CN108314762A - Polymer-doped Nano-meter SiO_22Oil suction gel resin and its preparation method and application - Google Patents
Polymer-doped Nano-meter SiO_22Oil suction gel resin and its preparation method and application Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to a kind of polymer-doped Nano-meter SiO_2s2Oil suction gel resin and its preparation method and application, by the way that styrene, function monomer and coupling agent are configured to mixed solution according to mass ratio, then by Nano-meter SiO_22Mixed solution is added to stir evenly；Through composite emulsifier aqueous solution under high speed shear dispersion and emulsion, form stable emulsion；Cause styrene through initiator and carry out in-situ emulsion polymerization, is prepared for stable, monodispersed polystyrene dopen Nano SiO2Lotion；The lotion is through demulsification, separation, drying, crushing to get polymer-doped nano silicon dioxide gel resin.Gel resin obtained is used as fragrant hydrocarbons and their derivates or the waste water treating agent of aromatic hydrocarbon nitro compound, or the waste water treating agent of the oil product containing arene, and oil absorption is big, and water-oil separating easy to implement.
Description
Technical field
The present invention relates to the preparation method of oil-absorbing resin more particularly to polymer-doped Nano-meter SiO_2s2Oil suction gel resin and
Preparation method and application.
Background technology
In petrochemical industry, such as the fragrant hydrocarbons and their derivates of benzene,toluene,xylene or itrated compound, or contain virtue
The oil product etc. of fragrant hydro carbons has extremely strong permeability, once leakage or discharge be not up to standard, will be caused sternly to soil and water body
Heavily contaminated, post-processing is extremely difficult, and pollutant is carcinogenic, teratogenesis and mutagenesis, causes damages to the mankind and ecological environment.
Common oxidizing process, biological degradation method, active carbon adsorption have certain effect to handling this pollutant, but deposit
In long processing period, chemical treatments can cause secondary pollution, very undesirable to removing Determination for trace aromatic hydrocarbon compound.Also there is use
The method that macroporous absorbent resin handles this pollutant, still, macroporous absorbent resin adsorbance be not high, and to prevent resin de-
Water is endured cold and is destroyed, and needs to be pre-processed before use, and there is also resin dress column operations to have blocking to occur etc. when practical application
Unfavorable factor.
Although Nano-meter SiO_22It has a wide range of applications in polymer hybridisation Material Field, but due to Nano-meter SiO_22Grain size it is small,
Large specific surface area, the adsorbed hydroxyl content are high, it is made easily to reunite.In order to improve agglomeration traits, it usually needs to Nano-meter SiO_22Into
Row surface treatment, there are two main classes for surface treatment method：One kind using such as coupling agent, organic solvent organic molecule to its into
Row surface treatment.Direct coupling agent functionalization processing Nano-meter SiO_22, it is commonly called as dry process nano silicon dioxide, though method is simple,
But coupling agent treatment Nano-meter SiO_22It can lead to Nano-meter SiO_22Reunite, and this method handles SiO2Surface is uneven.Solvent dilutes silicon
Wet-treating SiO after alkane coupling agent2, it is commonly called as wet method, there are the problem of environmental pollution that solvent volatilization leads to VOC emission, Er Qiehui
Lead to Nano-meter SiO_22It is difficult to disperse, there is the Nano-meter SiO_2 largely reunited2Particle, system are non-stable dispersion.It is another kind of logical
Cross macromolecule coated Si O2Particle surface processing.It is handled by polymeric PTC materials particle surface, realizes Nano-meter SiO_22The height on surface
Molecule coating modification.The technique uses coupling agent to Nano-meter SiO_2 first2Surface dry process or wet-treating, then use lotion
Prepared by polymerization or suspension polymerization, particle microstructure is Nano-meter SiO_22For core, surface is the nucleocapsid grain of polymer overmold
Son.Its application is modified mainly as rigid particles for enhancing by polymer.
With coupling agent dry process or organic solvent wet-treating silica, there is processing unevenness, crosslinking reunites, is molten
The problem of agent discharges or is difficult to recycle；Polystyrene coats Nano-meter SiO_22Obtained is Nano-meter SiO_22/ polystyrene core shell particles,
Silica surface is coated by polystyrene, and polystyrene apolar character is presented in particle surface.This hydrophobicity particle is difficult to
It has an effect with water, it is difficult to realize that the compounds such as the Determination for trace aromatic hydrocarbon in waste water absorb, and be separated from the water these hydrophobicities
Little particle particle is difficult, can lead to secondary pollution of water problem.
Chinese patent (application number：201310000491.5) disclose a kind of silicon dioxide carried polyamines water treatment agent, system
Preparation Method and its application, this application load to polyamines on silica, are conducive to quickly capture pollutant from water, while again
It easily can be separated from the water out.The patent is cooperateed with negative using the porous silica silicon particle of the macro-size of high surface area
It carries polyamines and prepares water treatment agent, but silica only serves the effect of absorption carrier in the material, and mainly for hydrophilic virtue
Fragrant dyestuff.
Chinese patent (application number：201310442823.5) disclose a kind of water-soluble polystyrene-silicon dioxide core-shell
The preparation method of type composite particles, this application use silicic acid Hydrolyze method, are prepared for polystyrene-compound of silica core shell mould
Grain, the use of ethyl orthosilicate TEOS, polystyrene-silica core prepared by this application when avoiding package outer silica shell
Shell mould composite particles be not using silica as doped chemical, and its be applied to machine polishing liquor.
It is received therefore, it is necessary to develop big the polymer-doped of environmental protection of a kind of good dispersion, large specific surface area and oil absorption
Rice SiO2Fragrant hydrocarbons and their derivates or itrated compound or the oil containing arene can be effectively treated in oil suction gel resin
The waste water solution of product.
