1.5 to 2 hours, the reaction is continued for 1 to 2 hours, and the polymer doped nano SiO is prepared2An emulsion;
(6) doping the polymer obtained after the reaction in the step (5) with nano SiO2Dropwise adding a demulsifier aqueous solution into the emulsion, heating to 80-90 ℃, stirring at a high speed of 200-1000 rpm until the system becomes viscous paste, continuing heating and stirring for 0.5-2 h, filtering the product, and performing suction filtration by a circulating water vacuum pump to obtain a white filter cake;
(7) putting the filter cake obtained in the step (6) into a drying oven for vacuum drying at the temperature of 80 ℃ for 24h, and crushing to obtain the polymer doped nano SiO2An oil-absorbing gel resin.
By adopting the technical scheme, the polymer doped nano SiO is prepared by adopting an in-situ emulsion polymerization method2Oil-absorbing gel resin prepared by mixing nano SiO2Adding into a mixed solution prepared by styrene, functional monomer and coupling agent according to the mass ratio, and uniformly stirring to obtain nano SiO2A mixture of polymerized monomers; the mixture and a compound emulsifier aqueous solution are emulsified at high speed and subjected to in-situ emulsion polymerization at a certain temperature and stirring speed to prepare monodisperse polystyrene-based polymer doped nano SiO2An emulsion; demulsifying, separating, drying and crushing the polymer emulsion to obtain the polystyrene-based polymer doped with nano SiO2A gel resin; the stable emulsion is formed by adopting the compounded emulsifier aqueous solution, no organic solvent is discharged in the preparation process, the surface treatment, the dispersion and the polymerization of the silicon dioxide are carried out in one step, and the process flow is simple; can effectively treat aromatic hydrocarbon and derivatives or nitrated compounds thereof or waste water solution of oil products containing aromatic hydrocarbon, and can solve the problems of treating silicon dioxide or macromolecule coating silicon dioxide by using a coupling agent in the prior art.
As a preferable scheme of the invention, the stirring time of the step (2) is 30-40 min; the dispersing and emulsifying time in the step (3) is 30-40 min; the temperature of the dropwise adding emulsion and the initiator in the step (5) is 70 ℃, and the dropwise adding time is 1.5 h; the temperature for continuing the reaction after the completion of the dropwise addition was 70 ℃ and the reaction time was 1.5 hours.
The invention also aims to solve the technical problem of providing the environment-friendly polymer doped nano SiO with good dispersibility, large specific surface area and large oil absorption2Application of oil-absorbing gel resin.
In order to solve the technical problems, the invention adopts the technical scheme that: the polymer is doped with nano SiO2The application of the oil-absorbing gel resin, namely the oil-absorbing gel resin is used as a waste water treatment agent of aromatic hydrocarbon and derivatives thereof or aromatic hydrocarbon nitro compounds or a waste water treatment agent of oil products containing aromatic hydrocarbon.
The invention is further improved in that the polymer is doped with nano SiO2The application method of the oil-absorbing gel resin comprises the following steps: doping polymer with nano SiO2Adding the oil-absorbing gel resin powder into the wastewater solution, stirring at a low speed of 120-180 r/min for 2-4 h at 25 ℃, standing for 30min, separating the oil-absorbing gel resin from the wastewater solution, and adopting a polymer doped nano SiO for testing2Concentration value of the wastewater solution after the oil absorption gel resin treatment.
