CN104479173A - Halloysite nanotube and hydrotalcite compound and preparation method thereof - Google Patents
Halloysite nanotube and hydrotalcite compound and preparation method thereof Download PDFInfo
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- CN104479173A CN104479173A CN201410734292.1A CN201410734292A CN104479173A CN 104479173 A CN104479173 A CN 104479173A CN 201410734292 A CN201410734292 A CN 201410734292A CN 104479173 A CN104479173 A CN 104479173A
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- halloysite nanotubes
- hydrotalcite
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Abstract
The invention relates to a halloysite nanotube and hydrotalcite compound and a preparation method of the halloysite nanotube and hydrotalcite compound. The compound is composed of two inorganic nano materials, namely halloysite nanotube and hydrotalcite, wherein the hydrotalcite grows on the surface of the halloysite nanotube in situ, and is in a flake structure. The preparation method specifically comprises the following steps: 1) dissolving a soluble magnesium salt and a soluble aluminum salt into deionized water, and stirring and mixing evenly at a room temperature; 2) adding the halloysite nanotube to the mixed salt liquid prepared from the step 1), and then ultrasonically dispersing to form a uniform liquid; 3) slowly adding a liquid prepared from sodium hydroxide and sodium carbonate to the liquid prepared from the step 2) in an intense agitation state, and putting into a drying oven after adding is ended, and standing and crystallizing for a certain period of time; and 4) filtering, washing and drying the sediments, and grinding to obtain the compound. The compound can be used as fire retardants of thermoplastic and thermosetting polymer materials, heat stabilizers of PVC-based high polymer materials and chlorine-resistant additives of polyurethane elastic fibers.
Description
Technical field
The invention belongs to inorganic non-metallic class technical field of function materials, particularly a kind of halloysite nanotubes hydrotalcite complex and preparation method thereof.
Background technology
Halloysite nanotubes (Halloysite Nanotubes, HNTs) is double-deck 1:1 type aluminosilicate (Al
2si
2o
5(OH)
4nH
2o), batched by the alumina octahedral of internal layer and outer field silicon-oxy tetrahedron lattice mismatch and form, having hollow nano tubular structure, there is crystal water in its interlayer, is a kind of nanoclay material.Natural halloysite nanotubes, at China's rich reserves, cheap and easy to get.In field of high polymer material processing, halloysite nanotubes can significantly improve the mechanical property of macromolecular material, as Chinese patent 100348655C discloses the method for a kind of halloysite nanotubes for the preparation of polymer composites, add the mechanical property that halloysite nanotubes can significantly improve polymkeric substance.In flame retardance of polymer field, halloysite nanotubes demonstrates good research and development and application prospect, as Chinese patent 102153744A discloses a kind of preparation method of halloysite nanotube reinforced flame-retardant anionic polymerization nylon, this patent carries out modification by halloysite nanotubes to anionic polymerization nylon, not only can play filling enhancement, and fire-retardant effect can also be played.
Hydrotalcite has another name called layered bi-metal oxide compound (Layered Double Hydroxide, LDH), is a kind of anionic inorganic stratified material, is made up of positively charged layers of metal hydroxides plate and the negatively charged ion and structural water molecule being filled in interlayer.Natural hydrotalcite (Mg
6al (OH)
16cO
34H
2o) be Mg-Al composite oxyhydroxide, exist at nature less, primarily of synthetic.Hydrotalcite has the performance of multiple excellence: (1) improves the flame retardant properties of polymkeric substance: as Chinese patent 102617979A discloses a kind of Intercalation hydrotalcite fire retardant and preparation method thereof, this fire retardant belongs to organic/inorganic composite, can significantly improve intensity and the flame retardant properties of macromolecular material; (2) improve the thermostability of macromolecular material: as Chinese patent 102531036B discloses a kind of PVC magnesium zinc-aluminium ternary houghite thermo-stabilizer and preparation method thereof, this product is used as polychloroethylene heat stabilizer and shows excellent thermostability; (3) improve the chlorine-resistant property of polyurethanes spandex fiber: as Chinese patent 101139751B discloses a kind of chlorine resistant polyurethaneurea elastic fiber and preparation method thereof, this patent improves resistance to chlorine and the homogeneity of polyurethaneurea elastic fiber by adding the inorganic chlorine-resistant agent of hydrotalcite.
The theoretical investigation that halloysite nanotubes (HNTs) and hydrotalcite (LDH) are existing more in polymer modification and production application, and the two is prepared inorganic/inorganic complex by chemical mode compound not yet have report.The invention provides a kind of preparation method of halloysite nanotubes hydrotalcite complex, innovation with halloysite nanotubes cheap and easy to get for matrix, hydrotalcite growth in situ is in the surface of halloysite nanotubes, utilize the synergy of halloysite nanotubes and hydrotalcite, efficiently solve fire-retardant, the technical problem such as the thermostability of PVC based high molecular material and the resistance to chlorine of polyurethanes spandex fiber of thermoplasticity and thermoset family macromolecule material.In addition, preparation method involved in the present invention also has the advantages such as simple to operate, mild condition.
