CN103059341A - Fluorescent and flame retarded functionalization hydrotalcite and preparation method thereof - Google Patents
Fluorescent and flame retarded functionalization hydrotalcite and preparation method thereof Download PDFInfo
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- CN103059341A CN103059341A CN201310016035XA CN201310016035A CN103059341A CN 103059341 A CN103059341 A CN 103059341A CN 201310016035X A CN201310016035X A CN 201310016035XA CN 201310016035 A CN201310016035 A CN 201310016035A CN 103059341 A CN103059341 A CN 103059341A
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Abstract
The invention discloses a fluorescent and flame retarded functionalization hydrotalcite and a preparation method thereof. Ionic liquid is mixed with impurities and adsorbed in the layer gaps and surfaces of the hydrotalcite by virtue of the high specific surface area and the stratified structure property of the hydrotalcite, so that the functionalization hydrotalcite which has both fluorescence and flame retardancy is prepared. The functionalization hydrotalcite combines the performances of fluorescence and flame retardancy of the hydrotalcite and the ionic liquid, a blue light area of 400-500nm has strong emission peak and also has good flame retardancy. The functionalization hydrotalcite prepared by the method is simple in manufacturing and is easy to operate, the product is environment friendly, the grain size is controllable, and the hydrotalcite has good compatibility with high polymer material.
Description
(1) technical field
The present invention relates to a kind of have fluorescence and fire-retardant functionalization houghite and preparation method thereof.
(2) background technology
Light-converting agent and fire retardant are one of important auxiliary agents of synthesized polymer material processing, and its function is synthetic materials to be had can turn photosensitiveness, flame retardancy, self-extinguishing and smoke elimination.
Light-converting agent is that a class can will be converted into the chemical substance of the required ruddiness of photosynthesis, blue light to the harmful or useless UV-light of photosynthesis of plant, green glow etc. in the daylight.Current light-converting agent commonly used mainly is divided into organic dye class light-converting agent, inorganic salts light-converting agent, rare earth compounding class light-converting agent.Recent study person attempts organic materials is combined with inorganic materials, synthesizes low cost, turns optical efficiency high, with macromolecular material the light-converting agent of fine consistency is arranged.
Houghite is a kind of layered metal hydroxides, because its unique laminate structure and laminate form and the adjustable sex change of interlayer anion, it all is widely used in catalysis, ion-exchange, absorption, medicine and other fields as inorganic functional material.By the houghite laminate structure, with its modification, mix various fluorescent ligands at interlayer, obtain new light conversion agent.The people such as Duan Xue in 2005 propose " having rare earth compounding intercalated houghite of fluorescent characteristic and preparation method thereof " patent application (number of patent application: 200510012245.7:; Publication number: CN1715365A), tie up to hydrotalcite layers and introduce the ammonia carboxylic title complex of the rare earth ion such as Eu by ion-exchange to obtain the epipolic hydrotalcite of tool.The people such as chapter in 2008 literary composition tribute disclose the (number of patent application: 200710144014.0 that has Zincium containing hydrotalcite of hyperfluorescenceCeng Yongminggaoyingguang and preparation method thereof; Publication number: CN101195741A), system is by replacing the magnesium ion in the magnesium aluminum-hydrotalcite with an amount of divalent zinc ion, with the part coordinations such as oxine that are dissolved or dispersed in the interlayer lipophilicity negatively charged ion, obtain the novel high fluorescence Zincium containing hydrotalcite that a class different from common non-blooming zinc-containing hydrotalcite can be sent corresponding zinc coordination inner complex intense fluorescence simultaneously.But it is lower that the described intercalation houghite of above-mentioned two pieces of patents turns light intensity, and poor with the macromolecular material consistency, practical application is restricted.The people such as the Sun Shuai of Shandong University were at " chemical journal " (2008 in 2008,66(2), 155.) reported the fluorescigenic Zn-Al houghite of a kind of new energy, namely in the situation that without any the fluorescent substance intercalation, itself just has photoluminescent property the Zn-Al houghite, its maximum excitation wavelength is positioned at 375nm, maximum emission wavelength is in 443nm, the fluorescence that shows is blue visible light, and shortcoming is that this houghite fluorescence intensity is very low, can not directly use as light-converting agent.
