CN102249255B - Anionic-nonionic composite organic montmorillonite and preparation method thereof - Google Patents
Anionic-nonionic composite organic montmorillonite and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 68
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000009830 intercalation Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
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- 238000006703 hydration reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 polyoxyethylene nonylphenol Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 4
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- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
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- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses nonionic-anionic composite intercalated organic montmorillonite and a preparation method thereof. The method comprises the following steps of: purifying montmorillonite; hydrating the montmorillonite, namely preparing water suspension from the purified montmorillonite, and hydrating in a mechanical stirring and ultrasonic action mixed mode; and preparing a nonionic-anioniccomposite intercalated organic montmorillonite material, namely cooperatively intercalating the montmorillonite by using an organic nonionic surfactant and an anionic surfactant under the action of ultrasonic dispersion and mechanical stirring. The organic montmorillonite has a long layer distance and high heat stability, stripping degree and performance, is uniformly dispersed in an organic phase, and can be used as a high-performance filler to be applied to the field of preparation of high polymer nanocomposite materials.
Description
Technical field
The present invention relates to the organically-modified novel process of montmorillonite, more specifically relate to nonionic-negatively charged ion composite intercalation type organic montmorillonite and preparation method thereof.By method provided by the invention, adopt negatively charged ion and nonionic surface active agent to come compound intercalation modifying montmorillonite, can make High interlayer spacing, high performance organic montmorillonite.
Background technology
Montmorillonite is a kind of moisture layer aluminosilicate mineral, forms by chlorine aluminium of two silicon-oxy tetrahedron therebetween (magnesium) oxygen (hydrogen-oxygen) are octahedra, and lattice spacing is about 0.96nm, and interlayer has tradable Na
+, Ca
2+, Mg
2+Deng positively charged ion, can exchange with other positively charged ions.
Organic montmorillonite has extensive use, has been applied to the departments such as lubricating grease, paint, printing ink, makeup, medical and health, environmental improvement, food and national defense industry.The organic montmorillonite interlamellar spacing d that sells in the market
001Value is many in the 2.0nm left and right, because organic degree is lower, causes dispersion effect and the extent of exfoliation of product in organic phase not good.
Produce at present organic montmorillonite both at home and abroad and adopt cationic surfactant more, exchange by the positively charged ion between positively charged ion and cheating engaging layer and introduce organic group between cheating engaging layer, product is single, performance can not satisfy still that requirement, especially its thermostability in each related application field is relatively poor, product colour has limited its application in the high molecule nano composite material field more deeply.
For example, the Chinese patent application of CN101774598A discloses the preparation method of the modified clay of alkyl ammonium salt surfactant intercalation, suspension in water with the solvent reaction that contains alkyl ammonium salt surfactant or by with clay powder and alkyl ammonium salt surfactant solubilizing reaction, obtains the modified clay of alkyl ammonium salt surfactant intercalation by clay for it.But, the interlamellar spacing of gained modified clay needs to be further increased.
L.Zampori etc. successfully make d take polyoxyethylene glycol as properties-correcting agent
001Value is the organic montmorillonite of 1.79nm, and points out that the intercalation effect of non-ionic type organic montmorillonite and temperature, PH have nothing to do, and is only relevant with modifier concentration.
Application for a patent for invention 200310122774.3 discloses a kind of sun, non-ionic type organic montmorillonite of preparing, its method is that wilkinite original soil dry, that pulverized 20～100 mesh sieves is poured in the mixed surfactants solutions of certain proportioning, at 50～80 ℃ of stirred in water bath 2～24h, product is used distilled water wash 2 times after filtration, after being filtered dry, oven dry under 60～90 ℃, then activate 30min～5h under 105 ℃, through grinding, cross 100 mesh sieves, make cationic-nonionic organobentonite.This technological reaction time is long, technique is loaded down with trivial details.
Domestic and international many scientific worker's will power are in the novel organic montmorillonite of research preparation at present.How to improve environment between montmorillonite layer, changing the montmorillonite layer spacing is study hotspot.
And there is no at present about common modified montmorillonite used with nonionic surface active agent and aniorfic surfactant and the report of organic montmorillonite product.