Compared with the prior art, the invention has the beneficial effects that:
(1) adopting styrene/functional monomer/coupling agent mixed solution to nano SiO2The particles are subjected to surface treatment, on one hand, the coupling agent diluted by the monomer can more uniformly treat the nano SiO2The surface of the material is not required to be removed with monomers such as styrene and the like; on the other hand, the monomer mixed solution containing the coupling agent is used for nano SiO2Has swelling effect and inhibits SiO2Agglomeration is carried out, thereby solving the problem of nano SiO2The problem of difficult surface treatment;
(2) adopting a compounded emulsifier aqueous solution to form a stable emulsion, and preparing the polystyrene-based polymer doped with the nano SiO through in-situ emulsion polymerization2The monodisperse polymerized emulsion has good product stability. The preparation process has no organic solvent emission, the surface treatment, dispersion and polymerization of the silicon dioxide are carried out in one step, and the process flow is simple;
(3) the carboxyl-containing functional monomer is easy to dissolve in water, such as acrylic acid, and is easy to generate sodium carboxylate to generate self-emulsification under the condition that the pH is more than 9, so that the emulsion is stable, and the carboxyl-containing monomer is bonded on the surface of the polymer colloidal particle through polymerization;
(4) the silane coupling agent solution is diluted by styrene/functional monomer to process the nano-silicon dioxide for in-situ copolymerization, and the nano-silicon dioxide processed by the silane coupling agent has surface functionality of more than 2, namely, the nano-silicon dioxide has a plurality of functional double bonds, so that the silicon dioxide micro-crosslinked polymer doped nano-SiO can be prepared2The oil absorption gel material is applied to the treatment of aromatic hydrocarbon polluted wastewater or soil, and the prepared gel resin has the capability of more easily capturing aromatic hydrocarbon and derivatives thereof in water or soil according to the similar compatibility principle;
(5) polymer doped nano SiO2The surface of the oil-absorbing gel material particle contains a carboxyl functional group and a silanol group, so that the oil-absorbing gel material has certain hydrophilicity, the gel material is easy to combine with water and soil, and the nonpolar characteristic of a styrene-coated nano material is overcome;
(6) polymer doped nano SiO2The specific surface area of the oil-absorbing gel material is extremely large, nano particles swell after oil absorption, the oil absorption is large, and silanol groups and carboxyl functional groups contained in surface silicon dioxide among particles form a gel block body due to hydrogen bond combination, so that the gel material is favorably separated from water.
Drawings
FIG. 1 shows the polymer doped with nano SiO prepared by the present invention2The particle structure of the oil-absorbing gel resin;
FIG. 2 shows the polymer doped with nano SiO prepared in example 12Microscopic topography of oil-absorbing gel resin;
FIG. 3 shows the polymer doped with nano SiO prepared in example 12TEM image of oil-absorbing gel resin;
FIG. 4 shows the polystyrene-doped nano SiO prepared in comparative example 12Microscopic topography of oil-absorbing gel resin;
FIG. 5 shows the polystyrene-doped nano SiO prepared in comparative example 12TEM image of oil-absorbing gel resin;
FIG. 6 shows the polystyrene-doped nano SiO prepared in comparative example 32TEM image of oil-absorbing gel resin;
FIG. 7 shows the polystyrene-doped nano SiO prepared in comparative example 42TEM image of oil-absorbing gel resin.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
The invention determines the polymer doped with nano SiO2The physical property method of the oil-absorbing gel resin comprises the following steps:
doping of polymers with nano-SiO for determination2The crosslinking degree and oil absorption swelling multiplying power of the oil absorption gel resin are realized by adopting methylbenzene as a purifying agent and doping the dried polymer with nano SiO2The oil-absorbing gel resin is wrapped by filter paper and is tightly tied by a cotton rope, and the wrapped oil-absorbing gel resin is placed into a Soxhlet extractor for swelling extraction, wherein the extraction time is 48 hours. And putting the extracted product in a drying oven for vacuum drying again for 24 hours, and taking out and weighing after drying. Calculation of polystyrene-doped nano SiO2The crosslinking degree and swelling ratio of the oil-absorbing gel resin are as follows:
in the formula: wRSwelling ratio,%; w1G, mass of the sample after being extracted, swelled and balanced by toluene; w2Mass of the sample after toluene extraction and drying, g.
WJDegree of crosslinking, the percentage of sample containing crosslinks expressed,%; w0Initial mass of the sample, g; w2Mass of the sample after toluene extraction and drying, g.
To observePolymer doped nano SiO2The oil-absorbing gel resin is prepared by doping the polymer with nano SiO2Diluting 1/5 emulsion sample, coating on glass slide, drying, and observing the polymer doped with nano SiO under microscope at 400 times magnification2Morphology of the particles.
Doping polymer with nano SiO2Adding the emulsion sample into a small beaker filled with 10ml of absolute ethyl alcohol in advance, carrying out ultrasonic oscillation for about 15 minutes by using an ultrasonic cleaner, dripping the solution after ultrasonic oscillation on a copper net (300 meshes) which is laid with filter paper and supported by a carbon film in advance by using a syringe type injector, baking for 5 minutes by using an infrared lamp, and then placing the solution into a transmission electron microscope for observation.
