CN106006656B - Modified attapulgite nano-particle and preparation method thereof - Google Patents
Modified attapulgite nano-particle and preparation method thereof Download PDFInfo
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- CN106006656B CN106006656B CN201610321751.2A CN201610321751A CN106006656B CN 106006656 B CN106006656 B CN 106006656B CN 201610321751 A CN201610321751 A CN 201610321751A CN 106006656 B CN106006656 B CN 106006656B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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Abstract
The invention discloses a kind of modified attapulgite nano-particles and preparation method thereof.The preparation method includes：Acid activation processing is carried out to attapulgite surface with acid solution, the attapulgite of acid activation is made；The attapulgite of acid activation and surface modifier are uniformly mixed to form uniform dispersion in organic solvent, after fully reacting, modified attapulgite nano-particle is made.The surface modifier is preferably from the silane coupling agent etc. containing lipophilic group.The preparation method of the modified attapulgite nano-particle of the present invention is simple for process, condition is controllable, the dispersibility between the stick crystalline substance of attapulgite can be substantially improved under conditions of reservation attapulgite original pattern, and the modified attapulgite nano-particle obtained is compared with conventional modified attapulgite, not only there is good dispersion in organic solvent, additionally it is possible to which that stablizes is suspended in aqueous phase system surface.
Description
Technical field
Present invention relates particularly to a kind of modified attapulgite nano-particles and preparation method thereof, and the modified attapulgite is received
Rice corpuscles can stable suspersion in the water surface.
Background technology
Attapulgite (abbreviation ATP) is the clay mineral of zeopan containing Shuifu County of a kind of layer of chain structure, and crystal is in
Needle-shaped, fibrous agrregate, in 30nm or so, length is a kind of natural one up to several microns for the diameter of single fiber crystalline substance
Dimension nano material, in China, reserves are very abundant, and low etc. with nontoxic, tasteless and nonirritant, chemical stabilization, easy drying, hardness
Advantage.Attapulgite is usually used in packing material and sorbent material of polymer etc., however when for sorbent material, in order to carry
Its high adsorption effect to organic dye molecule, needs to carry out it organically-modified.It is mentioned by recessed in 104028211 A of CN
The surface organic modification of convex stick stone can improve its suction-operated to organic matter；103305124 A of CN disclose one kind and are used for
The preparation method of CE resin catalysis and the modified attapulgite nano-particle of enhancing improves it in resin by organically-modified
In compatibility realize to the catalysis of CE resins and the enhancing of mechanical performance.The surface of attapulgite is changed in conventional method at present
Property is taken surfactant-modified, these surfactants generally comprise cetyl ammonium bromide, octadecyl trimethyl bromine
Change the silane coupling agents such as long-chain molecules, KH550, KH560 and KH570 such as ammonium.But it is modified using these conventional methods recessed
It is that convex stick stone can not be stablized mostly, aqueous phase system surface is scattered in suspended form.
Invention content
The main purpose of the application is to provide a kind of modified attapulgite nano-particle and preparation method thereof, existing to overcome
There is the deficiency in technology.
For realization aforementioned invention purpose, the technical solution that the application uses includes：
A kind of preparation method of modified attapulgite nano-particle is provided in the embodiment of the present application comprising：
Acid activation processing is carried out to attapulgite surface with acid solution, the attapulgite of acid activation is made；
The attapulgite of acid activation and surface modifier are uniformly mixed to form uniform dispersion in organic solvent, through filling
After dividing reaction, modified attapulgite nano-particle is made, the surface modifier, which is selected from, contains the silane coupled of lipophilic group
Agent.
More preferred, the surface modifier is selected from the silane coupling agent containing phenyl, for example, at least preferably from two
Any one in phenyl silane, phenyl trichlorosilane, tri-phenyl chloride and phenyl-trimethoxysilane.
In some more preferred embodiment, the preparation method includes：By the attapulgite and table of acid activation
Face modifying agent is uniformly mixed to form uniform dispersion in organic solvent, and be modified at 30 DEG C~100 DEG C reaction 5h~
For 24 hours, modified attapulgite nano-particle is made.