Summary of the invention
The object of the present invention is to provide the preparation method of nonionic-negatively charged ion composite intercalation type organic montmorillonite, the method comprises the following steps:
A. purifying montmorillonite: na-montmorillonite is purified;
B. montmorillonite is carried out hydration process: the montmorillonite after purifying is made aqeous suspension, carries out hydration process by the mode that mechanical stirring is mixed with ultrasonication;
C. prepare nonionic-negatively charged ion composite intercalation type organic montmorillonite material: fully the montmorillonite hydrating fluid of aquation is designated as A liquid, organic nonionic surface active agent and organic anion type tensio-active agent are dissolved in certain water gaging are mixed with emulsion through ultra-sonic dispersion and mechanical agitation and are designated as B liquid, add B liquid in A liquid and carry out the ultra-sonic dispersion effect, follow-up mechanical stirring again, constant temperature is standing, separate, drying obtains nonionic-negatively charged ion composite intercalation type organic montmorillonite material.
Another object of the present invention is to provide the nonionic that makes by aforesaid method-negatively charged ion composite intercalation type organic montmorillonite.
The present invention adopts the method for nonionic surface active agent and the compound intercalation of aniorfic surfactant to prepare novel organic montmorillonite, the inventive method technical process is simple, modifier source is easy to get, the gas producing formation spacing is high, thermostability is high, is uniformly dispersed in organic phase, and extent of exfoliation is high, excellent performance can be used as a kind of applying filler of excellent performance to preparation high molecule nano composite material field.
Description of drawings
Fig. 1 is na-montmorillonite crystalline structure schematic diagram.
Fig. 2 is the XRD figure of gained nonionic-negatively charged ion composite intercalation type organic montmorillonite in embodiment 2, and wherein MMT represents montmorillonite.
Fig. 3 is the XRD figure of gained nonionic-negatively charged ion composite intercalation type organic montmorillonite in embodiment 3, and wherein MMT represents montmorillonite.
Fig. 4 is the XRD figure of na-montmorillonite.
Embodiment
Below in conjunction with embodiment, the present invention is carried out in detail.By these descriptions, it is more clear that the features and advantages of the invention will become.
The invention provides the preparation method of nonionic-negatively charged ion composite intercalation type organic montmorillonite, the method comprises the following steps:
A. purifying montmorillonite: na-montmorillonite is purified;
B. montmorillonite is carried out hydration process: the montmorillonite after purifying is made aqeous suspension, carries out hydration process by the mode that mechanical stirring is mixed with ultrasonication;
C. prepare nonionic-negatively charged ion composite intercalation type organic montmorillonite material: fully the montmorillonite hydrating fluid of aquation is designated as A liquid, organic nonionic surface active agent and organic anion type tensio-active agent are dissolved in certain water gaging are mixed with emulsion through ultra-sonic dispersion and mechanical stirring and are designated as B liquid, then join B liquid in A liquid and carry out the ultra-sonic dispersion effect, follow-up mechanical stirring again, constant temperature is standing, separate, drying obtains nonionic-negatively charged ion composite intercalation type organic montmorillonite material.
Steps A
In preparation method of the present invention, the effect of steps A is that na-montmorillonite is carried out purifying, removes impurity, can by na-montmorillonite is pulverized, the settlement separate realization in water.
in a preparation method's of the present invention preferred embodiment, steps A comprises: with ball mill with the na-montmorillonite raw material pulverizing, cross 200 mesh sieves, montmorillonite is dispersed in water is made into suspension and makes its " concentration " be no more than 10g/L, electric stirring 15-60 minute, preferred 20-30 minute, more preferably 20 minutes, standing for some time of room temperature, preferred 6-20 hour, preferred 8-10 hour, take out the upper strata suspension liquid with siphon pipe, centrifugation, at elevated temperatures as 60-100 ℃, especially approximately dry under 70 ℃, get purifying montmorillonite, remaining part adds distilled water again, after being returned to former state, volume continues to stir 15-60 minute, preferred 20-30 minute, more preferably 20 minutes, standing for some time, preferred 6-20 hour, preferred after 8-10 hour, take out again the upper strata suspension liquid, so repeatedly several times, until remainder adds the distilled water rear suspension liquid relatively to clarify again.
Step B
In preparation method of the present invention, the effect of step B is that the montmorillonite after purifying is carried out abundant aquation, by the combination of ultra-sonic dispersion effect and mechanical agitation, montmorillonite effectively can be disperseed in water, promote cloudy, nonionic surface active agent to enter between montmorillonite layer.