Example 1:
the polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 3.0g of fumed silica, 91.2g of styrene (St), 0.4g of Acrylic Acid (AA), 0.6g of gamma-methacryloxypropyltrimethoxysilane as a coupling agent, 1.0g of ammonium persulfate as an initiator, 2.0g of a nonionic OP-10 emulsifier, 0.5g of sodium dodecyl sulfate (SDBS) as an anionic emulsifier, 1.0g of sodium bicarbonate as a pH regulator and 0.3g of aluminum potassium sulfate as a demulsifier.
The polymer is doped with nano SiO2The preparation method of the oil-absorbing gel resin specifically comprises the following steps:
(1) dissolving a nonionic emulsifier OP-10 and an anionic emulsifier SDBS in 165g of deionized water to prepare a composite emulsifier aqueous solution; dissolving an ammonium persulfate initiator in 20g of deionized water to prepare an initiator aqueous solution;
(2) adding styrene, acrylic acid and coupling agent gamma-methacryloxypropyltrimethoxysilane into a reaction kettle according to the mass ratio, uniformly stirring to prepare a monomer mixed solution, and then adding nano SiO2Adding into the monomer mixed solution, stirring for 30min to obtain nanometer SiO2A mixture of monomer mixed solutions;
(3) adding the emulsifier aqueous solution prepared in the step (1) into the nano SiO prepared in the step (2)2The mixture of the monomer mixed solution is stirred by a stirrer at a high speed, and the high-speed stirring rotating speed is more than 500r/min, dispersing and emulsifying for 30min, and then stopping, adding sodium bicarbonate to adjust the pH value to 9 to obtain milky emulsion with stable appearance;
(4) taking out 2/3 emulsion from the reaction kettle in the step (3) and adding the emulsion into a funnel, adding the 1/3 initiator aqueous solution prepared in the step (1) into the reaction kettle, and keeping the rest 2/3 initiator aqueous solution and the emulsion in the funnel for later use;
(5) controlling the stirring speed in the reaction kettle to be 150r/min, heating to 65 ℃, controlling the temperature in the reaction kettle to be 65 ℃, when the emulsion in the reaction kettle turns blue, synchronously dropwise adding the rest initiator aqueous solution and the emulsion in the funnel, controlling the dropwise adding speed to be synchronously dropwise added within 1.5h, continuously reacting for 1h, and obtaining the polymer doped nano SiO2An emulsion;
(6) the polymer obtained after the reaction in the step (5) is doped with nano SiO2Dropwise adding an aluminum potassium sulfate aqueous solution into the emulsion, heating to 80 ℃, stirring at a high speed of 200-1000 rpm until the system becomes viscous paste, continuing heating and stirring for 1h, filtering the product, and performing suction filtration by a circulating water vacuum pump to obtain a white filter cake;
(7) the filter cake is put in a drying oven for vacuum drying for 24 hours at the temperature of 80 ℃, and the polymer doped nano SiO is obtained after crushing2An oil-absorbing gel resin.
The polymer prepared by the invention is doped with nano SiO2The selectable particle structure of the oil-absorbing gel resin is shown in figure 1, and the polymer doped with nano SiO is obtained through various characterization results2Alternative particle structure diagram for oil absorbent gel resin.
Testing polystyrene doped nano SiO2The crosslinking degree of the gel resin, the swelling degree of toluene and the concentration value after treatment of the toluene aqueous solution; see table 1.
FIG. 2 is a microscopic image of the polystyrene-doped nano-silica oil-absorbing gel resin prepared in example 1, and it can be seen from FIG. 2 that the composite particles have uniform size and good dispersibility, and almost no agglomeration phenomenon exists.
FIG. 3 is a TEM image of the polystyrene-doped nano-silica oil-absorbing gel resin prepared in example 1, and it can be seen from FIG. 3 that the composite particle has a good morphology, the particles are in a free state, the particles do not have an agglomeration phenomenon, and the particle size distribution is 30-50 nm.