The modified attapulgite nano-particle prepared by aforementioned any method, length are additionally provided in the embodiment of the present application
Degree is 0.5~3 μm, a diameter of 30~80nm, and the modified attapulgite nano-particle can be dispersed in organic solvent,
And can stable suspersion in aqueous phase system surface.
Compared with prior art, include the advantages of the application：The preparation method of the modified attapulgite nano-particle of offer
Simple for process, condition is controllable, the stick crystalline substance of attapulgite can be substantially improved under conditions of reservation attapulgite original pattern
Between dispersibility, and the modified attapulgite nano-particle obtained is compared with conventional modified attapulgite, not only in organic solvent
With good dispersion, additionally it is possible to which that stablizes is suspended in aqueous phase system (such as water, aqueous solution etc.) surface.
Description of the drawings
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments described in application, for those of ordinary skill in the art, without creative efforts,
Other drawings may also be obtained based on these drawings.
Fig. 1 be in the embodiment of the present application 4 modified attapulgite nano-particle obtained in the photo of floating on water；
Fig. 2 is the photo that modified attapulgite nano-particle obtained is added to the water in the application comparative example 1.
Specific implementation mode
To keep the purpose, technical scheme and advantage of the application clearer, below in conjunction with the accompanying drawings to the specific reality of the application
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The presently filed embodiment of attached drawing description is only exemplary, and the application is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the application because of unnecessary details, in the accompanying drawings only
It shows with according to the scheme of the application closely related structure and/or processing step, and is omitted little with the application relationship
Other details.
A kind of preparation method of the modified attapulgite nano-particle provided in the embodiment of the present application includes：
Activation process is carried out to attapulgite with acid solution, obtains acid activation attapulgite；
Surface modification treatment is carried out to acid activation attapulgite with surface modifier, obtains modified attapulgite.
In some embodiments, the preparation method includes：
Acid activation processing is carried out to attapulgite surface with acid solution, the attapulgite of acid activation is made；
The attapulgite of acid activation and surface modifier are uniformly mixed to form uniform dispersion in organic solvent, through filling
After dividing reaction, modified attapulgite nano-particle is made, the surface modifier, which is selected from, contains the silane coupled of lipophilic group
Agent.
In some preferred embodiments, the preparation method further includes：Attapulgite is scattered in acid solution, is obtained
To dispersion liquid (being defined as dispersion liquid A), and 1h~for 24 hours is fully reacted under conditions of temperature is 30 DEG C~120 DEG C, it is living to obtain acid
The attapulgite of change.
More preferred, the pH value of the acid solution is 0~5.
It is more preferred, a concentration of 5g/L~100g/L of attapulgite in the dispersion liquid A.
More preferred, the acid solution includes one or more above combinations in organic acid, inorganic acid, especially excellent
Selected from inorganic acid solution, still more preferably from hydrochloric acid, sulfuric acid, phosphoric acid etc., but not limited to this.
In some preferred embodiments, the preparation method further includes：The attapulgite of acid activation and surface are changed
Property agent be added in organic solvent, and fully dispersed is formationed dispersion liquid (being defined as dispersion liquid B) is 10 DEG C~120 DEG C then at temperature
Under conditions of be modified reaction 2h~for 24 hours, obtain modified attapulgite nano-particle.
It is more preferred, a concentration of 0.1g/L~100g/L of the attapulgite of acid activation in the dispersion liquid B.
It is more preferred, a concentration of 0.001g/L~10g/L of surface modifier in the dispersion liquid B.
Wherein, the surface modifier can the further preferred silane coupling agent containing phenyl, and can still more preferably from
Any one or two kinds in diphenyl silane, phenyl trichlorosilane, tri-phenyl chloride and phenyl-trimethoxysilane etc. with
On combination, but not limited to this.
Wherein, the organic solvent in the dispersion liquid B may include in alkane, small molecular alcohol any one or it is two or more
Combination, such as preferably from alkane；It preferably further is selected from n-hexane, toluene, pentane etc., but not limited to this.
Especially preferred, the temperature of the modified-reaction is 50 DEG C~120 DEG C.
Especially preferred, time of the modified-reaction is 8h~for 24 hours.