Houghite has more significantly advantage as fire retardant material than traditional aluminium hydroxide, magnesium hydroxide.Heat absorption can discharge the incombustible substance such as carbonic acid gas, water when pyrolytic decomposition, and can impel the combustible matl carbonization, forms complex metal oxides.The complex metal oxides that forms can play the dual function that intercepts gas transfer and heat transmission.Patent CN102336926A discloses a kind of modification of Intumescent Flame-retardant Agent hydrotalcite and its production and use, described expansion type flame retardant is by the aminated compounds of acid anhydrides and phosphorous volution reaction preparation, then reacts with hydrotalcite by ion-exchange to make expanded polystyrene veneer modified hydrotalcite fire retardant.But the nitrogen element of the aminated compounds of the described phosphorous volution of this patent and the quality percentage composition of phosphoric are lower, and the rear carbon yield of burning is not high and swelling property is general, and is poor with the macromolecular material consistency.Patent CN102321274A discloses a kind of halogen-free flame retardants of ammonium polyphosphate anion intercalation hydrotalcite, and this patent foam performance is poor, and flame retardant effect is general, and the same existence problem poor with the macromolecular material consistency.
Ionic liquid refers to be also referred to as low temperature molten salt in room temperature or near presenting salt liquid, that be comprised of zwitterion fully under the room temperature.Ionic liquid generally is comprised of organic cation and inorganic anion, and common positively charged ion has quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazole salts ion and pyrroles's salt ion etc., and negatively charged ion has halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc.Ionic liquid is non-volatile, not flammable, electroconductibility is strong, under the room temperature ionic liquid viscosity very large (usually than high 1 ~ 3 order of magnitude of traditional organic solvent), thermal capacitance is large, vapour pressure is little, stable in properties, many inorganic salt and organism there are good solubility, are widely used in fields such as electrochemistry, organic synthesis, catalysis, separation.Recent study person finds that ionic liquid is not only a kind of good fire retardant material, and partial ion liquid has and well turns optical property, and very strong fluorescence emission peak is arranged between 400 ~ 500nm.The people such as Shanghai Communications University Li Si source had studied the impact of 1-butyl-3-Methylimidazole mesylate ionic liquid on PC flame retardant properties, thermal degradation performance and carbon residue pattern, structure in " polymer circular " (2010,11,76.) in 2010.The result shows that 1-butyl-3-Methylimidazole mesylate ionic liquid has significant fire retardation to PC.The people such as Aniruddha Paul in 2005 are at J.Phys.Chem.B.(2005,109,9148.) reported the photoluminescent property of imidazole salts ionic liquid, under ultraviolet excitation, ionic liquid has very strong fluorescence emission peak at blue light region.Although ionic liquid shows good fluorescence and flame retardant resistance, use separately ionic liquid, there is the high defective of price, therefore, a large amount of uses still are restricted in plastics.
(3) summary of the invention
Poor in order to solve the technical problem that exists in the aforesaid method and mineral-type hydrotalcite and macromolecular material consistency, use separately the problems such as ionic liquid price height, the invention provides a kind of with the Ionic Liquid Modified houghite have fluorescence and fire-retardant functionalization houghite and preparation method thereof, ionic liquid mixed on houghite bedding void and surface and adsorb.Combine the characteristic and advantage of houghite and ionic liquid, the material of preparation not only fluorescence and flame retardant resistance has obtained significantly improving, and with macromolecular material good consistency is arranged.And synthetic functionalization material has greatly reduced ionic liquid directly as fire-retardant or the usage quantity of light conversion agent in this way, has reduced cost, has improved performance.