Example 2
The polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 10.0g of fumed silica, 83g of styrene (St), 0.5g of Acrylic Acid (AA), 1.0g of gamma-methacryloxypropyltrimethoxysilane serving as a coupling agent, 1.0g of ammonium persulfate serving as an initiator, 102.0 g of a nonionic emulsifier OP, 1.0g of Sodium Dodecyl Sulfate (SDS) serving as an anionic emulsifier, 1.0g of sodium carbonate serving as a pH regulator and 0.5g of aluminum potassium sulfate serving as a demulsifier.
The preparation method is the same as example 1.
Testing polystyrene doped nano SiO2The degree of crosslinking, the degree of swelling with toluene and the concentration after treatment of the aqueous toluene solution of the gel resin are shown in Table 1.
Example 3
The polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 15.0g of fumed silica, 76.7g of styrene (St), 1.0g of alpha-methacrylic acid, 1.2g of coupling agent vinyltrimethoxysilane (A-171), 0.8g of initiator potassium persulfate, 2.5g of nonionic emulsifier polyoxyethylene monolaurate, 1.5g of anionic emulsifier sodium dodecyl benzene sulfonate, 0.5g of pH regulator potassium hydroxide and 0.8g of demulsifier calcium chloride.
The preparation method is the same as example 1.
Testing polystyrene doped nano SiO2The degree of crosslinking, the degree of swelling with toluene and the concentration after treatment of the aqueous toluene solution of the gel resin are shown in Table 1.
Example 4
The polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 8.0g of fumed silica, 85.4g of styrene (St), 0.8g of itaconic acid, 0.5g of vinyl ethoxysilane (A-151) coupling agent, 0.8g of potassium persulfate, 1.5g of nonionic emulsifier fatty alcohol polyoxyethylene ether, 1.0g of anionic emulsifier potassium oleate, 0.5g of pH regulator potassium hydroxide and 1.5g of demulsifier calcium chloride.
The preparation method is the same as example 1.
Testing polystyrene doped nano SiO2The degree of crosslinking, the degree of swelling with toluene and the concentration after treatment of the aqueous toluene solution of the gel resin are shown in Table 1.
Example 5
The polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 2.0g of fumed silica, 89.4g of styrene (St), 1.5g of itaconic acid, 0.1g of vinyl ethoxy silane, 1.0g of initiator potassium persulfate, 4.0g of nonionic emulsifier fatty alcohol polyoxyethylene ether, 1.0g of anionic emulsifier sodium oleate, 0.5g of pH regulator potassium hydroxide and 0.5g of demulsifier aluminum trichloride.
The preparation method is the same as example 1.
Testing polystyrene doped nano SiO2The degree of crosslinking, the degree of swelling with toluene and the concentration after treatment of the aqueous toluene solution of the gel resin are shown in Table 1.
Comparative example 1
This example differs from comparative example 1 in that the amount of silica used is increased and the amount of styrene used is decreased; the polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 20.0g of fumed silica, 74.2g of styrene (St), 0.4g of Acrylic Acid (AA), 0.6g of gamma-methacryloxypropyltrimethoxysilane serving as a coupling agent, 1.0g of ammonium persulfate serving as an initiator, 102.0 g of a nonionic emulsifier OP, 0.5g of sodium dodecyl sulfate serving as an anionic emulsifier, 1.0g of sodium bicarbonate serving as a pH regulator and 0.3g of aluminum potassium sulfate serving as a demulsifier.
The preparation process of the gel resin was the same as in example 1.
Testing polystyrene doped nano SiO2The degree of crosslinking of the gel resin, the degree of swelling with toluene and the concentration value after treatment of the aqueous toluene solution.
FIG. 4 is a microscopic image of the polystyrene-doped nano-silica oil-absorbing gel resin prepared in comparative example 1. As can be seen from FIG. 4, the composite particles have a severe agglomeration phenomenon, larger particles exist, the dispersibility is poor, and a large number of precipitated particles exist.
FIG. 5 is a TEM image of the polystyrene doped nano-silica oil absorption gel resin prepared in comparative example 1, and it can be seen from FIG. 5 that: the particles are deformed in a large amount, the coalescence phenomenon is serious, and the dispersibility of the particles is poor.
FIG. 4 and FIG. 5 illustrate, nano SiO2The excessive dosage causes difficult dispersion, serious agglomeration of particles and reduction of specific surface area.
