CN103059341B - 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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- CN103059341B CN103059341B CN201310016035.XA CN201310016035A CN103059341B CN 103059341 B CN103059341 B CN 103059341B CN 201310016035 A CN201310016035 A CN 201310016035A CN 103059341 B CN103059341 B CN 103059341B
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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 daylight.Current conventional light-converting agent is mainly 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 to be combined with inorganic materials, synthesizes low cost, turns optical efficiency high, has the light-converting agent of fine consistency with macromolecular material.
Houghite is a kind of layered metal hydroxides, and the adjustable sex change due to its unique laminate structure and laminate composition and interlayer anion, makes it as inorganic functional material, in catalysis, ion-exchange, absorption, medicine and other fields, all be widely used.By houghite laminate structure, by its modification, at interlayer, mix various fluorescent ligands, obtain new light conversion agent.The patent application of people's propositions " thering is rare earth compounding intercalated houghite of fluorescent characteristic and preparation method thereof " such as Duan Xue in 2005 (number of patent application: 200510012245.7:; Publication number: CN1715365A), tie up to hydrotalcite layers introduces the rare earth ions such as Eu ammonia carboxylic title complex by ion-exchange to obtain the epipolic hydrotalcite of tool.The people such as chapter in 2008 literary composition tributes disclose the (number of patent application: 200710144014.0 that has Zincium containing hydrotalcite of hyperfluorescenceZeng Yongminggaoyingguang and preparation method thereof; Publication number: CN101195741A), system is by replacing the magnesium ion in magnesium aluminum-hydrotalcite with appropriate divalent zinc ion, with the part coordinations such as oxine that are dissolved or dispersed in 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 intercalation houghite described in above-mentioned two pieces of patents turns light intensity, and poor with macromolecular material consistency, practical application is restricted.The people such as the Sun Shuai of Shandong University in 2008 are at " chemical journal " (2008,66(2), 155.) reported the fluorescigenic Zn-Al houghite of a kind of new energy, without any fluorescent substance intercalation in the situation that, itself just has photoluminescent property Zn-Al houghite, and its maximum excitation wavelength is positioned at 375nm, maximum emission wavelength is in 443nm, the fluorescence showing is blue visible light, and shortcoming is that this houghite fluorescence intensity is very low, can not directly as light-converting agent, use.
Houghite has more significantly advantage as fire retardant material than traditional aluminium hydroxide, magnesium hydroxide.When pyrolytic decomposition, heat absorption can discharge the incombustible substance such as carbonic acid gas, water, and can impel combustible matl carbonization, forms complex metal oxides.The complex metal oxides forming 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 acid anhydrides, to be reacted preparation with the aminated compounds of phosphorous volution, then by ion-exchange, reacts with hydrotalcite and makes expanded polystyrene veneer modified hydrotalcite fire retardant.But the nitrogen element of the aminated compounds of phosphorous volution and the quality percentage composition of phosphoric are lower described in this patent, the rear carbon yield of burning is not high and swelling property is general, poor with 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 macromolecular material consistency.
Ionic liquid refers in room temperature or approaches under room temperature and presents salt liquid, that be comprised of zwitterion completely, also referred to as low temperature molten salt.Ionic liquid is generally 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, non-combustible, electroconductibility is strong, under room temperature ionic liquid viscosity very large (conventionally 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 are had to good solubility, in fields such as electrochemistry, organic synthesis, catalysis, separation, be widely used.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, has very strong fluorescence emission peak between 400 ~ 500nm.The people such as the Li Si of Shanghai Communications University sources in 2010 have 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.).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 in blue light region.Although ionic liquid shows good fluorescence and flame retardant resistance, use separately ionic liquid, there is the defect that price is high, therefore, in plastics, a large amount of uses are still restricted.