In some embodiments, the preparation method may also include：It is anti-from mixing is obtained after the completion of modified-reaction
It answers sub-argument in object to go out solid content, after washed to neutral, then obtains the modified attapulgite nano-particle through drying process.
For example, in some typical case study on implementation, the preparation method may include steps of：
(1) Concave-convex clay rod is scattered in hydrochloric acid solution, stirring makes its dispersion, obtains dispersion liquid A；It is preferred that dispersion liquid
The pH value of a concentration of 10g/L~50g/L of attapulgite in A, hydrochloric acid solution are 0~2, and the reaction time is 2h~10h, reaction temperature
Degree is 60 DEG C~100 DEG C；
(2) attapulgite of acid activation and phenyl-trimethoxysilane are added in n-hexane, and fully dispersed formed is divided
Dispersion liquid B, a concentration of 0.1g/L~100g/L of attapulgite, a concentration of 0.001g/L~10g/L of surface modifier；Reaction one
The section time obtains target product；60 DEG C~100 DEG C of preferable reaction temperature, reaction time 10h~for 24 hours；
(3) by reaction system obtained by step (2) through separation, washing is multiple, you can the attapulgite for obtaining surface modification is received
Rice corpuscles (i.e. modified attapulgite nano-particle).
The embodiment of the present application also provides the modified attapulgite nano-particle prepared by aforementioned any method, length
Be 0.5~3 μm, a diameter of 30~80nm, the modified attapulgite nano-particle can be dispersed in organic solvent (such as
Ethyl alcohol etc.) in, and can stable suspersion in aqueous phase system surface.
The technical solution of the application is further explained below in conjunction with attached drawing and several exemplary embodiments.
Embodiment 1：A certain amount of Concave-convex clay rod being scattered in the hydrochloric acid solution that pH value is 2, stirring makes its dispersion,
A concentration of 10g/L of Concave-convex clay rod, 10h is reacted at 60 DEG C, and separating, washing obtains the attapulgite of acid activation；It will be a certain amount of
Acid activation attapulgite and diphenyl silane be added n-hexane in, make a concentration of 10g/L of wherein attapulgite, methyl-
A concentration of 2g/L of triethoxysilane, and fully dispersed, reaction time 10h under the conditions of 60 DEG C, after product separation, washing is more
It is secondary, you can modified attapulgite nano-particle is obtained, is powder body material, it can be in water surface stable suspersion.
Embodiment 2：A certain amount of Concave-convex clay rod being scattered in the sulfuric acid solution that pH value is 1, stirring makes its dispersion,
The wherein a concentration of 20g/L of attapulgite, reacts 8h under the conditions of 70 DEG C, and separating, washing obtains the attapulgite of acid activation；It will
The attapulgite and phenyl trichlorosilane of acid activation are added in n-hexane, make a concentration of 20g/L of wherein attapulgite, ethylene
A concentration of 3g/L of base-triethoxysilane, and it is fully dispersed, react 12h under the conditions of 60 DEG C；After separation product, washing is more
It is secondary, you can modified attapulgite nano-particle is obtained, it can be in water surface stable suspersion.
Embodiment 3：It is in 1 phosphoric acid solution that a certain amount of Concave-convex clay rod, which is scattered in pH value, and stirring makes its dispersion,
A concentration of 50g/L of middle attapulgite, reacts 4h under the conditions of 60 DEG C, and product separating, washing obtains the attapulgite of acid activation；
The attapulgite of acid activation and tri-phenyl chloride are added in n-hexane, a concentration of 1g/L of wherein attapulgite, tetramethyl are made
A concentration of 0.5g/L of oxysilane, and it is fully dispersed, react 5h under the conditions of 80 DEG C；After product separation, washing is multiple, you can
Modified attapulgite nano-particle is obtained, it can be in water surface stable suspersion.
Embodiment 4：Concave-convex clay rod is scattered in salpeter solution, stirring makes its dispersion, obtains dispersion liquid A；It is preferred that
The pH value of a concentration of 50g/L of attapulgite in dispersion liquid A, hydrochloric acid solution are 0, and reaction time 8h, reaction temperature is 80 DEG C；
The attapulgite of acid activation and phenyl-trimethoxysilane are added in n-hexane, a concentration of 50g/ of wherein attapulgite is made
L, a concentration of 10g/L of surface modifier, and fully dispersed formation dispersion liquid B, reaction a period of time obtain target product；It is preferred that
100 DEG C of reaction temperature, reaction time 20h；For gained reaction system through separation, washing is multiple, you can obtains modified attapulgite and receives
Rice corpuscles, can be in water surface stable suspersion (refering to fig. 1).
