CN102924647A - Method for preparing nano iron polymer composite with solution polymerization by ultrasounds - Google Patents
Method for preparing nano iron polymer composite with solution polymerization by ultrasounds Download PDFInfo
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- CN102924647A CN102924647A CN2012104594071A CN201210459407A CN102924647A CN 102924647 A CN102924647 A CN 102924647A CN 2012104594071 A CN2012104594071 A CN 2012104594071A CN 201210459407 A CN201210459407 A CN 201210459407A CN 102924647 A CN102924647 A CN 102924647A
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Abstract
The invention relates to a method for preparing a nano iron polymer composite with solution polymerization by ultrasounds. The method comprises the following steps that ferric trichloride, methyl methacrylate, styrene, toluene and azodiisobutyronitrile are uniformly mixed, ultrasound irradiation is carried out under the condition of nitrogen protection, and a reacted solution is obtained; absolute methanol is added into the reacted solution for precipitation, and a sediment is obtained after filtering; and the sediment is washed, dried in vacuum and is ground to obtain a nano iron polymer composite, and the polymer composite is grey solid powder. Under the conditions of nitrogen protection and no reducing agent, the ultrasound irradiation is carried out, iron ions are reduced into nano-iron particles, meanwhile, MMA and St are polymerized in situ, and the nano iron polymer composite is directly synthesized in one step. The method is relatively green, saves energy and protects environment.
Description
Technical field
The present invention relates to Nanoscale Iron-polymer composites field, particularly a kind of ultrasonic initiation solution polymerization prepares the method for Nanoscale Iron/PMMA-PS matrix material.
Background technology
At present, the research of relevant nano composite material is countless, metallic element is also too numerous to enumerate in the technology of polymer surfaces reduction, wherein modal metallic element has silver, copper, palladium, gallium etc., this type of polymer-based metal nano composite material has had nano material concurrently, metal and polymkeric substance be advantage separately, dispersed metal nanoparticle in polymeric matrix, metal nanoparticle performance and polymer performance are organically combined, so that this type of nano composite material not only has the surface effects of nano material, the character such as quantum size effect, and with the rigidity of metal, the toughness of dimensional stability and thermostability and polymkeric substance, processibility blends into one, therefore produce many special performances, further optimized the electricity of material, the performance such as calorifics and optics, thus opened up the application of nano composite material in field of functional materials.
The document of just reporting at home and abroad, the research of the oxide compound of Nanoscale Iron is full-fledged already, and is report about the aquatic foods of nano zero valence iron/polymer composites.The oxide compound of iron simple substance, iron is having a wide range of applications aspect magnet, electromagnetic wave absorbent material and the sewage disposal, and the oxide-based nanomaterial of iron is magnetic, and the environment remediation purposes, particularly Organic pollutants of nano zero valence iron and toxic heavy metal pollute.For Nanoscale Iron/polymer composites, pertinent literature has used high-energy ball milling method to prepare Nanoscale Iron/polyvinyl chloride composite materials, show that the combination between metal and the organism is contingent, and this material synthetic be close with the metallochemistry bond by organism rather than simply mix.
The preparation method of nano metal/polymer composites has a lot, such as irradiation chemosynthesis, high-energy ball milling method, sol-gel method, dispersion copolymerization method, graft process, blending method etc.Ultrasonic technique has unique effect as a kind of novel synthetic technology in the nano particle preparation.Ultrasonic polymerization is a kind of novel and polymerization process that efficient is higher.Ultrasonic polymerization utilizes hyperacoustic " cavitation effect " exactly, namely when ultrasonic wave is propagated in liquid medium, can in extremely short time and minimum space, produce localized hyperthermia, high pressure and the high rate of temperature change of moment, and be attended by strong shockwave and jet and Discharge illuminating effect at a high speed.Utilize this effect, can accelerate and control reaction, it is irregular to eliminate partial concn, improves reaction efficiency, accelerates mass transfer and heat transfer process between the interface, and reaction is carried out fast and effectively.