Comparative example 2
This example differs from comparative example 1 in that no nanosilica is added, i.e. a polymer resin is produced; the polymer resin comprises the following components in percentage by weight: 94.2g of styrene (St), 0.4g of Acrylic Acid (AA), 0.6g of coupling agent gamma-methacryloxypropyltrimethoxysilane, 1.0g of initiator ammonium persulfate, 102.0 g of nonionic emulsifier OP, 0.5g of anionic emulsifier sodium dodecyl sulfate, 1.0g of pH regulator sodium bicarbonate and 0.3g of demulsifier aluminum potassium sulfate.
The preparation method is the same as example 1.
The fumed silica is not added, the prepared emulsion is the silane modified styrene-acrylic emulsion, and the obtained product has no oil absorption effect. The emulsion is generally used in the fields of coatings or adhesives and the like; from comparative example 3, it can be seen that the polymer is doped with nano SiO2The oil-absorbing gel resin is formed by doping nano silicon dioxide into polystyrene resin, has an oil-absorbing function, and is mainly formed by doping nano silicon dioxide into a polymer to dope nano SiO2The surfaces of the gel material particles contain trace carboxyl functional groups and silanol groups, so that the gel material has certain hydrophilicity, is easy to combine with water and soil, and overcomes the nonpolar characteristic of a styrene-coated nano material; the specific surface area is extremely large, the nano particles swell after absorbing oil, the oil absorption is large, and silanol groups and carboxyl functional groups contained in the silicon dioxide on the surfaces among the particles form gel block bodies due to hydrogen bond combination, so that the gel material is favorably separated from water.
Comparative example 3
The polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 3g of fumed silica, 91.2g of styrene (St), 0.4g of Acrylic Acid (AA), 0.6g of coupling agent gamma-methacryloxypropyltrimethoxysilane, 1.0g of initiator ammonium persulfate, 2.0g of nonionic emulsifier and twelve anionic emulsifiers0.5g of alkyl sodium sulfate, 1.0g of pH regulator sodium bicarbonate and 0.3g of demulsifier potassium aluminum sulfate.
The gel resin was prepared as follows:
(1) dissolving two emulsifiers into 165g of deionized water to prepare a composite emulsifier aqueous solution for later use; dissolving an initiator in 20g of deionized water to prepare an initiator aqueous solution for later use;
(2) adding styrene (St) and a functional monomer into a reaction kettle according to a mass ratio, and uniformly stirring to prepare a monomer mixed solution; mixing nano SiO2Adding the coupling agent and the coupling agent into a conical flask, stirring for 60min by using a stirrer, then adding the mixture into the mixed solution of the reaction kettle, and stirring uniformly for 30min to obtain the nano SiO2A mixture of monomer mixed solutions;
the other steps are the same as in example 1.
Testing polystyrene doped nano SiO2The degree of crosslinking, the degree of swelling with toluene and the concentration after treatment of the aqueous toluene solution of the gel resin are shown in Table 1.
In this comparative example, the silica is subjected to a surface treatment by a vapor phase method, i.e., a silane coupling agent is reacted with the silica, so that the chemical bonds between the particles are easily crosslinked to form coalescence, and the re-separation is difficult.
FIG. 6 is a TEM image of a polystyrene-doped nano-silica oil-absorbing gel resin prepared in comparative example 3; as can be seen in fig. 6: the agglomeration phenomenon of the particles is serious, the dispersibility of the particles is poor, and the particles deform greatly.
Comparative example 4
The polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by weight: 3g of gas phase method silicon dioxide, 91.2g of styrene (St), 0.4g of Acrylic Acid (AA), 0.6g of coupling agent gamma-methacryloxypropyltrimethoxysilane, 1.0g of initiating agent ammonium persulfate, 2.5g of anionic emulsifier sodium dodecyl sulfate, 1.0g of pH regulator sodium bicarbonate and 0.3g of demulsifier aluminum potassium sulfate.
The preparation method is the same as example 1.
In this comparative example, only one emulsifier, sodium lauryl sulfate, was added, and at the end of the emulsification stage, the emulsion was phase separated, i.e., oil/water separation occurred, and the emulsion stability was poor.