Summary of the invention
Technical problem: the object of the invention is to solve the deficiencies in the prior art, a kind of preparation method of halloysite nanotubes hydrotalcite complex is provided, wherein halloysite nanotubes is as matrix, and hydrotalcite growth in situ is in the surface of halloysite nanotubes, in the form of sheets structure.The two, by playing synergy, effectively can improve the technical problems such as the flame retardant properties of thermoplasticity and thermoset family macromolecule material, the thermal stability of PVC based high molecular material and the chlorine-resistant property of polyurethanes spandex fiber.
Technical scheme: a kind of halloysite nanotubes hydrotalcite complex provided by the invention and preparation method thereof, it is characterized in that comprising halloysite nanotubes and hydrotalcite two kinds of inorganic components, wherein said hydrotalcite is assembled in halloysite nanotubes surface, in the form of sheets structure.
A kind of halloysite nanotubes hydrotalcite complex provided by the invention and preparation method thereof, described preparation method comprises following several step:
1) be dissolved in deionized water by the magnesium salts of solubility and aluminium salt, stirred at ambient temperature mixes;
2) to step 1) obtained by mixing salt solution in add halloysite nanotubes, then ultrasonic disperse formed homogeneous solution;
3) under strong stirring state, to step 2) obtained by solution in slowly add the solution be made up of sodium hydroxide and sodium carbonate, add terminate after, be placed on static crystallization certain hour in baking oven;
4) throw out is filtered, washing, dry, obtain mixture after grinding;
In preparation method of the present invention, step 1) described in the concentration of solubility magnesium salts be 0.02 ~ 1.5mol/L, magnesium ion and aluminum ions mol ratio are 2 ~ 4:1.
In preparation method of the present invention, step 2) described in halloysite nanotubes be long tubular structure, halloysite nanotubes and deionized water quality are than being 1:1000 ~ 1:50.
In preparation method of the present invention, step 3) described in sodium hydroxide and sodium carbonate composition solution in, the concentration of sodium hydroxide is 0.05 ~ 4mol/L, and the concentration of sodium carbonate is 0.005 ~ 0.6mol/L.
In preparation method of the present invention, step 3) described in static crystallization temperature be 60 ~ 100 DEG C, crystallization time is 8 ~ 24h.
Beneficial effect: the present invention is compared with current material, and tool has the following advantages and effect:
(1) specific surface area that natural halloysite nanotubes is larger and surperficial electronegativity is utilized, take halloysite nanotubes as matrix, hydrotalcite is with the surface of sheet structure growth in situ in halloysite nanotubes, and wherein hydrotalcite and halloysite nanotubes are in conjunction with firm difficult drop-off.
(2) halloysite nanotubes hydrotalcite complex has the performance of halloysite nanotubes and hydrotalcite concurrently, and the two plays synergy, can be used as fire retardant, thermo-stabilizer and resistance to chlorine additive.
Accompanying drawing illustrates:
Fig. 1 be halloysite nanotubes hydrotalcite complex prepare schematic diagram.
Fig. 2 is the XRD spectra of halloysite nanotubes hydrotalcite complex prepared by embodiment 1.
Embodiment
Describe the present invention in detail with example below, but these examples must not be interpreted as and go up limitation of the present invention in all senses.
Embodiment 1:
(1) MgCl is got
26H
2o (0.004mol) and AlCl
36H
2o (0.002mol) is dissolved in 200ml deionized water, and stirred at ambient temperature mixes, and wherein the concentration of solubility magnesium salts is 0.02mol/L, and the concentration of aluminum soluble salt is 0.01mol/L;
(2) join in above-mentioned mixing salt solution by 0.2g halloysite nanotubes, wherein the mass ratio of halloysite nanotubes and deionized water is 1:1000, after ultrasonic disperse 60min, forms homogeneous solution;
(3) by 0.012mol NaOH and 0.001mol Na
2cO
3be dissolved in 200ml deionized water, then under strong stirring state, it be slowly added drop-wise to step 2) prepared by mixing solutions in; Dropping terminates rear Keep agitation 1h, then by its static crystallization 24h at 60 DEG C;
(4) filtered by above-mentioned throw out, washing, dry, obtain mixture after grinding, wherein magnalium mol ratio is 2:1.
Embodiment 2:
(1) MgCl is got
26H
2o (0.06mol) and AlCl
36H
2o (0.02mol) is dissolved in 120ml deionized water, and stirred at ambient temperature mixes, and wherein the concentration of solubility magnesium salts is 0.5mol/L, and the concentration of aluminum soluble salt is 0.167mol/L;
(2) join in above-mentioned mixing salt solution by 1.2g halloysite nanotubes, wherein the mass ratio of halloysite nanotubes and deionized water is 1:100, after ultrasonic disperse 80min, forms homogeneous solution;
(3) by 0.16mol NaOH and 0.01mol Na
2cO
3be dissolved in 120ml deionized water, then under strong stirring state, it be slowly added drop-wise to step 2) prepared by mixing solutions in; Dropping terminates rear Keep agitation 1.5h, then by its static crystallization 12h at 80 DEG C;
(4) filtered by above-mentioned throw out, washing, dry, obtain mixture after grinding, wherein magnalium mol ratio is 3:1.