Invention content
The technical problem to be solved by the present invention is to provide a kind of good dispersion, large specific surface area and the big environmental protection of oil absorption
Polymer-doped Nano-meter SiO_22Oil suction gel resin can be effectively treated fragrant hydrocarbons and their derivates or itrated compound or contain
There is the waste water solution of the oil product of arene.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：The polymer-doped nanosized SiO_2 oil suction
The Formulation Ingredients of gel resin are by mass percentage：Styrene 70~95%；Nano silicon dioxide 0.1~15%；Function list
Body 0.01~1.5%；Coupling agent 0.01~2.5%；Initiator 0.1~2%；Compound emulsifying agent 0.5~8%；PH adjusting agent 0.1
~1.0%；Demulsifier 0.1~0.5%.
The present invention provides a kind of selectable polymer-doped Nano-meter SiO_22The chemical structural formula of oil suction gel resin is：
It is composite mixed by styrene, function monomer and silica using above-mentioned technical proposal, it is diluted using styrene
Coupling agent solution handles nano silicon dioxide in-situ copolymerization, because big using the nano-silica surface degree of functionality of coupling agent treatment
In 2, that is, possess multiple function double bonds, then can prepare a kind of micro- crosslinked polymer-doped Nano-meter SiO_2 of doping silicon dioxide2It is solidifying
Photomask resin material；That is Nano-meter SiO_22Similar to crosslinking agent；If being wherein only functionalized processing Nano-meter SiO_2 with coupling agent2, then can cause
Nano-meter SiO_22Reunite, surface is uneven；According to wet-treating SiO after solvent diluted silane coupling agent2, can there is solvent volatilization
Lead to the problem of environmental pollution of VOC emission；And use styrene/function monomer/coupling agent mixed solution to Nano-meter SiO_22Particle
It is surface-treated, styrene/function monomer/coupling agent and Nano-meter SiO_22The interaction on the one hand coupling after monomer dilutes
Agent can be evenly processing Nano-meter SiO_22Surface and the monomers such as styrene need not be removed；On the other hand, the monomer containing coupling agent
Mixed solution is to Nano-meter SiO_22Play swelling action, it is suppressed that SiO2Reunite, to solve Nano-meter SiO_22Surface treatment is difficult to ask
Topic；Make SiO2Good dispersion, surface after surface treatment are uniformly and there is no solvent volatilizations to cause the environment of VOC emission dirty
Dye problem；The polymer-doped Nano-meter SiO_22Gel resin material is due to being doped with SiO2Gel resin material particles surface is set to contain
There are micro carboxyl functional group and silanol groups, therefore there is certain hydrophily, gel rubber material is made easily to be combined with water, soil, gram
Take styrene cladding nano material apolar character；All the components in formula mutually act synergistically, and polymer obtained is made to mix
Miscellaneous Nano-meter SiO_22Gel resin material is gel, and specific surface area is very big, and nano-particle is swollen after oil suction, and oil absorption is big, grain
Silanol groups, carboxyl functional group contained by surface silica dioxide form gelinite blocks rather than titanium dioxide because of Hydrogenbond between son
Silicon directly forms core-shell composite material with styrene, is separated from water to be conducive to gel rubber material, aromatic hydrocarbon can be effectively treated
And its waste water solution of derivative or itrated compound or the oil product containing arene, according to various characterization results, the present invention carries
For a kind of selectable structural formula.
Further improvement of the present invention is that the nano silicon dioxide is that fumed nano silica or the precipitation method are received
Rice silica, preferably fumed nano silica.It is cotton-shaped for white-amorphous under fumed nano silica normality
Translucent solid colloidal nano-particle (grain size is less than 100nm), it is nontoxic, there is huge specific surface area (100~400m2/g)；Gas
Phase method nano silicon dioxide is entirely nano silicon dioxide, and product purity is up to 99%, and grain size is up to 10~20nm；The precipitation method are received
Rice silica is divided into as traditional precipitation method nano silicon dioxide and special precipitation nano silicon dioxide, the former refers to sulphur
Acid, hydrochloric acid, CO2With the nano silicon dioxide that waterglass is base stock production, the latter refers to using high-gravity technology, colloidal sol-
The nano silicon dioxide of the specific process such as gel method, chemical crystal method, second-crystallized method or reverse micelle microemulsion liquid method production；Cause
This preferred fumed nano silica.
Further improvement of the present invention is that the function monomer is α-methacrylic acid, methylene-succinic acid, propylene
Acid, one kind in maleic anhydride or at least two combination, preferably acrylic acid.The polarity of monomer directly affects oil suction gel
Resin plays decisive action to the size of oil product affinity to the oil absorbency of oil suction gel resin；When the solubility of resin and oil product
When parameter similar, resin reaches maximum oil absorbency, for acrylic resin, in general, the carbochain of monomer more it is long then
Better to the absorbent properties of nonpolar oil product, secondly, the space structure of monomer determines the quantity of the internal capillary of resin and big
It is small, selectively have a great impact to oil product, in general, selects the monomer of highly branched chain that can effectively improve micropore in resin
Quantity.By experimental results demonstrate choose acrylic acid to adulterate shape as function monomer and styrene and silica collective effect
At polymer-doped Nano-meter SiO_22The oil absorbency of gel resin material can reach maximum, and Nano-meter SiO_22Dispersibility it is best；Simultaneously
Monomer containing carboxyl function is soluble easily in water, such as acrylic acid, in PH ＞ 9, is easy to generate carboxylic acid sodium salt and generate self-emulsifying
Phenomenon is conducive to emulsion-stabilizing, and the aggregated reaction of carboxyl group-containing monomer is bonded in the surface of polymer billet.