Testing polystyrene doped nano SiO2The degree of crosslinking, the degree of swelling with toluene and the concentration after treatment of the aqueous toluene solution of the gel resin are shown in Table 1.
FIG. 6 is a TEM image of a polystyrene-doped nano-silica oil-absorbing gel resin prepared in comparative example 4; as can be seen in fig. 6: the agglomeration phenomenon of the particles is serious, the dispersibility of the particles is poor, and the particles deform greatly.
The oil-absorbing gel resin is used as a wastewater treatment agent for aromatic hydrocarbon and derivatives thereof or aromatic hydrocarbon nitro compounds, or a wastewater treatment agent for oil products containing aromatic hydrocarbon.
The polystyrene-doped nano SiO prepared in the above examples 1 to 5 and comparative examples 1 to 42The application method of the gel resin comprises the following steps: an aqueous toluene solution (25 ℃, 0.050g/100ml) is taken as an example, but not limited to, the aqueous toluene solution is prepared by the following steps: adding 1g of polymer-doped nano SiO2 oil-absorbing gel resin powder into 100ml of toluene aqueous solution at 25 ℃, stirring at a low speed of 100r/min for 2h, standing for 30min after stirring, separating oil-absorbing gel, and testing the concentration value of the oil-absorbing gel after the toluene aqueous solution is treated by adopting a UV7504 type ultraviolet-visible spectrophotometer of Shanghai Xinmao instruments Co.
Table 1 shows the polystyrene-doped nano SiO particles obtained in examples 1-5 and comparative examples 1-42The cross-linking degree of the gel resin, the swelling degree of toluene and the concentration value after treating the toluene aqueous solution were measured.
Table 1 results of performance testing
The present invention is not limited to the above-described specific embodiments, and various modifications and changes may be made without departing from the basic technical idea of the invention within the scope of the claims of the present invention.
Claims (8)
1. Polymer doped nano SiO2Oil-absorbing gel resin, characterized in that the polymer is doped with nano SiO2The oil-absorbing gel resin comprises the following components in percentage by mass: 70-95% of styrene; 0.1-15% of nano silicon dioxide; 0.01-1.5% of functional monomer; 0.01-2.5% of a coupling agent; 0.1-2% of an initiator; 0.5-8% of a composite emulsifier; 0.1-1.0% of a pH regulator; 0.1-0.5% of demulsifier;
the composite emulsifier is a composite consisting of a nonionic emulsifier and an anionic emulsifier;
the polymer is doped with nano SiO2The preparation method of the oil-absorbing gel resin specifically comprises the following steps:
(1) dissolving the composite emulsifier in deionized water to prepare an emulsifier aqueous solution for later use; dissolving an initiator in deionized water to prepare an initiator aqueous solution for later use;
(2) adding styrene, functional monomer and coupling agent into a reaction kettle according to the mass ratio, uniformly stirring to prepare monomer mixed solution, and then adding nano SiO2Adding the mixture into the monomer mixed solution and stirring the mixture evenly to prepare the nano SiO2A mixture of monomer mixed solutions;
(3) adding the emulsifier aqueous solution prepared in the step (1) into the nano SiO prepared in the step (2)2Stirring the mixture of the monomer mixed solution at a high speed by a stirrer, wherein the high-speed stirring speed is more than 500r/min, and after dispersing and emulsifying, adding a pH value regulator to regulate the pH value to 9-10 to obtain a milky stable emulsion;
(4) taking 2/3 emulsion out of the reaction kettle in the step (3) and adding the emulsion into a funnel, adding 1/3 initiator aqueous solution prepared in the step (1) into the reaction kettle, and keeping the rest 2/3 initiator aqueous solution and the emulsion in the funnel for later use;
(5) controlling the stirring speed in the reaction kettle to be 120-180 r/min, heating to 65-80 ℃, controlling the temperature in the kettle to be 65-80 ℃, when the emulsion in the reaction kettle turns blue, synchronously dropwise adding the rest initiator aqueous solution and the emulsion in the funnel, controlling the dropwise adding speed to be synchronously dropwise added within 1.5-2 h, continuously reacting for 1-2 h, and preparing the polymer doped nano SiO2An emulsion;
(6) doping the polymer obtained after the reaction in the step (5) with nano SiO2Dropwise adding a demulsifier aqueous solution into the emulsion, heating to 80-90 ℃, stirring at a high speed of 200-1000 rpm until the system becomes viscous paste, continuing heating and stirring for 0.5-2 h, filtering the product, and performing suction filtration by a circulating water vacuum pump to obtain a white filter cake;
(7) putting the filter cake obtained in the step (6) into a drying oven for vacuum drying at the temperature of 80 ℃ for 24h, and crushing to obtain the polymer doped nano SiO2An oil-absorbing gel resin.