Embodiment 5：Concave-convex clay rod is scattered in benzene sulfonic acid solution, stirring makes its dispersion, obtains dispersion liquid A；It is excellent
A concentration of 30g/L of attapulgite in dispersion liquid A is selected, the pH of hydrochloric acid solution is 0, reaction time 2h, reaction temperature 100
℃；The attapulgite of acid activation and phenyl-trimethoxysilane are added in n-hexane, a concentration of 100g/L of attapulgite,
A concentration of 1g/L of surface modifier, and fully dispersed formation dispersion liquid B, reaction a period of time obtain target product；It is preferred that anti-
80 DEG C of temperature is answered, the reaction time is for 24 hours；For gained reaction system through separation, washing is multiple, you can obtains modified attapulgite nanoparticle
Son, can be in water surface stable suspersion.
Reference examples 1：With reference to CN104877394A, 1g attapulgites are added in 50mL hydrochloric acid (5mol/L), at 75 DEG C
Isothermal reaction 1h, filters later, and is washed with deionized to neutrality, dry at 70 DEG C, the attapulgite being acidified.
1g acidification attapulgites are dispersed in 60mL toluene by the preparation of amination attapulgite, and ultrasonic disperse 30min is obtained uniform
Dispersion liquid A；6mL gamma-aminopropyl-triethoxy-silanes are added in dispersion liquid A, under agitation, and are reacted at 90 DEG C
8h；It filters, it is dry at 60 DEG C after ethyl alcohol washing for several times, amidized attapulgite is obtained, can not be stablized in the water surface outstanding
It is floating, and can sink in aqueous solution (refering to Fig. 2).
Reference examples 2：Refering to CN104028211A, by 10g attapulgites, 3g acid and 50ml water mixings, in 60 DEG C of constant temperature with
The speed of 400r/min stirs 60min, and 200 mesh sieve, 100 DEG C of calcination activation 10h are crossed in dry, crushing, obtain acid activation concave convex rod
Soil；20g acid activation attapulgites are weighed, 8g gamma-aminopropyl-triethoxy-silanes are added, 92g toluene flows back 24 hours, dry,
It crushes, cross 200 mesh sieve, obtain the concave convex rod soil matrix refining agent in powder shaped, which can not soak in water surface stable suspersion
Enter in aqueous solution.
It is embodiment 1- embodiments 5 and modified attapulgite nano-particle made from reference examples 1- reference examples 2 referring to table 1
Zeta potential.It is connecing for modified attapulgite and water made from embodiment 1- embodiments 5 and reference examples 1- reference examples 2 referring to table 2
Feeler.
The Zeta potential of 1 modified attapulgite nano-particle of table
The water contact angle of 2 modified attapulgite nano-particle of table
| Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Reference examples 1 | Reference examples 2 |
| Contact angle | 65° | 110° | 72° | 98° | 76° | Nothing | Nothing |
It should be noted that as above the various reaction partners employed in embodiment and process conditions are more typical
Case, but by inventor's a large number of experiments verify, in those listed above other different types of reaction partners and
Other process conditions etc. are also applicable, and the technique effect that also equal attainable cost application is claimed.
It should be appreciated that above-described embodiment is only the technical concepts and features for illustrating the application, its object is to allow be familiar with this
The personage of item technology can understand present context and implement according to this, and the protection domain of the application can not be limited with this.It is all
According to equivalent change or modification made by the application Spirit Essence, should all cover within the protection domain of the application.