The preparation process of the ion liquid functionalization houghite with fluorescence and flame retardant properties of the present invention is as follows:
1) have the preparation of the carbonate intercalated houghite precursor of fluorescence property:
A. obtain solution A is with solubility divalent metal M
2+With solubility trivalent metal cation M
3+Nitrate solution by containing M
2+/ M
3+Mix mol ratio=2.0 ~ 4.0, wherein M
2+Concentration be 0.2 ~ 1.0M;
B. prepare urea soln B, urea-containing mole number is divalence and trivalent metal cation total moles 3 ~ 10 times in the solution A in the solution B;
C. solution A and solution B are mixed, logical nitrogen protection continues magneton and stirs, and react 20 ~ 50 hours, adopts the deionized water centrifuge washing to neutrality, and 30 ~ 80 ℃ of dryings 10 ~ 30 hours obtain having the carbonate intercalated houghite precursor of fluorescence property;
2) the hydrotalcite precursor with fluorescence property that step 1) is prepared and ionic liquid C join in the anhydrous ethanol solvent and react, adding hydrotalcite precursor 50 ~ 200g/L, ionic liquid C in the anhydrous ethanol solvent is 100 ~ 500gL, stirring velocity is 2000 ~ 4000 rev/mins, stirring reaction 12 ~ 24 hours, left standstill 10 ~ 20 hours, use the ethanol centrifuge washing, 30 ~ 60 ℃ of dryings 10 ~ 30 hours obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Described divalent metal M
2+Be Fe
2+, Co
2+, Cu
2+, Zn
2+, Mn
2+, Ca
2+, Mg
2+Or Ni
2+In any, trivalent metal cation M
3+Be Al
3+, Cr
3+, Mn
3+, Fe
3+Or Ce
3+In any.
Described ionic liquid C is the two trifluoromethane sulfimide salt of tetramethyl-ammonium, tetraethyl ammonium trifluoromethane sulfimide salt, the two fluoroform sulfimide salt of tributyl hexyl phosphine, the two fluoroform sulfimide salt of tetrabutyl phosphine, 1-vinyl-3-Methylimidazole trifluoromethane sulfimide salt, the two trifluoro methyl yellow imide salts of 1-ethyl-3-methylimidazole, the N-propyl group, the crassitude hexafluorophosphate, the N-methyl, the two fluoroform sulfimide salt of propyl pyrrole alkane, N-ethylpyridine hexafluorophosphate, the N-methyl, the two fluoroform sulfimide salt of propyl group morpholine, the N-ethyl, any in methyl piperidine tosilate or the 1-fluorenyl-3-methyl imidazolium tetrafluoroborate.
Utilize the functionalization houghite of the dopant ion liquid that the present invention prepares to possess simultaneously fluorescence and the flame retardant resistance of houghite and ionic liquid, at blue light region very strong fluorescence emission peak is arranged, equipment is simple, easy to operate, Product Green is environment friendly and pollution-free, particle diameter is controlled, with macromolecular material good consistency is arranged.
Compared with prior art, advantage of the present invention is:
1. the functionalization houghite of preparation has solved the poor problem of houghite and macromolecular material consistency, so that the functionalization houghite of acquisition can well be dispersed in the macromolecular material, plays and well turns light and flame retardant effect.
2. the consumption when the functionalization houghite of preparation has greatly reduced ionic liquid directly as light-converting agent and fire retardant, reduced cost, increased the consistency with macromolecular material, and with the houghite of original carbonate intercalation turn photosensitiveness and flame retardant resistance mutually combines, turn light intensity and flame retardant properties and all be improved.
4. the functionalization houghite of preparation is environment-friendly type light-converting agent and the fire retardant of a kind of environmental protection, nontoxicity gas.