Adopt ultrasonic technique to prepare that the metal of nano metal/polymer composites is reported gold and silver, copper, a palladium etc., this type of nano composite material mainly is to adopt emulsion polymerisation process, solution polymerization process is compared it, and water not in the solution polymerization process does not have sewage handling problem; Do not add additive in the production, the foreign matter content that makes product is relatively less; The performance index such as thermally-stabilised, transmittance that make product are also better, and adopt the organic phase reaction, thereby avoided having the water of extremely strong coordination ability to participate in reaction process with iron ion.
Because the synthetic report of nano zero valence iron is bright few, adopting the work of ultrasonic solution polymerization synthesis of nano iron/polymer composites only is a beginning, awaits to study further deeply.
Summary of the invention
Nano metal reduces and the deficiency of the synchronization extent of polymer polymerizing in order to overcome, and the object of the invention is to adopt a kind of new synthetic technology, i.e. ultrasonic initiation solution polymerization prepares the method for Nanoscale Iron polymer composites.
The operation steps that the present invention specifically prepares the Nanoscale Iron polymer composites is as follows:
The concrete operation step that ultrasonic initiation solution polymerization prepares the Nanoscale Iron polymer composites is as follows:
(1) 0.250～0.300g FERRIC CHLORIDE ANHYDROUS, 15～25ml methyl methacrylate, 15～25ml vinylbenzene, 45～60ml toluene, 0.200～0.300g Diisopropyl azodicarboxylate and 1～2ml dehydrated alcohol are mixed, form homodisperse mixing solutions, with mixing solutions ultrasonic radiation under the nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 55～65min, ultrasonic power 550～650W obtains reacting rear solution;
(2) add 250～300ml anhydrous methanol in the solution after the reaction and precipitate, filter and be precipitated thing, with throw out washing, vacuum drying and grind, obtained the Nanoscale Iron polymer composites; The Nanoscale Iron polymer composites is the dark gray powder shape.
The monomer that the present invention selects is simpler, is easy to polymerization; Wherein polystyrene has certain intensity and thermal characteristics because having rigidity phenyl ring and flexible alkyl, and good fluidity; Polymethylmethacrylate has the good transparency, but the defective such as its existence is crisp and not shock-resistant; Copolyreaction by both can change the Nomenclature Composition and Structure of Complexes of polymkeric substance, thereby improves its performance; The multipolymer of the two combines the advantage of polystyrene and polymethylmethacrylate, not only has good transparency, glossiness and higher resistance to impact shock, and when machine-shaping, melt viscosity is little, better mobile, uses more extensive.
The Nanoscale Iron particle diameter is little, very easily reunites, thereby has reduced reactive behavior.In addition, nano iron particles is easily oxidation in air, also for it use and transportation is made troubles; Modally prevent that Nanoscale Iron from reuniting and the method for oxidation is to load on the carrier at Nanoscale Iron surface coating one deck organic macromolecule or with it.The Nanoscale Iron polymer composites is along with the rapid decline of particle diameter, volume effect, surface effects, quantum size effect and macro quanta tunnel effect etc. cause nanoparticle to have good electricity, heat, magnetic, light characteristic and catalytic etc., as being used for magnetic recording material, electromagnetic wave absorbent material, catalyzer and underground water and soil remediation etc., this is prospect so that it is widely used in fields such as chemical industry, electronics, biology, medical science.
The present invention adopts the solution polymerization process under ultrasonic technique, and being reduced with the polymerization of monomer of metal carried out simultaneously, and metal is wrapped in the polymkeric substance.Solution itself just has fabulous dispersiveness, and utilizes hyperacoustic cavitation effect, and it is irregular to eliminate partial concn, adds mass transfer and heat transfer process between strong interface.So just can effectively control the agglomeration traits of nano particle.In addition, metallic iron also is a kind of widely used metallic element, it is combined the anti-oxidation processing that should note iron when making nano composite material with organic monomer, in experimentation, need always endlessly nitrogen injection, and ultrasonic power, time and ultrasonic gap are all on synthetic to some extent impact.The present invention's solution polymerization under ultrasound condition, a step has directly been synthesized the Nanoscale Iron polymer composites, and this is a kind of relatively method of green, energy-conservation again environmental protection.