(3) summary of the invention
Poor in order to solve the technical problem that exists in 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 Ionic Liquid Modified houghite there is fluorescence and fire-retardant functionalization houghite and preparation method thereof, ionic liquid is adulterated and is adsorbed in houghite bedding void and surface.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 has good consistency with macromolecular material.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) there is the preparation of the carbonate intercalated houghite precursor of fluorescence property:
A. obtain solution A, by 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, in solution B, urea-containing mole number is divalence and trivalent metal cation total moles 3 ~ 10 times in solution A;
C. solution A and solution B are mixed, logical nitrogen protection, lasting magneton stirs, and reacts 20 ~ 50 hours, adopts deionized water centrifuge washing to neutral, and 30 ~ 80 ℃ are dried 10 ~ 30 hours, obtain having the carbonate intercalated houghite precursor of fluorescence property;
2) the hydrotalcite precursor with fluorescence property of being prepared by step 1) and ionic liquid C join in anhydrous ethanol solvent and react, in anhydrous ethanol solvent, adding hydrotalcite precursor 50 ~ 200g/L, ionic liquid C is 100 ~ 500gL, stirring velocity is 2000 ~ 4000 revs/min, stirring reaction 12 ~ 24 hours, standing 10 ~ 20 hours, use ethanol centrifuge washing, 30 ~ 60 ℃ dry 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+for Fe
2+, Co
2+, Cu
2+, Zn
2+, Mn
2+, Ca
2+, Mg
2+or Ni
2+in any, trivalent metal cation M
3+for 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, N-propyl group, crassitude hexafluorophosphate, N-methyl, the two fluoroform sulfimide salt of propyl pyrrole alkane, N-ethylpyridine hexafluorophosphate, N-methyl, the two fluoroform sulfimide salt of propyl group morpholine, N-ethyl, any in methyl piperidine tosilate or 1-fluorenyl-3-methyl imidazolium tetrafluoroborate.
Utilize the functionalization houghite of dopant ion liquid prepared by the present invention to possess fluorescence and the flame retardant resistance of houghite and ionic liquid simultaneously, in blue light region, there is very strong fluorescence emission peak, equipment is simple, easy to operate, Product Green is environment friendly and pollution-free, particle diameter is controlled, has good consistency with macromolecular material.
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, and the functionalization houghite of acquisition can well be dispersed in macromolecular material, plays and well turns light and flame retardant effect.
2. the consumption when 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 be all 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) accompanying drawing explanation
Fig. 1 is embodiment 1 gained hydrotalcite precursor fluorescence excitation and utilizing emitted light spectrogram (maximum excitation wavelength is positioned at 344nm, and 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 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 optimum transmit wavelength is positioned at 436nm) of embodiment 1 gained functionalization houghite
(5) embodiment
Below by by concrete example, the present invention is described in further detail.The present invention's dehydrated alcohol used is chemical pure.
Embodiment 1.
Preparation is containing the Zn (NO of 0.5mol/L
3)
2al (NO with 0.25mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 3mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 30 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 10 hours, obtain carbonate intercalated houghite precursor.The hydrotalcite precursor of preparation and ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate (C) are joined in anhydrous ethanol solvent and reacted, in every 10mL anhydrous ethanol solvent, adding hydrotalcite precursor 0.5g and ionic liquid 3g(is hydrotalcite precursor 50g/L, ionic liquid 300g/L), stirring velocity is 2000 revs/min, stirring reaction 12 hours, 50 ℃ standing 10 hours, use 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 is containing the Co (NO of 1.0mol/L
3)
2al (NO with 0.3mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 10mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 40 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 12 hours, obtain carbonate intercalated houghite precursor.The hydrotalcite precursor of preparation and ionic liquid N-octyl group-pyridine hexafluorophosphate (C) are joined in anhydrous ethanol solvent and reacted, add hydrotalcite precursor 100g/L, ionic liquid 450gL, stirring velocity is 2000 revs/min, stirring reaction 12 hours, 50 ℃ standing 12 hours, use 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 is containing the Zn (NO of 1.0mol/L
3)
2al (NO with 0.5mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 9mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 30 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 10 hours, obtain carbonate intercalated houghite.The hydrotalcite precursor of preparation and ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid salt (C) are joined in anhydrous ethanol solvent and reacted, add hydrotalcite precursor 80gL, ionic liquid 400g/L, stirring velocity is 3000 revs/min, stirring reaction 12 hours, 60 ℃ standing 10 hours, use 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 is containing the Cu (NO of 0.6mol/L