(4) description of drawings
Fig. 1 is embodiment 1 gained hydrotalcite precursor fluorescence excitation and utilizing emitted light spectrogram (maximum excitation wavelength is positioned at 344nm, and the optimum transmit wavelength is positioned at 448nm)
Fig. 2 is fluorescence excitation and the utilizing emitted light spectrogram (maximum excitation wavelength is positioned at 365nm, and the optimum transmit wavelength is positioned at 431nm) of embodiment 1 intermediate ion liquid
Fig. 3 is fluorescence excitation and the utilizing emitted light spectrogram (maximum excitation wavelength is positioned at 364nm, and the optimum transmit wavelength is positioned at 436nm) of embodiment 1 gained functionalization houghite
(5) embodiment
The below will the present invention is described in further detail by concrete example.The used dehydrated alcohol of the present invention is chemical pure.
Embodiment 1.
Preparation contains the Zn (NO of 0.5mol/L
3)
2Al (NO with 0.25mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 3mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 30 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 10 hours obtain carbonate intercalated houghite precursor.Hydrotalcite precursor and the ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate (C) of preparation are joined in the anhydrous ethanol solvent and react, adding hydrotalcite precursor 0.5g and ionic liquid 3g(are hydrotalcite precursor 50g/L, ionic liquid 300g/L in every 10mL anhydrous ethanol solvent), stirring velocity is 2000 rev/mins, stirring reaction 12 hours, 50 ℃ left standstill 10 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 2.
Preparation contains the Co (NO of 1.0mol/L
3)
2Al (NO with 0.3mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 10mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 40 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 12 hours obtain carbonate intercalated houghite precursor.Hydrotalcite precursor and the ionic liquid N-octyl group-pyridine hexafluorophosphate (C) of preparation are joined in the anhydrous ethanol solvent and react, add hydrotalcite precursor 100g/L, ionic liquid 450gL, stirring velocity is 2000 rev/mins, stirring reaction 12 hours, 50 ℃ left standstill 12 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 3.
Preparation contains the Zn (NO of 1.0mol/L
3)
2Al (NO with 0.5mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 9mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 30 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 10 hours obtain the carbonate intercalated houghite.Hydrotalcite precursor and the ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid salt (C) of preparation are joined in the anhydrous ethanol solvent and reacts, add hydrotalcite precursor 80gL, ionic liquid 400g/L, stirring velocity is 3000 rev/mins, stirring reaction 12 hours, 60 ℃ left standstill 10 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 4.
Preparation contains the Cu (NO of 0.6mol/L
3)
2Fe (NO with 0.2mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 6mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 40 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 10 hours obtain carbonate intercalated houghite precursor.Hydrotalcite precursor and the ionic liquid 1-butyl-3-methyl imidazolium a tetrafluoro borate (C) of preparation are joined in the anhydrous ethanol solvent and react, add hydrotalcite precursor 75g/L, ionic liquid 350g/L, stirring velocity is 2000 rev/mins, stirring reaction 12 hours, 50 ℃ left standstill 12 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 5.
Preparation contains the Zn (NO of 0.6mol/L
3)
2Fe (NO with 0.2mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 6mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 40 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 10 hours obtain carbonate intercalated houghite precursor.Hydrotalcite precursor and the ionic liquid 1-amine ethyl-3-methylimidazole a tetrafluoro borate (C) of preparation are joined in the anhydrous ethanol solvent and react, add hydrotalcite precursor 55g/L, ionic liquid 200g/L, stirring velocity is 2000 rev/mins, stirring reaction 12 hours, 50 ℃ left standstill 12 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 6.
Preparation contains the Cu (NO of 0.6mol/L
3)
2Fe (NO with 0.2mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 6mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 40 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 10 hours obtain the carbonate intercalated houghite.Hydrotalcite precursor and the ionic liquid 1-nitrile propyl group-3-methyl imidazolium tetrafluoroborate (C) of preparation are joined in the anhydrous ethanol solvent and react, add hydrotalcite precursor 125gL, ionic liquid 500gL, stirring velocity is 2000 rev/mins, stirring reaction 12 hours, 50 ℃ left standstill 12 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 7.