The inventor finds by research, compares with simple mechanical agitation, and the dispersion effect in water is well a lot of for montmorillonite for the mode that the ultra-sonic dispersion effect is combined with mechanical agitation.Found through experiments, compare with the interlamellar spacing of carrying out the aquation montmorillonite that aquation obtains by mechanical stirring, the interlayer of the aquation montmorillonite that carries out the aquation acquisition of being combined with mechanical agitation by the ultra-sonic dispersion effect on average increases 0.5-1.0nm.Reason for this reason may be that ultrasonic physical influence to montmorillonite and chemical effect have promoted the further dispersion of montmorillonite.
In a preparation method's of the present invention preferred embodiment, step B comprises: with the montmorillonite of purifying and water 3-15 in mass ratio: 100, and preferred 3-10: 100, more preferably 4-6: 100, also more preferably the proportional arrangement of 5: 100 becomes suspension, transfer in flask, control temperature at 50-80 ℃, preferred 60-70 ℃, more preferably 70 ℃ of left and right, adopt mechanical stirring to be aided with the mode aquation of ultra-sonic dispersion, hydration time is preferably 20-120 minute, more preferably 30-60 minute.
In the step B of the inventive method, ultrasonic power used is preferably 50-400W, more preferably from about 250W.
Step C
In preparation method of the present invention, the effect of step C is to make the collaborative intercalation of emulsion by nonionogenic tenside and anion surfactant to enter between montmorillonite layer, thereby the support of montmorillonite layer spacing is large, thereby prepare strippable nonionic-negatively charged ion composite intercalation type organic montmorillonite material.
find unexpectedly, when by ultra-sonic dispersion effect and mechanical agitation, after using nonionic surface active agent to carry out the intercalation improvement to montmorillonite, again by ultra-sonic dispersion effect and mechanical agitation, aniorfic surfactant and nonionic surface active agent are entered between montmorillonite layer, support large montmorillonite layer spacing, obtain large modified montmorillonite used of interlamellar spacing support, in addition, especially thermostability is high due to the stability of nonionic surface active agent and aniorfic surfactant, therefore, the modified montmorillonite used stability of gained especially thermostability obviously improves.
By the inventive method obtain nonionic-negatively charged ion composite intercalation type organic montmorillonite material interlamellar spacing is high, its separability, thermostability and the excellent dispersion in organic phase can be used as the applying filler of excellent performance in the field of preparation high molecule nano composite material.
In a preparation method's of the present invention preferred embodiment, step C comprises: fully the montmorillonite hydrating fluid of aquation is A liquid, organic nonionic surface active agent and organic anion type tensio-active agent are dissolved in certain water gaging are mixed with emulsion through ultra-sonic dispersion and mechanical stirring and are designated as B liquid, join B liquid in A liquid and carry out the ultra-sonic dispersion effect, follow-up mechanical stirring again, constant temperature is standing, separates, drying obtains nonionic-negatively charged ion composite intercalation type organic montmorillonite material.
In a preparation method's of the present invention preferred embodiment, in step C, separating, after drying, the aftertreatment manufacturing procedure such as can pulverize.
In a preparation method's of the present invention preferred embodiment, in step C, in the process of whole step C, the temperature of reaction system is controlled in 40-80 ℃ of scope, in preferred 50-70 ℃ of scope, and more preferably from about 60 ℃.
In a preparation method's of the present invention preferred embodiment, in step C, the time of carrying out each ultra-sonic dispersion effect is preferably respectively below 60 minutes independently, more preferably below 30 minutes, also more preferably below 20 minutes.
In a preparation method's of the present invention preferred embodiment, in step C, the time of carrying out each mechanical agitation is preferably respectively more than 30 minutes independently, more preferably more than 1 hour, and also more preferably 1-2 hour.
In a preparation method's of the present invention preferred embodiment, in step C, nonionic surface active agent used is selected from polyoxyethylene nonylphenol ether (OP-10), Witco 1298 Soft Acid, dodecyl sodium sulfonate, polyoxyethylene glycol and polyvinyl alcohol.These nonionic surface active agent can use separately, also can arbitrary combination use.