3)
2fe (NO with 0.2mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 6mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 40 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 10 hours, obtain carbonate intercalated houghite precursor.The hydrotalcite precursor of preparation and ionic liquid 1-butyl-3-methyl imidazolium a tetrafluoro borate (C) are joined in anhydrous ethanol solvent and reacted, add hydrotalcite precursor 75g/L, ionic liquid 350g/L, stirring velocity is 2000 revs/min, stirring reaction 12 hours, 50 ℃ standing 12 hours, use 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 is containing the Zn (NO of 0.6mol/L
3)
2fe (NO with 0.2mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 6mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 40 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 10 hours, obtain carbonate intercalated houghite precursor.The hydrotalcite precursor of preparation and ionic liquid 1-amine ethyl-3-methylimidazole a tetrafluoro borate (C) are joined in anhydrous ethanol solvent and reacted, add hydrotalcite precursor 55g/L, ionic liquid 200g/L, stirring velocity is 2000 revs/min, stirring reaction 12 hours, 50 ℃ standing 12 hours, use 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 is containing the Cu (NO of 0.6mol/L
3)
2fe (NO with 0.2mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 6mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 40 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 10 hours, obtain carbonate intercalated houghite.The hydrotalcite precursor of preparation and ionic liquid 1-nitrile propyl group-3-methyl imidazolium tetrafluoroborate (C) are joined in anhydrous ethanol solvent and reacted, add hydrotalcite precursor 125gL, ionic liquid 500gL, stirring velocity is 2000 revs/min, stirring reaction 12 hours, 50 ℃ standing 12 hours, use 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 is containing the Zn (NO of 1.0mol/L
3)
2al (NO with 0.5mol/L
3)
3the aqueous solution (A); Preparation is containing the aqueous solution of urea (B) of 9mol/L; Under nitrogen protection, solution (A) and solution (B) are mixed, lasting magneton stirs, and reacts 30 hours, adopts deionized water centrifuge washing to neutral, and 50 ℃ are dried 10 hours, obtain carbonate intercalated houghite.The hydrotalcite precursor of preparation and ionic liquid 1-allyl group-3-Methylimidazole villaumite (C) are joined in anhydrous ethanol solvent and reacted, add hydrotalcite precursor 100g/L, ionic liquid 400g/L, stirring velocity is 3000 revs/min, stirring reaction 12 hours, 60 ℃ standing 10 hours, use 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, the flame retardant effect of the fire retardant of preparing with the present invention of 4 parts of above-described embodiment function class hydrotalcites mensuration of 100 parts of matrixes interpolations.
Enumerated 8 case study on implementation herein principle of the present invention and implementation method are set forth, 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.Meanwhile, 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. a preparation method with the 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, by 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, in solution B, the mole number of urea is divalence and trivalent metal cation total moles 3～10 times in solution A;
C. solution A and solution B are mixed, lead to nitrogen protection, continue magneton and stir, react 20～50 hours, deionized water centrifuge washing is to neutral, and 30～80 ℃ are dried 10～30 hours, obtain having the carbonic acid intercalation hydrotalcite-like precursor of fluorescence property;
2) the houghite precursor of being prepared by step 1) and ionic liquid C join in alcohol solvent and react, in alcohol solvent, add houghite precursor 50-200g/L, add ionic liquid C100-500g/L, stirring velocity is 2000～4000 revs/min, stirring reaction 12～24 hours, standing 10～20 hours, use ethanol centrifuge washing, 30～60 ℃ are dried 10～30 hours, obtain having the ion liquid functionalization houghite of fluorescence and flame retardant properties;
Described divalent metal M
2+for Co
2+, Cu
2+or Zn
2+in a kind of, described trivalent metal cation M
3+for Al
3+or Fe
3+in a kind of;
Described ionic liquid C is a kind of in 1-butyl-3-Methylimidazole hexafluorophosphate, N-octyl group-pyridine hexafluorophosphate, 1-ethyl-3-methylimidazole sulfovinic acid salt, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-amine ethyl-3-methylimidazole a tetrafluoro borate, 1-nitrile propyl group-3-methyl imidazolium tetrafluoroborate or 1-allyl group-3-Methylimidazole villaumite.
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| 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 |
| 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 |
| 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 |
| CN105727686B (en) * | 2016-03-25 | 2017-12-08 | 张玲 | A kind of method for adsorbing purification sulfur hexafluoride |
| 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 |
| CN111282583B (en) * | 2020-02-19 | 2022-11-18 | 天津大学 | Fluorine-doped hydrotalcite material loaded metal-based catalyst, preparation method and application |
| 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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| 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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