Preparation contains the Zn (NO of 1.0mol/L
3)
2Al (NO with 0.5mol/L
3)
3The aqueous solution (A); Preparation contains the aqueous solution of urea (B) of 9mol/L; Under nitrogen protection solution (A) and solution (B) are mixed, continue magneton and stir, react 30 hours, adopt the deionized water centrifuge washing to neutrality, 50 ℃ of dryings 10 hours obtain the carbonate intercalated houghite.Hydrotalcite precursor and the ionic liquid 1-allyl group-3-Methylimidazole villaumite (C) of preparation are joined in the anhydrous ethanol solvent and react, add hydrotalcite precursor 100g/L, ionic liquid 400g/L, stirring velocity is 3000 rev/mins, stirring reaction 12 hours, 60 ℃ left standstill 10 hours, use the dehydrated alcohol centrifuge washing, dry 10 hours, obtain having the functionalization houghite of the dopant ion liquid of strong blue-fluorescence and flame retardant properties.
Embodiment 8
Adopting the homo-polypropylene of Korea S's import is matrix, adds the flame retardant effect that 4 parts of above-described embodiment function class hydrotalcites are measured the fire retardant of the present invention's preparation with 100 parts of matrixes.
This paper has enumerated 8 case study on implementation principle of the present invention and implementation method has been set forth, and the explanation of above case study on implementation can be used to help to understand principle of the present invention and method.But above case study on implementation is not unique, should not be construed as limitation of the present invention.Simultaneously, for one of ordinary skill in the art, according to the principle of the invention and method, can change flexibly in specific embodiments and applications.
Claims (1)
1. preparation method with ion liquid functionalization houghite of fluorescence and flame retardant properties is characterized in that step is as follows:
1) preparation has the carbonic acid intercalation hydrotalcite-like precursor of fluorescence property:
A. obtain solution A is with solubility divalent metal M
2+With solubility trivalent metal cation M
3+Nitrate solution by containing M
2+/ M
3+Mix concentration ratio=2.0 ~ 4.0, wherein M
2+Concentration be 0.2 ~ 1.0M;
B. prepare urea-containing solution B, the mole number of urea is divalence and trivalent metal cation total moles 3 ~ 10 times in the solution A in the solution B;
C. solution A and solution B are mixed, logical nitrogen protection continues magneton and stirs, and react 20 ~ 50 hours, and the deionized water centrifuge washing is to neutrality, and 30 ~ 80 ℃ of dryings 10 ~ 30 hours obtain having the carbonic acid intercalation hydrotalcite-like precursor of fluorescence property;
2) the houghite precursor that step 1) is prepared and ionic liquid C join in the alcohol solvent and react, add houghite precursor 50 ~ 200g/L in the alcohol solvent, add ionic liquid C100 ~ 500gL, stirring velocity is 2000 ~ 4000 rev/mins, stirring reaction 12 ~ 24 hours, left standstill 10 ~ 20 hours, use the ethanol centrifuge washing, 30 ~ 60 ℃ of dryings 10 ~ 30 hours, the ion liquid functionalization houghite that obtains having fluorescence and flame retardant properties;
Described divalent metal M
2+Be Fe
2+, Co
2+, Cu
2+, Zn
2+, Mn
2+, Ca
2+, Mg
2+Or Ni
2+In a kind of, described trivalent metal cation M
3+Be Al
3+, Cr
3+, Mn
3+, Fe
3+Or Ce
3+In a kind of;