Further improvement of the present invention is that the coupling agent is titanate coupling agent or silane coupling agent, as this hair
Bright preferred embodiment, the coupling agent be silane coupling agent, the silane coupling agent be vinyltrimethoxysilane A-171,
(methoxy ethoxy) silane of vinyl three A-172, vinylethoxysilane A-151, vinyl triisopropyl trimethoxy
One kind in silane, gamma-methyl allyl acyloxypropyl trimethoxysilane or at least two combination；As the optimal of the present invention
It is gamma-methyl allyl acyloxypropyl trimethoxysilane to select scheme, the coupling agent.
Further improvement of the present invention is that the initiator is in potassium peroxydisulfate, ammonium persulfate, dibenzoyl peroxide
One kind or at least two combination, as the present invention preferred embodiment, the initiator be potassium peroxydisulfate and/or persulfuric acid
Ammonium.In free radical polymerization, the dosage of initiator has molecular weight and the degree of cross linking critically important influence, with initiator concentration
Increase, the oil absorbency of oil suction gel resin, which has peak value, to be occurred and then continuously decrease, because initiator amount is excessive, causes to hand over
Connection degree increases and molecular weight reduces, therefore oil absorbency declines, but the too small then reaction speed of initiator amount is slower, and the degree of cross linking is too small,
Oil absorbency can also reduce.Prior art multiselect oil-soluble initiator, such as dibenzoyl peroxide；And the application preferably sulfuric acid potassium
And/or ammonium persulfate, then it is to obtain to select in the polymer oil-absorbing resin material of doping silicon dioxide after many experiments
Potassium sulfate and/or ammonium persulfate can make oil absorbency reach peak value as initiator.
Further improvement of the present invention is that the compound emulsifying agent is：The emulsifier be by nonionic emulsifier and
The compound of anion emulsifier composition, the wherein mass ratio of nonionic emulsifier and anion emulsifier are 0.01~4:1.
Further improvement of the present invention is that anion emulsifier is enuatrol, potassium oleate, disproportionated rosin sodium, lauric acid
Sodium, neopelex, lauryl sodium sulfate, one kind in acrylamido sodium isopropyl xanthate or at least two
Combination；The nonionic emulsifier is nonylphenol polyoxyethylene ether (OP-10), Vinlub 73 (PEG), polyoxy alkene
Sorbitan acid monoleate (T-80) or one kind in fatty alcohol polyoxyethylene ether (AEO-22) or at least two combination.
Further improvement of the present invention is that the PH conditioning agents are sodium carbonate, sodium bicarbonate, ammonium hydroxide, potassium hydroxide, hydrogen
One kind in sodium oxide molybdena or at least two combination；As the present invention preferred embodiment, the pH adjusting agent be sodium carbonate or/
And sodium bicarbonate.
Further improvement of the present invention is that the demulsifier is alum, alchlor, magnesium sulfate, calcium chloride, chlorine
Change magnesium, dilute hydrochloric acid, one kind in dilute sulfuric acid or at least two combination, as the preferred embodiment of the present invention, the demulsifier is
Alum.
The present invention also technical problems to be solved, which are to provide one kind, can prepare good dispersion, large specific surface area and suction
The polymer-doped Nano-meter SiO_2 of the big environmental protection of oil mass2The method of oil suction gel resin；And coupling agent in the prior art can be solved
Handle silica or polymeric PTC materials silica there are the problem of.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：The polymer-doped Nano-meter SiO_22Oil suction
The preparation method of gel resin is prepared for polymer-doped nano silicon dioxide oil suction gel resin using in-situ emulsion polymerization,
Specifically comprise the following steps：
(1) compound emulsifying agent is dissolved in deionized water, is configured to emulsifier aqueous solution, for use；Initiator is dissolved
In deionized water, it is configured to initiator solution, for use；
(2) reaction kettle is added according to quality proportioning in styrene (St), function monomer and coupling agent to stir evenly, is configured to
Monomer mixture solution, then by Nano-meter SiO_22It is added in monomer mixture solution and stirs evenly, Nano-meter SiO_2 is made2The mixing of/monomer is molten
The mixture of liquid, wherein mixing time is 30~40min；
(3) Nano-meter SiO_2 made from step (2) is added in the prepared emulsifier aqueous solution of step (1)2The mixing of/monomer is molten
In the mixture of liquid, agitated device high-speed stirred, high-speed stirred rotating speed is more than 500r/min；After dispersion and emulsion, pH value tune is added
It is 9~10 to save agent and adjust pH value, obtains the emulsion of appearance milky white stabilization；
(4) 2/3 emulsion is taken out out of step (3) reaction kettle and funnel or storage tank is added, and step (1) is taken to prepare
1/3 initiator solution is added in reaction kettle, and the emulsion in remaining 2/3 initiator solution and funnel or storage tank is standby
With；
(5) it is 120~180r/min to control mixing speed in reaction kettle, is heated to 65~80 DEG C, and control in kettle
Temperature is 65~80 DEG C, when lotion blueing light in reaction kettle, start it is synchronous be added dropwise remaining initiator solution and funnel or
Emulsion in storage tank, and control rate of addition and synchronized in 1.5~2h and dripped, the reaction was continued 1~2h, obtained polymer are mixed
Miscellaneous Nano-meter SiO_22Lotion；
(6) the polymer-doped Nano-meter SiO_2 obtained after being reacted to step (5)2Demulsifier aqueous solution, heating are added dropwise in lotion
80~90 DEG C are warming up to, and with the rotating speed high-speed stirred of 200~1000rpm, the paste until system becomes sticky continues heating stirring
0.5~2h, product filter and filter to obtain white filter cake through vacuum pump using circulatory water；
(7) filter cake that step (6) obtains is placed in drying box at 80 DEG C and is dried in vacuo for 24 hours, crushing obtains polymer
Dopen Nano SiO2Oil suction gel resin.
