CN102249255A - Anionic-nonionic composite organic montmorillonite and its preparation method - Google Patents
Anionic-nonionic composite organic montmorillonite and its preparation method Download PDFInfo
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Abstract
本发明公开了非离子-阴离子复合插层型有机蒙脱石极其制备方法，该方法包括以下步骤：提纯蒙脱石；对蒙脱石进行水化处理：将提纯后的蒙脱石制成水悬浮液，通过机械搅拌与超声作用混合的方式进行水化处理；制备非离子-阴离子复合插层型有机蒙脱石材料：使用有机非离子型表面活性剂和阴离子型表面活性剂，在超声分散作用和机械搅拌作用下，协同对蒙脱石进行插层。本发明的有机蒙脱石层间距高，热稳定性高，在有机相中分散均匀，剥离程度高，性能优异，可作为一种性能优异的填料应用到制备高分子纳米复合材料领域。
The invention discloses a non-ion-anion compound intercalation type organic montmorillonite and a preparation method thereof. The method comprises the following steps: purifying the montmorillonite; performing hydration treatment on the montmorillonite: making the purified montmorillonite into water Suspension, hydration treatment by mixing with mechanical stirring and ultrasonic action; preparation of non-ionic-anionic composite intercalation type organic montmorillonite material: using organic non-ionic surfactant and anionic surfactant, dispersed in ultrasonic Intercalation of montmorillonite is carried out synergistically under the action of mixing and mechanical stirring. The organic montmorillonite of the invention has high layer spacing, high thermal stability, uniform dispersion in the organic phase, high exfoliation degree and excellent performance, and can be used as a filler with excellent performance in the field of preparing polymer nanocomposite materials.
Description
Technical field
The present invention relates to the organically-modified novel process of montmorillonite, more specifically relate to compound intercal type organic montmorillonite of nonionic-negatively charged ion 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 interlamellar spacing, high performance organic montmorillonite.
Background technology
Montmorillonite is a kind of aqueous layer aluminosilicate mineral that contain, and 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 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 of Chu Shouing in the market
001Value is many about 2.0nm, because of organic degree is lower, causes dispersion effect and the extent of exfoliation of product in organic phase not good.
Produce organic montmorillonite at present 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 between cheating engaging layer, to introduce organic group, product is single, performance still can not satisfy the requirement in each related application field, and especially relatively poor, the product colour of its thermostability 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, it 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 the suspension of clay in water.But, the interlamellar spacing of gained modified clay remains further to be increased.
L.Zampori etc. are that properties-correcting agent successfully makes d with the polyoxyethylene glycol
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 preparation sun, non-ionic type organic montmorillonite, 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 filter is done, 60～90 ℃ of oven dry down, activate 30min～5h down at 105 ℃ again, through grinding, cross 100 mesh sieves, make sun-nonionic organobentonite.This technological reaction time is long, technology 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 interfloor distance is the research focus.
And still have nothing to do at present in report common modified montmorillonite used with nonionic surface active agent and aniorfic surfactant and must the organic montmorillonite product.
Summary of the invention
The object of the present invention is to provide the preparation method of the compound intercal type organic montmorillonite of nonionic-negatively charged ion, this method may further comprise the steps:
A. purifying montmorillonite: na-montmorillonite is purified;
B. montmorillonite being carried out aquation handles: the montmorillonite after will purifying is made aqeous suspension, carries out aquation by mechanical stirring and ultrasonication blended mode and handles;
C. prepare the compound intercal type organic montmorillonite of nonionic-negatively charged ion 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 be dissolved in certain water gaging be mixed with emulsion through ultra-sonic dispersion and mechanical agitation and be designated as B liquid, add B liquid in the A liquid and carry out the ultra-sonic dispersion effect, follow-up mechanical stirring again, constant temperature leaves standstill, separate, drying obtains the compound intercal type organic montmorillonite of nonionic-negatively charged ion material.