2. The polymer doped nano SiO of claim 12Oil-absorbing gel resin, characterized in that the polymer is doped with nano SiO2The chemical structural formula of the oil absorption gel resin is as follows:
3. the polymer doped nano SiO of claim 12The oil-absorbing gel resin is characterized in that the nano silicon dioxide is gas-phase nano silicon dioxide or precipitation nano silicon dioxide, and the functional monomer is one or the combination of at least two of alpha-methacrylic acid, itaconic acid, acrylic acid and maleic anhydride; the coupling agent is a titanate coupling agent or a silane coupling agent, and the initiator is one or the combination of at least two of potassium persulfate, ammonium persulfate and dibenzoyl peroxide.
4. The polymer doped nano SiO of claim 12The oil-absorbing gel resin is characterized in that the mass ratio of the nonionic emulsifier to the anionic emulsifier is 0.01-4: 1.
5. The polymer doped nano SiO of claim 42The oil-absorbing gel resin is characterized in that the anionic emulsifier is sodium oleate, potassium oleate, disproportionated rosin sodium and lauric acidOne or the combination of at least two of sodium, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and acrylamide isopropyl sulfonate; the nonionic emulsifier is one or the combination of at least two of nonylphenol polyoxyethylene ether, polyoxyethylene monolaurate, polyoxyethylene sorbitan monooleate and fatty alcohol polyoxyethylene ether.
6. The polymer doped nano SiO of claim 12The oil-absorbing gel resin is characterized in that the pH regulator is one or the combination of at least two of sodium carbonate, sodium bicarbonate, ammonia water, potassium hydroxide and sodium hydroxide; the demulsifier is one or the combination of at least two of aluminum potassium sulfate, aluminum trichloride, magnesium sulfate, calcium chloride, magnesium chloride, dilute hydrochloric acid and dilute sulfuric acid.
7. The polymer doped nano SiO of claim 12The oil-absorbing gel resin is characterized in that the stirring time in the step (2) is 30-40 min; the dispersing and emulsifying time in the step (3) is 30-40 min; the temperature of the dropwise adding emulsion and the initiator in the step (5) is 70 ℃, and the dropwise adding time is 1.5 h; the temperature for continuing the reaction after the completion of the dropwise addition was 70 ℃ and the reaction time was 1.5 hours.
8. Polymer doped nano SiO according to any of claims 1 to 72The application of the oil-absorbing gel resin is characterized in that the polymer is doped with nano SiO2Oil-absorbing gel resin used as waste water treatment agent of aromatic hydrocarbon and its derivative or aromatic hydrocarbon nitro compound, or nano SiO doped with the polymer2The oil-absorbing gel resin is used as a wastewater treatment agent of oil products containing aromatic hydrocarbons; the polymer is doped with nano SiO2The application method of the oil-absorbing gel resin comprises the following steps: doping polymer with nano SiO2Adding the oil-absorbing gel resin powder into the wastewater solution, stirring at a low speed of 120-180 r/min for 2-4 h at 25 ℃, standing for 30min, separating the oil-absorbing gel resin from the wastewater solution, and adopting a polymer doped nano SiO for testing2Oil absorptionConcentration value of the wastewater solution after gel resin treatment.
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| CN103059188A (en) * | 2012-12-18 | 2013-04-24 | 华中科技大学 | Preparing method of composite styrene-acrylic emulsion containing silicon dioxide |
| JP2015113276A (en) * | 2013-12-16 | 2015-06-22 | 旭硝子株式会社 | Spherical silica and method for manufacturing the same |
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| JP2015113276A (en) * | 2013-12-16 | 2015-06-22 | 旭硝子株式会社 | Spherical silica and method for manufacturing the same |
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