Embodiment 3:
(1) MgCl is got
26H
2o (0.15mol) and AlCl
36H
2o (0.0375mol) is dissolved in 100ml deionized water, and stirred at ambient temperature mixes, and wherein the concentration of solubility magnesium salts is 1.5mol/L, and the concentration of aluminum soluble salt is 0.375mol/L;
(2) join in above-mentioned mixing salt solution by 2g halloysite nanotubes, wherein the mass ratio of halloysite nanotubes and deionized water is 1:50, after ultrasonic disperse 100min, forms homogeneous solution;
(3) by 0.375mol NaOH and 0.01875mol Na
2cO
3be dissolved in 100ml deionized water, then under strong stirring state, it be slowly added drop-wise to step 2) prepared by mixing solutions in; Dropping terminates rear Keep agitation 2h, then by its static crystallization 8h at 100 DEG C;
(4) filtered by above-mentioned throw out, washing, dry, obtain mixture after grinding, wherein magnalium mol ratio is 4:1.
Claims (6)
1. a halloysite nanotubes hydrotalcite complex, it is characterized in that this mixture comprises halloysite nanotubes and hydrotalcite two kinds of inorganic components, wherein said hydrotalcite in the form of sheets structure is assembled in halloysite nanotubes surface.
2. the preparation method of a kind of halloysite nanotubes hydrotalcite complex according to claim 1, is characterized in that described preparation method comprises following several step:
1) be dissolved in deionized water by the magnesium salts of solubility and aluminium salt, stirred at ambient temperature mixes, obtained mixing salt solution;
2) in the mixing salt solution obtained by step 1), add halloysite nanotubes, then ultrasonic disperse forms homogeneous solution;
3) under strong stirring state, to step 2) obtained by solution in slowly add the solution be made up of sodium hydroxide and sodium carbonate, add terminate after, be placed on static crystallization in baking oven;
4) throw out is filtered, washing, dry, obtain halloysite nanotubes hydrotalcite complex after grinding.
3. the preparation method of a kind of halloysite nanotubes hydrotalcite complex according to claim 2, it is characterized in that the concentration of the solubility magnesium salts described in step 1) is 0.02 ~ 1.5mol/L, magnesium ion and aluminum ions mol ratio are 2 ~ 4:1.
4. the preparation method of a kind of halloysite nanotubes hydrotalcite complex according to claim 2, is characterized in that step 2) described in halloysite nanotubes be long tubular structure, halloysite nanotubes and deionized water quality are than being 1:1000 ~ 1:50.
5. the preparation method of a kind of halloysite nanotubes hydrotalcite complex according to claim 2, it is characterized in that in the solution of sodium hydroxide described in step 3) and sodium carbonate composition, the concentration of sodium hydroxide is 0.05 ~ 4mol/L, and the concentration of sodium carbonate is 0.005 ~ 0.6mol/L.
6. the preparation method of a kind of halloysite nanotubes hydrotalcite complex according to claim 2, it is characterized in that the oven temperature described in step 3) is 60 ~ 100 DEG C, static crystallization time is 8 ~ 24h.
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| CN106751144A (en) * | 2016-11-29 | 2017-05-31 | 广东联塑科技实业有限公司 | A kind of drainpipe environment-friendlyflame-retardant flame-retardant polyvinyl chloride composition and preparation method thereof |
| CN108018617A (en) * | 2017-12-06 | 2018-05-11 | 邱龙海 | A kind of preparation method of moisture absorption anti-electrostatic polyester |
| CN111153420A (en) * | 2020-01-14 | 2020-05-15 | 北京化工大学 | Magnesium-aluminum hydrotalcite nanotube and preparation method thereof |
| CN112886029A (en) * | 2021-01-12 | 2021-06-01 | 深圳清华大学研究院 | Bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier, preparation and application |
| CN115382521A (en) * | 2022-08-05 | 2022-11-25 | 浙江工业大学 | Halloysite hydrotalcite composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106751144A (en) * | 2016-11-29 | 2017-05-31 | 广东联塑科技实业有限公司 | A kind of drainpipe environment-friendlyflame-retardant flame-retardant polyvinyl chloride composition and preparation method thereof |
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| CN112886029A (en) * | 2021-01-12 | 2021-06-01 | 深圳清华大学研究院 | Bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier, preparation and application |
| CN112886029B (en) * | 2021-01-12 | 2022-05-17 | 深圳清华大学研究院 | Preparation and application of bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier |
| CN115382521A (en) * | 2022-08-05 | 2022-11-25 | 浙江工业大学 | Halloysite hydrotalcite composite material and preparation method and application thereof |
| CN115382521B (en) * | 2022-08-05 | 2023-09-29 | 浙江工业大学 | Halloysite-based hydrotalcite-like composite material and preparation method and application thereof |
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Address after: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee after: Huafeng Chemical Co.,Ltd. Address before: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee before: ZHEJIANG HUAFENG SPANDEX Co.,Ltd. |