Another object of the present invention is to provide the nonionic-negatively charged ion that makes by aforesaid method compound intercal 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, gas producing formation spacing height, the thermostability height is uniformly dispersed in organic phase, the extent of exfoliation height, excellent performance, the applying filler that can be used as a kind of excellent performance is to preparation high molecule nano composite material field.
Description of drawings
Fig. 1 is a na-montmorillonite crystalline structure synoptic diagram.
Fig. 2 is the XRD figure of the compound intercal type organic montmorillonite of gained nonionic-negatively charged ion among the embodiment 2, and wherein MMT represents montmorillonite.
Fig. 3 is the XRD figure of the compound intercal type organic montmorillonite of gained nonionic-negatively charged ion among the 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 characteristics of the present invention and advantage will become.
The invention provides the preparation method of the compound intercal type organic montmorillonite of nonionic-negatively charged ion, this method may further comprise the steps:
A. purifying montmorillonite: na-montmorillonite is purified;
B. montmorillonite being carried out aquation handles: the montmorillonite after will purifying is made aqeous suspension, carries out aquation by mechanical stirring and ultrasonication blended mode and handles;
C. prepare the compound intercal type organic montmorillonite of nonionic-negatively charged ion 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 be dissolved in certain water gaging be mixed with emulsion through ultra-sonic dispersion and mechanical stirring and be designated as B liquid, join B liquid in the A liquid then and carry out the ultra-sonic dispersion effect, follow-up mechanical stirring again, constant temperature leaves standstill, separate, drying obtains the compound intercal type organic montmorillonite of nonionic-negatively charged ion 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 embodiment preferred, steps A comprises: with ball mill with the na-montmorillonite raw material pulverizing, cross 200 mesh sieves, montmorillonite is dispersed in is made into suspension in the water and makes its " concentration " be no more than 10g/L, electronic stirring 15-60 minute, preferred 20-30 minute, more preferably 20 minutes, room temperature leaves standstill for some time, preferred 6-20 hour, preferred 8-10 hour, take out the upper strata suspension liquid with siphon pipe, centrifugation, as 60-100 ℃, about especially 70 ℃ of following dryings get purifying montmorillonite at elevated temperatures, remaining part adds distilled water again, volume returned to continue after the former state to stir 15-60 minute, preferred 20-30 minute, more preferably 20 minutes, leave standstill for some time, preferred 6-20 hour, preferred after 8-10 hour, take out the upper strata suspension liquid again, so repeatedly several times, add again till the distilled water rear suspension liquid relatively clarifies up to remainder.
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 combining 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 compares with simple mechanical agitation by discovering, ultra-sonic dispersion effect and mechanical agitation bonded mode are well a lot of for the dispersion effect of montmorillonite in water.Found through experiments, compare with the interlamellar spacing of the aquation montmorillonite that carries out the aquation acquisition by mechanical stirring, the interlayer that combines the aquation montmorillonite that carries out the aquation acquisition by the ultra-sonic dispersion effect with mechanical agitation on average increases 0.5-1.0nm.Reason for this reason may be the ultrasonic further dispersion that the physical influence and the chemical effect of montmorillonite have been promoted montmorillonite.
In a preparation method's of the present invention embodiment preferred, step B comprises: montmorillonite and the water of purifying are pressed mass ratio 3-15: 100, and preferred 3-10: 100, more preferably 4-6: 100, also more preferably 5: 100 proportional arrangement becomes suspension, transfer in the flask, controlled temperature is at 50-80 ℃, preferred 60-70 ℃, more preferably about 70 ℃, 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, used ultransonic power 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 big, thereby prepare the compound intercal type organic montmorillonite of strippable nonionic-negatively charged ion material.