Using above-mentioned technical proposal, polymer-doped Nano-meter SiO_2 is prepared for using the method for in-situ emulsion polymerization2Oil suction is solidifying
Gum resin, by Nano-meter SiO_22It is added in the mixed solution being configured to according to mass ratio by styrene, function monomer and coupling agent, stirs
It mixes uniformly, obtains Nano-meter SiO_22The mixture of/polymerized monomer；The mixture is emulsified with composite emulsifier aqueous solution through high speed, one
In-situ emulsion polymerization is carried out under constant temperature degree, mixing speed, prepares monodispersed polystyrene based polymers dopen Nano SiO2Breast
Liquid；Polymer emulsion is through demulsification, separation, drying, crushing to get polystyrene based polymers dopen Nano SiO2Gel resin；
The emulsifier aqueous solution of compounding is taken to form stable emulsion, the discharge of preparation process organic solvent-free, silica surface
Processing, dispersion and polymerisation step carry out, and technological process is simple；Fragrant hydrocarbons and their derivates or itrated compound can be effectively treated, or
Person contains the waste water solution of the oil product of arene, and can solve coupling agent treatment silica or high score in the prior art
Sub- coated silica there are the problem of.
As the preferred embodiment of the present invention, the mixing time of the step (2) is 30~40min；The step (3)
The dispersion and emulsion time is 30~40min；The be added dropwise emulsion and the temperature of initiator of the step (5) are 70 DEG C, time for adding
For 1.5h；It is 70 DEG C to be added dropwise to complete the rear temperature that the reaction was continued, reaction time 1.5h.
The present invention also technical problems to be solved are to provide a kind of good dispersion, large specific surface area and the big ring of oil absorption
The polymer-doped Nano-meter SiO_2 protected2The application of oil suction gel resin.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：The polymer-doped Nano-meter SiO_22Oil suction
The application of gel resin, i.e. the oil suction gel resin are used as the wastewater treatment of fragrant hydrocarbons and their derivates or aromatic hydrocarbon nitro compound
Agent, or the oil product containing arene waste water treating agent.
Further improvement of the present invention is, the polymer-doped Nano-meter SiO_22The method packet of the application of oil suction gel resin
Include following steps：Take polymer-doped Nano-meter SiO_22The powder of oil suction gel resin is added in waste water solution, low at 25 DEG C
Speed 2~4h of stirring, mixing speed are 120~180r/min, and oil suction gel tree is isolated from waste water solution after standing 30min
Fat, test use polymer-doped Nano-meter SiO_22The concentration value of oil suction gel resin treated waste water solution.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) use styrene/function monomer/coupling agent mixed solution to Nano-meter SiO_22Particle is surface-treated, a side
Coupling agent of the face after monomer dilutes can be evenly processing Nano-meter SiO_22Surface, and the monomers such as styrene need not be removed；Separately
On the one hand, the monomer mixture solution containing coupling agent is to Nano-meter SiO_22Play swelling action, it is suppressed that SiO2Reunite, to solve
Nano-meter SiO_22It is surface-treated difficult problem；
(2) it takes the emulsifier aqueous solution of compounding to form stable emulsion, polyphenyl second is prepared through in-situ emulsion polymerization
Alkenyl polymer dopen Nano SiO2Monodisperse polymer lotion, product stability are good.Preparation process organic solvent-free discharges, dioxy
SiClx surface treatment, dispersion and polymerisation step carry out, and technological process is simple；
(3) monomer containing carboxyl function is soluble easily in water, such as acrylic acid, in PH ＞ 9, be easy to generate carboxylic acid sodium salt and
It is produced from emulsion, is conducive to emulsion-stabilizing, and the aggregated reaction of carboxyl group-containing monomer is bonded in the surface of polymer billet；
(4) styrene/function monomer diluted silane coupling agent solution is used to handle nano silicon dioxide in-situ copolymerization, because of silicon
The nano-silica surface degree of functionality of alkane coupling agent treatment is more than 2, that is, possesses multiple function double bonds, can prepare a kind of titanium dioxide
The micro- crosslinked polymer-doped Nano-meter SiO_2 of silicon2Oil suction gel rubber material is applied to the waste water or soil treatment of arene pollution,
According to the principle of similar compatibility, gel resin obtained has the energy for being easier to capture water or the fragrant hydrocarbons and their derivates in soil
Power；
(5) polymer-doped Nano-meter SiO_22Oil suction gel rubber material particle surface contains carboxyl functional group and silanol groups, tool
There are certain hydrophily, gel rubber material easily to be combined with water, soil, styrene is overcome to coat nano material apolar character；
(6) polymer-doped Nano-meter SiO_22Oil suction gel rubber material specific surface area is very big, and nano-particle is swollen after oil suction, oil suction
Amount is big, and silanol groups, carboxyl functional group contained by surface silica dioxide form gelinite blocks because of Hydrogenbond between particle, from
And is conducive to gel rubber material and is separated from water.