Claims (11)
1. a kind of preparation method of modified attapulgite nano-particle, it is characterised in that including：
Acid activation processing is carried out to attapulgite surface with acid solution, the attapulgite of acid activation is made；
The attapulgite of acid activation and surface modifier are uniformly mixed to form uniform dispersion, the dispersion in organic solvent
Liquid includes the attapulgite and 0.001g/L~10g/L surface modifiers of 0.1g/L~100g/L acid activations, is 10 then at temperature
DEG C~120 DEG C under conditions of be modified reaction 2h~for 24 hours, modified attapulgite nano-particle, the surface modifier is made
Any one in diphenyl silane, phenyl trichlorosilane, tri-phenyl chloride and phenyl-trimethoxysilane.
2. preparation method according to claim 1, it is characterised in that including：Attapulgite is scattered in acid solution and is formed
Dispersion liquid reacts 1h~for 24 hours in 30 DEG C~120 DEG C later, obtains the attapulgite of acid activation.
3. preparation method according to claim 2, it is characterised in that：The pH value of the acid solution is 0~5.
4. preparation method according to claim 2, it is characterised in that：The dispersion liquid includes 5g/L~100g/L concave convex rods
Stone.
5. according to the preparation method described in any one of claim 1-4, it is characterised in that：It is molten that the acid solution is selected from inorganic acid
Liquid, the inorganic acid include any one or two or more combinations in hydrochloric acid, sulfuric acid and phosphoric acid.
6. preparation method according to claim 1, it is characterised in that including：The attapulgite of acid activation and surface are modified
Agent is uniformly mixed to form uniform dispersion in organic solvent, and reacts at 30 DEG C~100 DEG C 5h~for 24 hours, is made modified concave-convex
Stick stone nano-particle.
7. preparation method according to claim 6, it is characterised in that including：The attapulgite of acid activation and surface are modified
Agent is uniformly mixed to form uniform dispersion in organic solvent, and is modified at 60 DEG C~100 DEG C reaction 10h~for 24 hours, is made
Modified attapulgite nano-particle.
8. according to the preparation method described in claim 1,6 or 7, it is characterised in that：The organic solvent includes alkane and small point
The combination of any one or two kinds in sub- alcohol.
9. preparation method according to claim 8, it is characterised in that：The organic solvent is selected from alkane, the alkane packet
Include any one in n-hexane, toluene, pentane or two or more combinations.
10. preparation method according to claim 7, it is characterised in that further include：After the completion of modified-reaction, from obtained mixed
It closes in reactant and isolates solid content, after washed to neutral, then obtain the modified attapulgite nanometer through drying process
Particle.
11. the modified attapulgite nano-particle prepared by any one of claim 1-10 the methods, the length of 0.5~
3 μm, a diameter of 30~80nm, the modified attapulgite nano-particle can be dispersed in organic solvent, and can be steady
Surely it is suspended in aqueous phase system surface.
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| CN106495174B (en) * | 2016-12-02 | 2018-08-07 | 中科院广州能源所盱眙凹土研发中心 | Attapulgite wet method bisgallic acid activation method |
| CN108047687A (en) * | 2017-12-14 | 2018-05-18 | 中国科学院宁波材料技术与工程研究所 | A kind of nylon/attapulgite composite granule, its preparation method and application |
| CN108774035B (en) * | 2018-06-27 | 2021-03-09 | 湖北工业大学 | Preparation method of nano-attapulgite bonded composite material |
| CN108840348A (en) * | 2018-09-06 | 2018-11-20 | 河南理工大学 | A kind of preparation method of Citrated method modified paligorskite explosion-suppressing material |
| CN111154270B (en) * | 2020-01-16 | 2024-08-16 | 中国科学院兰州化学物理研究所 | Modified nano dissociated attapulgite composite silicone rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN101613112A (en) * | 2009-07-06 | 2009-12-30 | 江南大学 | A kind of preparation of attapulgite modified by silane coupling agent |
| CN102992337A (en) * | 2012-12-05 | 2013-03-27 | 常州大学 | Functional attapulgite particle with amido on surface and preparation method thereof |
-
2016
- 2016-05-16 CN CN201610321751.2A patent/CN106006656B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN101613112A (en) * | 2009-07-06 | 2009-12-30 | 江南大学 | A kind of preparation of attapulgite modified by silane coupling agent |
| CN102992337A (en) * | 2012-12-05 | 2013-03-27 | 常州大学 | Functional attapulgite particle with amido on surface and preparation method thereof |
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