Find unexpectedly, when by ultra-sonic dispersion effect and mechanical agitation, after using nonionic surface active agent that montmorillonite is carried out the intercalation improvement, again by ultra-sonic dispersion effect and mechanical agitation, aniorfic surfactant and nonionic surface active agent are entered between montmorillonite layer, support big montmorillonite layer spacing, obtain big modified montmorillonite used of interlamellar spacing support, in addition, because the stability of nonionic surface active agent and aniorfic surfactant is the thermostability height especially, therefore, the modified montmorillonite used stability of gained especially thermostability obviously improve.
The compound intercal type organic montmorillonite of nonionic-negatively charged ion material layer spacing height by the inventive method acquisition, its separability, thermostability and the excellent dispersion in organic phase, the applying filler that can be used as excellent performance is in the field of preparation high molecule nano composite material.
In a preparation method's of the present invention embodiment preferred, step C comprises: fully the montmorillonite hydrating fluid of aquation is an A liquid, organic nonionic surface active agent and organic anion type tensio-active agent be dissolved in certain water gaging be mixed with emulsion through ultra-sonic dispersion and mechanical stirring and be designated as B liquid, join B liquid in the A liquid and carry out the ultra-sonic dispersion effect, follow-up mechanical stirring again, constant temperature leaves standstill, and separates, drying obtains the compound intercal type organic montmorillonite of nonionic-negatively charged ion material.
In a preparation method's of the present invention preferred embodiment, in step C, separating, after the 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 steps C, the temperature of reaction system is controlled in the 40-80 ℃ of scope, in the 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, used nonionic surface active agent 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 used nonionic surface active agent is the 0.5-10 weight % of A liquid gross weight,, preferred 0.5-6 weight %, also more preferably 1-3 weight %.
In a preparation method's of the present invention preferred embodiment, in step C, used aniorfic surfactant 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 used aniorfic surfactant is the 0.5-10 weight % of A liquid gross weight,, preferred 0.5-6 weight %, also more preferably 1-3 weight %.
The inventor discovers, 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 compound intercal type organic montmorillonite of the high strippable nonionic-negatively charged ion of interlamellar spacing.
In a preparation method's of the present invention preferred embodiment, step C comprises: fully the montmorillonite slurry of aquation is an A liquid, with an amount of 0.5-10 weight % as A liquid gross weight, preferred 0.5-6 weight %, also more preferably organic nonionic surface active agent of 1-3 weight % with in right amount as the 0.5-10 weight % of A liquid gross weight, preferred 0.5-6 weight %, also more preferably the aniorfic surfactant of 1-3 weight % joins in the 80-100ml water, make emulsion B liquid through ultra-sonic dispersion and mechanical agitation 10-30min, B liquid is joined in the A liquid, and follow-up mechanical stirring 1-2 hour, stopping to stir also, constant temperature left standstill 1-2 hour, constant temperature carries out under the temperature of said process in 40-80 ℃ of scope, centrifugal, drying, pulverize the compound intercal type organic montmorillonite of negatively charged ion-nonionic.
The present invention also provides by the compound intercal type organic montmorillonite of the nonionic-negatively charged ion of method for preparing.
The compound intercal type organic montmorillonite of preparation method of the present invention and nonionic-negatively charged ion 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. the ultrasonic radiation technology is applied to montmorillonite aquation and properties-correcting agent intercalation process, has realized in high-content montmorillonite slurries and high density nonionic surface active agent system, aniorfic surfactant system, preparing the purpose of nonionic-anionic organic montmorillonite powder;
The compound intercal type organic montmorillonite of the nonionic-negatively charged ion of gained of the present invention in organic solvent through high speed shear can realize the layer with layer peel off, with nano level lamella homodisperse, significantly improve the rotary viscosity of system, and embody good rheological, thixotropy, therefore can be used as a kind of polymers of excellent properties filler and use.