In a preparation method's of the present invention preferred embodiment, in step C, the amount of nonionic surface active agent used is the 0.5-10 % by weight of A liquid gross weight,, preferred 0.5-6 % by weight, also more preferably 1-3 % by weight.
In a preparation method's of the present invention preferred embodiment, in step C, aniorfic surfactant used is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium oleate and sodium stearate.These aniorfic surfactant can use separately, also can arbitrary combination use.
In a preparation method's of the present invention preferred embodiment, in step C, the amount of aniorfic surfactant used is the 0.5-10 % by weight of A liquid gross weight,, preferred 0.5-6 % by weight, also more preferably 1-3 % by weight.
The inventor studies discovery, by above-mentioned nonionic surface active agent and the combination of above-mentioned aniorfic surfactant are used for the intercalation modifying montmorillonite, can obtain the high strippable nonionic of interlamellar spacing-negatively charged ion composite intercalation type organic montmorillonite.
in a preparation method's of the present invention preferred embodiment, step C comprises: fully the montmorillonite slurry of aquation is A liquid, with appropriate 0.5-10 % by weight as A liquid gross weight, , preferred 0.5-6 % by weight, also more preferably organic nonionic surface active agent of 1-3 % by weight with in right amount as the 0.5-10 % by weight of A liquid gross weight, preferred 0.5-6 % by weight, also more preferably the aniorfic surfactant of 1-3 % by weight joins in 80-100ml water, make emulsion B liquid through ultra-sonic dispersion and mechanical agitation 10-30min, B liquid is joined in A liquid, follow-up mechanical stirring 1-2 hour, stop stirring and the standing 1-2 of constant temperature hour, at the temperature of said process in 40-80 ℃ of scope, constant temperature carries out, centrifugal, dry, pulverize to get the Anionic-nonionic composite intercalation type organic montmorillonite.
The present invention also provides the nonionic for preparing by aforesaid method-negatively charged ion composite intercalation type organic montmorillonite.
Preparation method of the present invention and nonionic-negatively charged ion composite intercalation type organic montmorillonite has the following advantages:
1. non-ionic type and two kinds of surfactant-modified montmorillonites of anionic are used in this invention first, and make intercalation effect excellence, well behaved organic montmorillonite;
2. Ultrasonic Irradiation is applied to montmorillonite aquation and properties-correcting agent intercalation process, has realized preparing the purpose of nonionic-anionic organic montmorillonite powder in high-content montmorillonite slurries and high density nonionic surface active agent system, aniorfic surfactant system;
The nonionic of gained of the present invention-negatively charged ion composite intercalation type organic montmorillonite in organic solvent through high speed shear can realize the layer with layer peel off, with nano level lamella Uniform Dispersion, significantly improve the rotary viscosity of system, and embodying good rheological, thixotropy, the polymer packing that therefore can be used as a kind of excellent performance uses.
4. the nonionic of gained of the present invention-negatively charged ion composite intercalation type organic montmorillonite material possesses good thickening power, can be widely used in the fields such as lubricating grease, coating, paint, printing ink, environmental improvement; And this organic montmorillonite shows the not available characteristic of general inorganic powder, can combine closely with organic matrix, and this provides the filler of excellent performance for preparing Montmorillonite/Nanocomposite dissimilar, excellent combination property.
Embodiment
Experimental section
The X-ray diffraction experiment
The D/MAX2000 type X ray powder crystal diffractometer (Cu target K alpha-ray) that uses HIT to produce at λ=0.15406nm, goes on foot wide=0.02, operating voltage 40Kv, and under working current 100mA condition, analytic sample.
Thermogravimetric analysis
The SHB-D type differential thermal analyzer that uses HIT to produce is at 10 ℃ of min-1 of temperature rise rate, analytic sample under the air atmosphere condition.
In each embodiment, ultrasonic power is 250W.
The purification of embodiment 1 montmorillonite
1. with ball mill, the montmorillonite raw ore is pulverized, crossed 200 mesh sieves, get montmorillonite powder;
2. taking the 80g montmorillonite powder is dissolved in 8L distilled water and (uses barreled), the electricity consumption agitator stirred 20 minutes, montmorillonite is made into the suspension that " concentration " is no more than 10g/L, continued standing 8 hours under room temperature state, take out the part of height＜10cm with siphon pipe;
3. get upper strata 10cm suspension liquid, centrifugal, vacuum-drying (70 ℃) gets refining montmorillonite;
4. remaining part adds distilled water again, continues to stir 20 minutes after volume is returned to original volume, makes not " taking apart " and the residual particle greater than 2 μ m disperses, after 8 hours again with it taking-up.So repeatedly several times, until remainder adds after distilled water the suspension of gained relatively to clarify again.