Description of the drawings
Fig. 1 is polymer-doped Nano-meter SiO_2 produced by the present invention2The particle structure of oil suction gel resin；
Fig. 2 is polymer-doped Nano-meter SiO_2 made from embodiment 12The microscope shape appearance figure of oil suction gel resin；
Fig. 3 is polymer-doped Nano-meter SiO_2 made from embodiment 12The TEM of oil suction gel resin schemes；
Fig. 4 is polystyrene dopen Nano SiO made from comparative example 12The microscope shape appearance figure of oil suction gel resin；
Fig. 5 is polystyrene dopen Nano SiO made from comparative example 12The TEM of oil suction gel resin schemes；
Fig. 6 is polystyrene dopen Nano SiO made from comparative example 32The TEM of oil suction gel resin schemes；
Fig. 7 is polystyrene dopen Nano SiO made from comparative example 42The TEM of oil suction gel resin schemes.
Specific implementation mode
In order to deepen the understanding of the present invention, the present invention is done below in conjunction with drawings and examples and is further retouched in detail
It states, the embodiment is only for explaining the present invention, does not constitute and limits to protection scope of the present invention.
The present invention measures polymer-doped Nano-meter SiO_22The method of the physical property of oil suction gel resin is：
To measure polymer-doped Nano-meter SiO_22The degree of cross linking and oil suction swelling ratio of oil suction gel resin, use toluene for
Scarvenger, by the polymer-doped Nano-meter SiO_2 after drying2Oil suction gel resin is wrapped with filter paper and is tightened with cotton cord, and rope is put into
Swelling extracting, extraction times 48h are carried out in family name's extractor.Product after extracting is placed in drying box and is dried in vacuo again,
Drying time is for 24 hours, to take out and weigh after dry.Calculate polystyrene dopen Nano SiO2The oil suction gel resin degree of cross linking and molten
Swollen multiplying power such as following formula：
In formula：WR, swelling ratio, %；W1, sample quality, g after toluene extracts swelling equilibrium；W2, sample takes out through toluene
Material mass after carrying and drying, g.
WJ, the degree of cross linking, the expression of sample percentage containing cross-linking agent, %；W0, sample initial mass, g；W2, sample takes out through toluene
Material mass after carrying and drying, g.
To observe polymer-doped Nano-meter SiO_22The microscopic feature of oil suction gel resin, by manufactured polymer-doped nanometer
SiO2It is coated on glass slide and dries after emulsion sample dilution 1/5, be subsequently placed under microscope and amplify 400 times of observation polymerizations
Object dopen Nano SiO2The pattern of particle.
By polymer-doped Nano-meter SiO_22Emulsion sample is added in the small beaker equipped with 10ml absolute ethyl alcohols in advance, is used
Ultrasonic cleaner ultrasonic vibration 15 minutes or so, the solution after ultrasound is dropped in syringe-type syringe and is covered with filter paper in advance
On the copper mesh supported with carbon film (300 mesh), is dried after five minutes using infrared lamp, be put into transmission electron microscope and be observed.
Embodiment 1：
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 3.0g, benzene second
Alkene (St) 91.2g, acrylic acid (AA) 0.4g, coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane 0.6g, initiator mistake
Ammonium sulfate 1.0g, nonionic OP-10 emulsifier 2.0g, anion emulsifier lauryl sodium sulfate (SDBS) 0.5g, pH are adjusted
Agent sodium bicarbonate 1.0g, demulsifier alum 0.3g.
The polymer-doped Nano-meter SiO_22The preparation method of oil suction gel resin, specifically comprises the following steps：
(1) nonionic emulsifier OP-10 and anion emulsifier SDBS are dissolved in 165g deionized waters, are configured to multiple
Co-emulsifier aqueous solution；Ammonium persulfate initiator is dissolved in 20g deionized waters, initiator solution is configured to；
(2) by styrene, acrylic acid and coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane according to quality proportioning
Reaction kettle is added to stir evenly, monomer mixture solution is configured to, then by Nano-meter SiO_22It is added in monomer mixture solution and stirs
Even, Nano-meter SiO_2 is made in mixing time 30min2The mixture of/monomer mixture solution；
(3) the prepared emulsifier aqueous solution of step (1) is added to the Nano-meter SiO_2 of step (2)2/ monomer mixture solution
In mixture, agitated device high-speed stirred, high-speed stirred rotating speed is more than 500r/min, stops after dispersion and emulsion 30min, and carbon is added
It is 9 that sour hydrogen sodium, which adjusts pH value, obtains the emulsion of appearance milky white stabilization；
(4) 1/3 initiation taken out 2/3 lotion out of step (3) reaction kettle and funnel is added, and step (1) is taken to prepare
Agent aqueous solution is added in reaction kettle, and the emulsion in remaining 2/3 initiator solution and funnel is spare；
(5) it is 150r/min to control mixing speed in reaction kettle, is heated to 65 DEG C, and control temperature in the kettle is 65 DEG C,
When lotion blueing light in reaction kettle, start the synchronous emulsion being added dropwise in remaining initiator solution and funnel, and control
Rate of addition is synchronized in 1.5h and is dripped, the reaction was continued 1h, and polymer-doped Nano-meter SiO_2 is made2Lotion；
(6) the polymer-doped Nano-meter SiO_2 obtained after reacting step (5)2Lotion is added dropwise alum aqueous solution, adds
Heat is warming up to 80 DEG C, and with the rotating speed high-speed stirred of 200~1000rpm, the paste until system becomes sticky, and continues heating stirring
1h, product filter and filter to obtain white filter cake through vacuum pump using circulatory water；
(7) filter cake, which is placed in drying box at 80 DEG C, is dried in vacuo for 24 hours, and crushing obtains polymer-doped Nano-meter SiO_22It inhales
Oleogel resin.