Described ionic liquid C is the two trifluoromethane sulfimide salt of tetramethyl-ammonium, tetraethyl ammonium trifluoromethane sulfimide salt, the two fluoroform sulfimide salt of tributyl hexyl phosphine, the two fluoroform sulfimide salt of tetrabutyl phosphine, 1-vinyl-3-Methylimidazole trifluoromethane sulfimide salt, the two trifluoro methyl yellow imide salts of 1-ethyl-3-methylimidazole, the N-propyl group, the crassitude hexafluorophosphate, the N-methyl, the two fluoroform sulfimide salt of propyl pyrrole alkane, N-ethylpyridine hexafluorophosphate, the N-methyl, the two fluoroform sulfimide salt of propyl group morpholine, the N-ethyl, a kind of in methyl piperidine tosilate or the 1-fluorenyl-3-methyl imidazolium tetrafluoroborate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394327A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Silanized functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN103394326A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Amino functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN105218861A (en) * | 2015-11-16 | 2016-01-06 | 济南泰星精细化工有限公司 | A kind of flame-retardant smoke inhibition organically-modified hydrotalcite and preparation method thereof |
| CN105727686A (en) * | 2016-03-25 | 2016-07-06 | 张玲 | Method for adsorbing and purifying sulfur hexafluoride |
| CN106916336A (en) * | 2017-02-24 | 2017-07-04 | 江苏斯德瑞克化工有限公司 | The method of ion liquid modified hollow glass micropearl and using it as the flame retardant thermoplastic polyurethane elastomer of fire retardant |
| CN111282583A (en) * | 2020-02-19 | 2020-06-16 | 天津大学 | Fluorine-doped hydrotalcite material loaded metal-based catalyst, preparation method and application |
| CN115109588A (en) * | 2022-07-19 | 2022-09-27 | 中国农业科学院农业环境与可持续发展研究所 | Rare earth doped hydrotalcite nanometer optical fertilizer and preparation method and application thereof |
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| CN102533263A (en) * | 2010-12-08 | 2012-07-04 | 北京化工大学 | Preparation method for lamellar inorganic-organic composite energy storage and conversion material |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103394327A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Silanized functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN103394326A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Amino functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN103394327B (en) * | 2013-08-20 | 2014-12-10 | 青岛科技大学 | Silanized functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN103394326B (en) * | 2013-08-20 | 2014-12-10 | 青岛科技大学 | Amino functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN105218861A (en) * | 2015-11-16 | 2016-01-06 | 济南泰星精细化工有限公司 | A kind of flame-retardant smoke inhibition organically-modified hydrotalcite and preparation method thereof |
| CN105727686A (en) * | 2016-03-25 | 2016-07-06 | 张玲 | Method for adsorbing and purifying sulfur hexafluoride |
| CN106916336A (en) * | 2017-02-24 | 2017-07-04 | 江苏斯德瑞克化工有限公司 | The method of ion liquid modified hollow glass micropearl and using it as the flame retardant thermoplastic polyurethane elastomer of fire retardant |
| CN106916336B (en) * | 2017-02-24 | 2019-03-05 | 江苏斯德瑞克化工有限公司 | The method of ion liquid modified hollow glass micropearl and using it as the flame retardant thermoplastic polyurethane elastomer of fire retardant |
| CN111282583A (en) * | 2020-02-19 | 2020-06-16 | 天津大学 | Fluorine-doped hydrotalcite material loaded metal-based catalyst, preparation method and application |
| CN111282583B (en) * | 2020-02-19 | 2022-11-18 | 天津大学 | Fluorine-doped hydrotalcite material loaded metal-based catalyst, preparation method and application |
| CN115109588A (en) * | 2022-07-19 | 2022-09-27 | 中国农业科学院农业环境与可持续发展研究所 | Rare earth doped hydrotalcite nanometer optical fertilizer and preparation method and application thereof |
| CN115109588B (en) * | 2022-07-19 | 2024-05-28 | 中国农业科学院农业环境与可持续发展研究所 | Rare earth doped hydrotalcite nano-optical fertilizer and preparation method and application thereof |
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