Description of drawings
Fig. 1 is the infrared spectrogram of Nanoscale Iron polymer composites.
Fig. 2 is the XRD figure of Nanoscale Iron polymer composites.
Embodiment
Below in conjunction with embodiment the present invention is further described.
The source of raw material:
(1) monomer: methyl methacrylate, analytical pure, Dihua worker company limited is won in Tianjin; Vinylbenzene, analytical pure, west, Shantou City Gansu Province chemical industry company limited;
(2) solvent: toluene, analytical pure, Shanghai Su Yi chemical reagent company limited;
(3) initiator: Diisopropyl azodicarboxylate, chemical pure, upper seamount Pu chemical industry company limited;
(4) other reagent: FERRIC CHLORIDE ANHYDROUS, analytical pure, Wuxi City prospect chemical reagent company limited; Dehydrated alcohol, analytical pure, Shanghai Su Yi chemical reagent company limited; Anhydrous methanol, analytical pure, the inferior chemical industry company limited of containing of Wuxi City.
Embodiment 1:
The concrete operation step that ultrasonic initiation solution polymerization prepares the Nanoscale Iron polymer composites is as follows:
(1) 0.300g FERRIC CHLORIDE ANHYDROUS, 20ml methyl methacrylate, 20ml vinylbenzene, 60ml toluene, 0.250g Diisopropyl azodicarboxylate and 1ml dehydrated alcohol are placed in the beaker, fully mix and form homodisperse mixing solutions, the beaker that mixing solutions is housed is put into ultrasonic apparatus ultrasonic radiation under the nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 60min, ultrasonic power 650W; Obtain reacting rear solution;
(2) adding 300ml anhydrous methanol precipitates in the rear solution to reacting, and filters and is precipitated thing, with the also grinding of throw out washing, vacuum drying, has obtained the Nanoscale Iron polymer composites, and polymer composites is the grey black pressed powder.
Embodiment 2:
(1) 0.300g FERRIC CHLORIDE ANHYDROUS, 25ml methyl methacrylate, 15ml vinylbenzene, 60ml toluene, 0.250g Diisopropyl azodicarboxylate and 1ml dehydrated alcohol are placed in the beaker, fully mix and form homodisperse mixing solutions, the beaker that mixing solutions is housed is put into ultrasonic apparatus ultrasonic radiation under the nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 60min, ultrasonic power 650W; Obtain reacting rear solution;
(2) adding 300ml anhydrous methanol precipitates in the rear solution to reacting, and filters and is precipitated thing, with the also grinding of throw out washing, vacuum drying, has obtained the Nanoscale Iron polymer composites, and polymer composites is the grey black pressed powder;
(3) with VECTOR 33 Fourier transform infrared spectrometer (FT-IR) Nanoscale Iron polymer composites powder is carried out infrared spectrum characterization, from the infrared spectrogram (see figure 1) of gained as can be known: infrared spectrum absorpting peak value and the literature value of experiment products obtained therefrom meet better, measured value is basically identical with literature value, proves the existence that truly has each group of multipolymer in the product.
Embodiment 3:
(1) 0.300g FERRIC CHLORIDE ANHYDROUS, 15ml methyl methacrylate, 25ml vinylbenzene, 60ml toluene, 0.250g Diisopropyl azodicarboxylate and 1ml dehydrated alcohol are placed in the beaker, fully mix and form homodisperse mixing solutions, the beaker that mixing solutions is housed is put into ultrasonic apparatus ultrasonic radiation under the nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 60min, ultrasonic power 650W; Obtain reacting rear solution;
(2) adding 300ml anhydrous methanol precipitates in the rear solution to reacting, and filters and is precipitated thing, with the also grinding of throw out washing, vacuum drying, has obtained the Nanoscale Iron polymer composites, and polymer composites is the grey black pressed powder;
(3) with DX-2000 type X-ray diffractometer (XRD) Nanoscale Iron polymer composites powder being carried out XRD characterizes, from gained XRD figure (see figure 2) as can be known: the existence of iron is arranged the product really, because it is very few to add the amount of iron trichloride in the nano material, the diffraction peak of iron is not sharp-pointed, but proof has iron to exist in the matrix material.