Polymer-doped Nano-meter SiO_2 produced by the present invention2Selectable particle structure such as Fig. 1 institutes of oil suction gel resin
Show, by various characterization results, obtains a kind of polymer-doped Nano-meter SiO_22The selectable particle knot of oil suction gel resin
Composition.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value；It is shown in Table 1.
Fig. 2 is the microscope shape appearance figure of polystyrene mixed with nano-silicon dioxide oil suction gel resin made from embodiment 1,
Composite particles size uniformity as can be seen from Fig. 2, favorable dispersibility exist almost without agglomeration.
Fig. 3 is the TEM figures of polystyrene mixed with nano-silicon dioxide oil suction gel resin made from embodiment 1, from Fig. 3
It can be seen that compound particle form is preferable, free state, particle soilless sticking phenomenon is presented in particle, and particle diameter distribution is 30~50nm.
Embodiment 2
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 10.0g, benzene second
Alkene (St) 83g, acrylic acid (AA) 0.5g, coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane 1.0g, initiator over cure
Sour ammonium 1.0g, nonionic emulsifier OP-10 2.0g, anion emulsifier lauryl sodium sulfate (SDS) 1.0g, pH adjusting agent
Sodium carbonate 1.0g, demulsifier alum 0.5g.
The preparation method is the same as that of Example 1.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value, be shown in Table 1.
Embodiment 3
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 15.0g, benzene second
Alkene (St) 76.7g, α-methacrylic acid 1.0g, coupling agent vinyltrimethoxysilane (A-171) 1.2g, initiator persulfuric acid
Potassium 0.8g, nonionic emulsifier Vinlub 73 2.5g, anion emulsifier neopelex 1.5g, pH
Conditioning agent potassium hydroxide 0.5g, demulsifier calcium chloride 0.8g.
The preparation method is the same as that of Example 1.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value, be shown in Table 1.
Embodiment 4
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 8.0g, benzene second
Alkene (St) 85.4g, methylene-succinic acid 0.8g, vinylethoxysilane (A-151) coupling agent 0.5g, potassium peroxydisulfate 0.8g,
Nonionic emulsifier fatty alcohol polyoxyethylene ether 1.5g, anion emulsifier potassium oleate 1.0g, pH adjusting agent potassium hydroxide
0.5g, demulsifier calcium chloride 1.5g.
The preparation method is the same as that of Example 1.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value, be shown in Table 1.
Embodiment 5
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 2.0g, benzene second
Alkene (St) 89.4g, methylene-succinic acid 1.5g, vinylethoxysilane 0.1g, initiator potassium persulfate 1.0g, nonionic Emulsion
Agent fatty alcohol polyoxyethylene ether 4.0g, anion emulsifier enuatrol 1.0g, pH conditioning agent potassium hydroxide 0.5g, demulsifier
Alchlor 0.5g.
The preparation method is the same as that of Example 1.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value, be shown in Table 1.
Comparative example 1
Difference lies in increase the dosage of silica, reduce the use of styrene the embodiment with comparative example 1
Amount；The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 20.0g, styrene
(St) 74.2g, acrylic acid (AA) 0.4g, coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane 0.6g, initiator over cure
Sour ammonium 1.0g, nonionic emulsifier OP-10 2.0g, anion emulsifier lauryl sodium sulfate 0.5g, pH adjusting agent bicarbonate
Sodium 1.0g, demulsifier alum 0.3g.
The preparation process of gel resin is the same as embodiment 1.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value.
Fig. 4 is the microscope shape of polystyrene mixed with nano-silicon dioxide oil suction gel resin made from comparative example 1
Looks figure, figure 4, it is seen that compound particle has serious agglomeration, with the presence of larger particle, dispersibility is very poor, has
A large amount of precipitation particles.
Fig. 5 is polystyrene mixed with nano-silicon dioxide oil suction gel resin TEM figures made from comparative example 1, from figure
It can be seen that in 5：Particle largely deforms, and coalescence phenomenon is serious, and particle dispersibility is very poor.
Fig. 4 and Fig. 5 explanations, Nano-meter SiO_22Dosage is excessive, leads to its difficulties in dispersion, particle aggregation phenomenon is serious, specific surface
Product declines.
Comparative example 2
Difference lies in do not add nano silicon dioxide, what is obtained is polymer tree to the embodiment with comparative example 1
Fat；The Formulation Ingredients of the fluoropolymer resin are：Styrene (St) 94.2g, acrylic acid (AA) 0.4g, coupling agent γ-metering system
Monomethacryloxypropyl trimethoxy silane 0.6g, initiator ammonium persulfate 1.0g, nonionic emulsifier OP-10 2.0g, it is anionic emulsifying
Agent lauryl sodium sulfate 0.5g, pH adjusting agent sodium bicarbonate 1.0g, demulsifier alum 0.3g.
The preparation method is the same as that of Example 1.
It is not added with fumed silica, the lotion of preparation is silane-modified styrene-acrylic emulsion, and obtained product does not have suction
Oily effect.The lotion is commonly used in fields such as coating or adhesives；From comparative example 3 it is found that the polymer-doped nanometer
SiO2Oil suction gel resin is due to being doped with nano silicon dioxide into polystyrene resin so as to form oil suction gel tree
Fat has oil absorptive function, mainly due to being doped with nano silicon dioxide to make polymer-doped Nano-meter SiO_22Gel rubber material
Particle surface contains micro carboxyl functional group and silanol groups, have certain hydrophily, gel rubber material easily with water, soil knot
It closes, styrene is overcome to coat nano material apolar character；And specific surface area is very big, nano-particle is swollen after oil suction, oil absorption
Greatly, silanol groups, carboxyl functional group contained by surface silica dioxide form gelinite blocks because of Hydrogenbond between particle, to
Be conducive to gel rubber material to be separated from water.