The preparation of embodiment 2 nonionics-negatively charged ion composite intercalation type organic montmorillonite
be 88meq/100g with the cation exchange capacity of purifying through water law that obtains in embodiment 1, the na-montmorillonite 5g that particle diameter is crossed 200 mesh sieves joins in the there-necked flask that fills 100ml water, the ultrasonic mechanical stirring aquation that adds was designated as A liquid in 1 hour, 2g polyoxyethylene nonylphenol ether and 3g Sodium dodecylbenzene sulfonate are slowly joined in 80g water, 30 minutes postscripts of ultra-sonic dispersion and mechanical stirring are B liquid, then B liquid joined in A liquid and continue mechanical stirring 1.5 hours, stop stirring, be cooled to the room temperature centrifugation, with deionized water washing sample 1 time, dry a few hours under 80 ℃ of conditions in loft drier, be ground to 200 mesh sieves, namely get nonionic-negatively charged ion composite intercalation type organic montmorillonite.
The x-ray diffraction spectra (XRD figure) of gained nonionic-negatively charged ion composite intercalation type organic montmorillonite as shown in Figure 2.As shown in Figure 2, the interlamellar spacing of this organic montmorillonite is 4.40nm.
The preparation of embodiment 3 nonionics-negatively charged ion composite intercalation type organic montmorillonite
be 88meq/100g with the cation exchange capacity of purifying through water law that obtains in embodiment 1, the na-montmorillonite 5g that particle diameter is crossed 200 mesh sieves joins in the there-necked flask that fills 100ml water, the ultrasonic mechanical stirring aquation that adds was designated as A liquid in 1 hour, 2g polyoxyethylene nonylphenol ether and 3g sodium stearate are joined in 80g water, 30 minutes postscripts of ultra-sonic dispersion and mechanical stirring are B liquid, then B liquid joined in A liquid and continue mechanical stirring 1.5 hours, stop stirring, be cooled to the room temperature centrifugation, with deionized water washing sample 1 time, dry a few hours under 80 ℃ of conditions in loft drier, be ground to 200 mesh sieves, namely get nonionic-negatively charged ion composite intercalation type organic montmorillonite.
The x-ray diffraction spectra (XRD figure) of gained nonionic-negatively charged ion composite intercalation type organic montmorillonite as shown in Figure 3.As shown in Figure 3, the interlamellar spacing of this organic montmorillonite is 4.51nm.
Comparative example 1
Prepare organically modified montmorillonite clay according to the method for embodiment in CN101182393B 1.
The interlamellar spacing of this organic montmorillonite is 1.21nm.
Compare with the organically modified montmorillonite clay that obtains in comparative example, in the embodiment of the present invention, the interlamellar spacing of gained nonionic-negatively charged ion composite intercalation type organic montmorillonite is larger, and thermostability is higher, and performance is excellent more different.
Comparative example is to prepare organobentonite by anion surfactant and the absorption of precipitation agent precipitation.In sodium bentonite suspension, add anion surfactant, by reacting with precipitation agent, form chemisorption and physisorption on bentonite bed.Precipitation agent mainly is adsorbed in the wilkinite surface, but not enters interlayer.
And in the present invention, nonionic surface active agent and aniorfic surfactant all enter between montmorillonite layer, by the synergy of both intercalation modifyings, the montmorillonite layer spacing is by further support is large, and the interlamellar spacing that causes the organically modified montmorillonite clay that makes is higher than comparative example.
In addition, the thermostability of nonionogenic tenside and anionic is all fine, causes the thermostability of the organically modified montmorillonite clay that makes also correspondingly high.
Above in conjunction with embodiment extremely preferred embodiment the present invention is described in detail, but these are described and not to be consisted of limitation of the scope of the invention.Be to be understood that; in the situation that do not depart from the scope of the invention and spirit; can carry out multiple modification, improvement and replacement to technical scheme of the present invention and embodiment thereof, these are modified, improve and replace and all should fall in the protection domain of appended claims.