4. the compound intercal type organic montmorillonite of the nonionic-negatively charged ion of gained of the present invention material possesses good thickening power, can be widely used in 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 polymkeric substance/montmorillonite nano-composite material 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 the 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, ultransonic 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. take by weighing the 80g montmorillonite powder and be dissolved in the 8L distilled water and (use barreled), the electricity consumption agitator stirred 20 minutes, and montmorillonite is made into the suspension that " concentration " is no more than 10g/L, continued to leave standstill 8 hours under room temperature state, took out the part of height＜10cm with siphon pipe;
3. get upper strata 10cm suspension liquid, centrifugal, vacuum-drying (70 ℃) must be made with extra care montmorillonite;
4. Sheng Xia part adds distilled water again, volume is returned to continue behind the original volume to stir 20 minutes, makes not " taking apart " and the residual particles dispersed greater than 2 μ m, after 8 hours again with it taking-up.So repeatedly several times, till the suspension of gained is relatively clarified after remainder adds distilled water again.
The preparation of the compound intercal type organic montmorillonite of embodiment 2 nonionics-negatively charged ion
With the cation exchange capacity of purifying through water law that obtains among the embodiment 1 is 88meq/100g, 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 the 80g water, 30 minutes postscripts of ultra-sonic dispersion and mechanical stirring are B liquid, then B liquid is joined and also continue mechanical stirring 1.5 hours in the A liquid, stop to stir, be cooled to the room temperature centrifugation, with deionized water wash sample 1 time, dry a few hours under 80 ℃ of conditions in loft drier, be ground to 200 mesh sieves, promptly got the compound intercal type organic montmorillonite of nonionic-negatively charged ion.
The x-ray diffraction spectra (XRD figure) of the compound intercal type organic montmorillonite of gained nonionic-negatively charged ion as shown in Figure 2.As shown in Figure 2, the interlamellar spacing of this organic montmorillonite is 4.40nm.
The preparation of the compound intercal type organic montmorillonite of embodiment 3 nonionics-negatively charged ion
With the cation exchange capacity of purifying through water law that obtains among the embodiment 1 is 88meq/100g, 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 the 80g water, 30 minutes postscripts of ultra-sonic dispersion and mechanical stirring are B liquid, then B liquid is joined and also continue mechanical stirring 1.5 hours in the A liquid, stop to stir, be cooled to the room temperature centrifugation, with deionized water wash sample 1 time, dry a few hours under 80 ℃ of conditions in loft drier, be ground to 200 mesh sieves, promptly got the compound intercal type organic montmorillonite of nonionic-negatively charged ion.
The x-ray diffraction spectra (XRD figure) of the compound intercal type organic montmorillonite of gained nonionic-negatively charged ion as shown in Figure 3.As shown in Figure 3, the interlamellar spacing of this organic montmorillonite is 4.51nm.
Comparative example 1
Method according to embodiment among the CN101182393B 1 prepares organically modified montmorillonite clay.
The interlamellar spacing of this organic montmorillonite is 1.21nm.
Compare with the organically modified montmorillonite clay that obtains in the comparative example, the interlamellar spacing of the compound intercal type organic montmorillonite of gained nonionic-negatively charged ion is bigger in the embodiment of the invention, 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, on bentonite bed, form chemisorption and physisorption with precipitation agent.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 interfloor distance is by further support is big, causes the interlamellar spacing of the organically modified montmorillonite clay that makes to be 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 constituted limitation of the scope of the invention.Be to be understood that; under the situation that does 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.
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| CN105733316A (en) * | 2016-01-27 | 2016-07-06 | 北京理工大学 | Preparation method of organic acid salt intercalated modified montmorillonite |
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| CN107620207A (en) * | 2017-09-12 | 2018-01-23 | 吉林大学 | A kind of preparation method of the water-based anti UV finishing liquid based on illite minerals |
| CN107814388A (en) * | 2016-09-12 | 2018-03-20 | 先声药业有限公司 | A kind of preparation method of montmorillonite |
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| CN102406616A (en) * | 2011-11-30 | 2012-04-11 | 上海景峰制药有限公司 | Montmorillonite-combined propranolol sustained-release dry suspension, preparation method thereof and preparation method of sodium-based montmorillonite used therein |
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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 |
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