Comparative example 3
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 3g, styrene
(St) 91.2g, acrylic acid (AA) 0.4g, coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane 0.6g, initiator over cure
Sour ammonium 1.0g, nonionic emulsifier 2.0g, anion emulsifier lauryl sodium sulfate 0.5g, pH adjusting agent sodium bicarbonate
1.0g, demulsifier alum 0.3g.
Gel resin is prepared according to following technique：
(1) two kinds of emulsifiers are dissolved in 165g deionized waters, are configured to compound emulsifying agent aqueous solution, for use；It will draw
Hair agent is dissolved in 20g deionized waters, is configured to initiator solution, for use；
(2) styrene (St) and function monomer are stirred evenly according to quality proportioning addition reaction kettle and is configured to monomer mixing
Solution；By Nano-meter SiO_22Conical flask is added with coupling agent, stirs 60min with blender, the mixed solution of reaction kettle is then added
In stir evenly, mixing time 30min obtains Nano-meter SiO_22The mixture of/monomer mixture solution；
Other steps are the same as embodiment 1.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value, be shown in Table 1.
The comparative example is used and is first surface-treated to fumed silica, i.e. silane coupling agent and silica
Reaction, result are easy to cause chemical bond crosslinking generation coalescence between particle, it is difficult to detach again.
Fig. 6 is polystyrene mixed with nano-silicon dioxide oil suction gel resin TEM figures made from comparative example 3；From figure
It can be seen that in 6：Particle aggregation phenomenon is serious, and particle dispersibility is poor, and particle largely deforms.
Comparative example 4
The polymer-doped Nano-meter SiO_22The Formulation Ingredients of oil suction gel resin are：Fumed silica 3g, styrene
(St) 91.2g, acrylic acid (AA) 0.4g, coupling agent gamma-methyl allyl acyloxypropyl trimethoxysilane 0.6g, initiator over cure
Sour ammonium 1.0g, anion emulsifier lauryl sodium sulfate 2.5g, pH adjusting agent sodium bicarbonate 1.0g, demulsifier alum
0.3g。
The preparation method is the same as that of Example 1.
Only add a kind of emulsifier sodium lauryl sulfate in the comparative example, at the end of emulsifying stage, emulsion goes out
Existing split-phase, that is, generate oil/water separation, and stability of emulsion is poor.
Test polystyrene dopen Nano SiO2After the degree of cross linking of gel resin, toluene swell degree and processing toluene aqueous solution
Concentration value, be shown in Table 1.
Fig. 6 is polystyrene mixed with nano-silicon dioxide oil suction gel resin TEM figures made from comparative example 4；From figure
It can be seen that in 6：Particle aggregation phenomenon is serious, and particle dispersibility is poor, and particle largely deforms.
The oil suction gel resin is used as fragrant hydrocarbons and their derivates or the waste water treating agent of aromatic hydrocarbon nitro compound, or contains
The waste water treating agent of the oil product of arene.
Above-described embodiment 1~5 and polystyrene dopen Nano SiO obtained by comparative example 1~42Gel resin
Using application process is：By taking toluene aqueous solution (25 DEG C, 0.050g/100ml) as an example, but it is not limited only to toluene aqueous solution,
Method is：The polymer-doped nanosized SiO_2 oil suction gel resin powder of 1g is taken, is added in 100ml, 25 DEG C of toluene aqueous solutions, low speed
2h, mixing speed 100r/min are stirred, after stirring, oil suction gel is isolated after standing 30min, then uses Shanghai glad
Luxuriant Instrument Ltd. UV7504 type ultraviolet-visible spectrophotometers test oil suction gel toluene aqueous solution treated concentration
Value.
Table 1 is Examples 1 to 5 and the polystyrene dopen Nano SiO obtained by comparative example 1~42Gel resin
Concentration value test result after the degree of cross linking, toluene swell degree and processing toluene aqueous solution.
1 the performance test results of table
The present invention is not limited to above-mentioned particular implementation, is made under the premise of not departing from above-mentioned basic fundamental thought
Various deformations or amendments all fall within the row of rights protection scope of the present invention.
Claims (10)
1. a kind of polymer-doped Nano-meter SiO_22Oil suction gel resin, which is characterized in that the polymer-doped Nano-meter SiO_22Oil suction is solidifying
The Formulation Ingredients of gum resin are by mass percentage：Styrene 70~95%；Nano silicon dioxide 0.1~15%；Function monomer
0.01~1.5%；Coupling agent 0.01~2.5%；Initiator 0.1~2%；Compound emulsifying agent 0.5~8%；PH adjusting agent 0.1~
1.0%；Demulsifier 0.1~0.5%.
2. polymer-doped Nano-meter SiO_2 according to claim 12Oil suction gel resin, which is characterized in that the polymer is mixed
Miscellaneous Nano-meter SiO_22The chemical structural formula of oil suction gel resin is：
3. polymer-doped Nano-meter SiO_2 according to claim 12Oil suction gel resin, which is characterized in that the nano-silica
SiClx is fumed nano silica or precipitation method nano silicon dioxide, and the function monomer is α-methacrylic acid, methylene
One kind in base succinic acid, acrylic acid, maleic anhydride or at least two combination；The coupling agent is titanate coupling agent or silicon
Alkane coupling agent, the initiator be potassium peroxydisulfate, ammonium persulfate, one kind in dibenzoyl peroxide or at least two group
It closes.
4. polymer-doped Nano-meter SiO_2 according to claim 12Oil suction gel resin, which is characterized in that the composite emulsifying
Agent is：The emulsifier is the compound being made of nonionic emulsifier and anion emulsifier, wherein nonionic emulsifier and
The mass ratio of anion emulsifier is 0.01~4:1.