Claims (9)
1. the preparation method of nonionic-negatively charged ion composite intercalation type organic montmorillonite, the method comprises the following steps:
A. purifying montmorillonite: na-montmorillonite is purified;
B. montmorillonite is carried out hydration process: the montmorillonite after purifying is made aqeous suspension, carries out hydration process by the mode that mechanical stirring is mixed with ultrasonication;
C. prepare nonionic-negatively charged ion composite intercalation type organic montmorillonite material: fully the montmorillonite hydrating fluid of aquation is designated as A liquid, organic nonionic surface active agent and organic anion type surfactant dissolves ultra-sonic dispersion and mechanical stirring certain hour in certain water gaging are got B liquid, then B liquid is joined in A liquid, follow-up mechanical stirring again, constant temperature is standing, separate, drying obtains nonionic-negatively charged ion composite intercalation type organic montmorillonite material;
Wherein, in step C, described nonionic surface active agent is one or more in polyoxyethylene nonylphenol ether, Witco 1298 Soft Acid, dodecyl sodium sulfonate, polyoxyethylene glycol and polyvinyl alcohol,
Described aniorfic surfactant is one or more in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium oleate and sodium stearate.
2. method according to claim 1, wherein, rapid A comprises: with ball mill with the na-montmorillonite raw material pulverizing, cross 200 mesh sieves, montmorillonite is dispersed in water is made into suspension and makes its " concentration " be no more than 10g/L, electric stirring 15-60 minute, the standing 6-20 of room temperature hour, take out the upper strata suspension liquid with siphon pipe, centrifugation, dry under 60-100 ° of C, get purifying montmorillonite, remaining part adds distilled water again, after being returned to former state, volume continues to stir 15-60 minute, standing 6-20 hour, take out again the upper strata suspension liquid, so repeatedly several times, until remainder adds the distilled water rear suspension liquid relatively to clarify again.
3. method according to claim 1 and 2, wherein, step B comprises: with the montmorillonite of purifying and water in mass ratio the proportional arrangement of 3-15:100 become suspension, transfer in flask, control temperature at 50-80 ℃, adopt mechanical stirring to be aided with the mode aquation of ultra-sonic dispersion, hydration time is 20-120 minute.
4. method according to claim 1, wherein, in step B, ultrasonic power used is preferably 50-400W.
5. method according to claim 1, wherein, in step C, in the process of whole step C, the temperature of reaction system is controlled in 40～80 ℃ of scopes.
6. method according to claim 1, wherein, in step C, the time of carrying out each ultra-sonic dispersion effect is respectively below 60 minutes independently; The time of carrying out each mechanical agitation is respectively more than 30 minutes independently.
7. method according to claim 1, wherein, in step C, the consumption of described nonionic surface active agent is the 0.5-10 % by weight of A liquid gross weight.
8. the method for stating according to claim 1, wherein, in step C, the consumption of described aniorfic surfactant is the 0.5-10 % by weight of A liquid gross weight.
9. nonionic-negatively charged ion composite intercalation type organic montmorillonite, it is by method preparation described in any one according to claim 1-8.
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| CN105733316B (en) * | 2016-01-27 | 2018-03-30 | 北京理工大学 | A kind of preparation method of acylate intercalation modifying montmorillonite |
| CN107814388A (en) * | 2016-09-12 | 2018-03-20 | 先声药业有限公司 | A kind of preparation method of montmorillonite |
| CN106268654A (en) * | 2016-09-21 | 2017-01-04 | 安徽瀚景观规划设计院有限公司 | A kind of preparation method of water pollution adsorbing material |
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| CN106587086A (en) * | 2016-12-02 | 2017-04-26 | 中国矿业大学(北京) | Nonionic surfactant modified montmorillonite and preparation method thereof |
| CN107620207B (en) * | 2017-09-12 | 2020-10-30 | 吉林大学 | Preparation method of aqueous anti-ultraviolet finishing liquid based on illite mineral |
| CN109110772B (en) * | 2018-02-13 | 2020-12-01 | 应急管理部天津消防研究所 | Preparation method of loaded metal organic montmorillonite |
| CN111545763B (en) * | 2020-05-26 | 2022-01-04 | 江苏大方金属粉末有限公司 | Preparation method of modified copper-gold powder |
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