Claims (1)
1. ultrasonic initiation solution polymerization prepares the method for Nanoscale Iron polymer composites, it is characterized in that concrete operation step is as follows:
(1) 0.250～0.300g FERRIC CHLORIDE ANHYDROUS, 15～25ml methyl methacrylate, 15～25ml vinylbenzene, 45～60ml toluene, 0.200～0.300g Diisopropyl azodicarboxylate and 1～2ml dehydrated alcohol are mixed, form homodisperse mixing solutions, with mixing solutions ultrasonic radiation under the nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 55～65min, ultrasonic power 550～650W obtains reacting rear solution;
(2) add 250～300ml anhydrous methanol in the solution after the reaction and precipitate, filter and be precipitated thing, with throw out washing, vacuum drying and grind, obtained the Nanoscale Iron polymer composites; The Nanoscale Iron polymer composites is the dark gray powder shape.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105080027A (en) * | 2014-05-09 | 2015-11-25 | 中国人民解放军63971部队 | Disinfecting material taking nano zero-valent iron as main disinfecting component and preparation method thereof |
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| CN101579745A (en) * | 2008-05-15 | 2009-11-18 | 南开大学 | Cladding nanometer iron stable in air and preparation method thereof |
| CN102614918A (en) * | 2012-03-08 | 2012-08-01 | 昆明理工大学 | Preparation method of dispersant modified iron nanoparticles |
| CN102775548A (en) * | 2012-07-30 | 2012-11-14 | 安徽理工大学 | Method for polymerizing and preparing nanometer silver-PAAEM (Ploy Acetoacetoxyethyl Methacrylate) composite material through ultrasonically initiating emulsifier-free emulsion |
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Patent Citations (4)
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| DE3617903A1 (en) * | 1986-05-28 | 1987-12-03 | Michail Lazarevic Fridman | Process for the production of products based on polyethylene |
| CN101579745A (en) * | 2008-05-15 | 2009-11-18 | 南开大学 | Cladding nanometer iron stable in air and preparation method thereof |
| CN102614918A (en) * | 2012-03-08 | 2012-08-01 | 昆明理工大学 | Preparation method of dispersant modified iron nanoparticles |
| CN102775548A (en) * | 2012-07-30 | 2012-11-14 | 安徽理工大学 | Method for polymerizing and preparing nanometer silver-PAAEM (Ploy Acetoacetoxyethyl Methacrylate) composite material through ultrasonically initiating emulsifier-free emulsion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080027A (en) * | 2014-05-09 | 2015-11-25 | 中国人民解放军63971部队 | Disinfecting material taking nano zero-valent iron as main disinfecting component and preparation method thereof |
| CN105080027B (en) * | 2014-05-09 | 2018-10-12 | 安徽与时环保工程技术有限公司 | With the pasteurization material and preparation method thereof that nano zero valence iron is main disinfection composition |
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Effective date of registration: 20161028 Address after: 232007 LITE-ON Road, Huainan economic and Technological Development Zone, Anhui 68, China Patentee after: Anhui Guoao Sporting Goods Making Co., Ltd. Address before: 232001 Anhui Province, Huainan city Shungeng Road No. 168 Patentee before: Anhui University Of Science And Technology |
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Denomination of invention: Method for preparing nano iron polymer composite with solution polymerization by ultrasounds Effective date of registration: 20180824 Granted publication date: 20141105 Pledgee: Huainan commercial and Commercial Bank of China Limited by Share Ltd Pledgor: Anhui Guoao Sporting Goods Making Co., Ltd. Registration number: 2018340000435 |
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