5. polymer-doped Nano-meter SiO_2 according to claim 42Oil suction gel resin, which is characterized in that the anion breast
Agent is enuatrol, potassium oleate, disproportionated rosin sodium, sodium laurate, neopelex, lauryl sodium sulfate, propylene
One kind in amide groups sodium isopropyl xanthate or at least two combination；The nonionic emulsifier is Nonyl pheno
Ether, Vinlub 73, polyoxy alkene Sorbitan acid monoleate or one kind in fatty alcohol polyoxyethylene ether or extremely
Few two kinds of combination.
6. polymer-doped Nano-meter SiO_2 according to claim 12Oil suction gel resin, which is characterized in that the pH adjusting agent
For in sodium carbonate, sodium bicarbonate, ammonium hydroxide, potassium hydroxide, sodium hydroxide one kind or at least two combination；The demulsifier is
One kind in alum, alchlor, magnesium sulfate, calcium chloride, magnesium chloride, dilute hydrochloric acid, dilute sulfuric acid or at least two combination.
7. a kind of preparing the polymer-doped Nano-meter SiO_2 as described in claim any one of 1-62The method of oil suction gel resin, it is special
Sign is, specifically comprises the following steps：
(1) compound emulsifying agent is dissolved in deionized water, is configured to emulsifier aqueous solution, for use；Initiator is dissolved in
In ionized water, it is configured to initiator solution, for use；
(2) reaction kettle is added according to quality proportioning in styrene, function monomer and coupling agent to stir evenly, is configured to monomer mixing
Solution, then by Nano-meter SiO_22It is added in monomer mixture solution and stirs evenly, Nano-meter SiO_2 is made2The mixing of/monomer mixture solution
Object；
(3) Nano-meter SiO_2 made from step (2) is added in the prepared emulsifier aqueous solution of step (1)2/ monomer mixture solution mixes
It closes in object, agitated device high-speed stirred, high-speed stirred rotating speed is more than 500r/min, and after dispersion and emulsion, pH adjusting agent tune is added
It is 9~10 to save pH value, obtains the emulsion of the stabilization of appearance milky white；
(4) 1/3 initiator for taking out 2/3 emulsion out of step (3) reaction kettle and funnel being added, and step (1) is taken to prepare
Aqueous solution is added in reaction kettle, and the emulsion in remaining 2/3 initiator solution and funnel is spare；
(5) it is 120~180r/min to control mixing speed in reaction kettle, is heated to 65~80 DEG C, and control temperature in the kettle
It is 65~80 DEG C, when lotion blueing light in reaction kettle, starts the synchronous breast being added dropwise in remaining initiator solution and funnel
Change liquid, and control rate of addition and synchronized in 1.5~2h and dripped, polymer-doped Nano-meter SiO_2 is made in the reaction was continued 1~2h2
Lotion；
(6) the polymer-doped Nano-meter SiO_2 obtained after being reacted to step (5)2Demulsifier aqueous solution, heat temperature raising are added dropwise in lotion
To 80~90 DEG C, and with the rotating speed high-speed stirred of 200~1000rpm, the paste until system becomes sticky continues heating stirring 0.5
~2h, product filter and filter to obtain white filter cake through vacuum pump using circulatory water；
(7) filter cake that step (6) obtains is placed in drying box at 80 DEG C and is dried in vacuo for 24 hours, crushing obtains polymer-doped
Nano-meter SiO_22Oil suction gel resin.
8. polymer-doped Nano-meter SiO_2 according to claim 72The preparation method of oil suction gel resin, which is characterized in that institute
The mixing time for stating step (2) is 30~40min；The dispersion and emulsion time of the step (3) is 30~40min；The step
(5) be added dropwise emulsion and the temperature of initiator is 70 DEG C, time for adding 1.5h；Being added dropwise to complete the rear temperature that the reaction was continued is
70 DEG C, reaction time 1.5h.
9. a kind of according to any one of the claim 1-6 polymer-doped Nano-meter SiO_2s2The application of oil suction gel resin, feature
It is, the polymer-doped Nano-meter SiO_22Oil suction gel resin is used as the useless of fragrant hydrocarbons and their derivates or aromatic hydrocarbon nitro compound
Water treatment agent or the polymer-doped Nano-meter SiO_22Oil suction gel resin is used as the wastewater treatment of the oil product containing arene
Agent.
10. polymer-doped Nano-meter SiO_2 according to claim 92The application of oil suction gel resin, which is characterized in that the polymerization
Object dopen Nano SiO2The method of the application of oil suction gel resin includes the following steps：Take polymer-doped Nano-meter SiO_22Oil suction is solidifying
The powder of gum resin is added in waste water solution, and at 25 DEG C, 2~4h of stirring at low speed, mixing speed is 120~180r/min, quiet
Oil suction gel resin is isolated from waste water solution after setting 30min, test uses polymer-doped Nano-meter SiO_22Oil suction gel tree
The concentration value of fat treated waste water solution.
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| CN111607895A (en) * | 2020-06-23 | 2020-09-01 | 常州工程职业技术学院 | Melt-blown fabric suitable for filtering oily particles and preparation method thereof |
| CN113088104A (en) * | 2021-03-29 | 2021-07-09 | 苏州达米昂科技有限公司 | Process for preparing high-dispersion homogeneous nano silicon dioxide spheres |
| CN118109089A (en) * | 2024-04-30 | 2024-05-31 | 拓迪化学(上海)股份有限公司 | Polyolefin emulsion and preparation method and application thereof |
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