CN102924647B - 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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- CN102924647B CN102924647B CN201210459407.1A CN201210459407A CN102924647B CN 102924647 B CN102924647 B CN 102924647B CN 201210459407 A CN201210459407 A CN 201210459407A CN 102924647 B CN102924647 B CN 102924647B
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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 the method for Nanoscale Iron/PMMA-PS matrix material is prepared in a kind of ultrasonic initiation solution polymerization.
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, make this type of nano composite material not only there is the surface effects of nano material, the character such as quantum size effect, and by 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, thereby opened up the application of nano composite material in field of functional materials.
The document that just China and foreign countries report, the research of the oxide compound of Nanoscale Iron is full-fledged already, and is report about the fresh 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 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 organism is contingent, and this material synthetic be by organism, close with metallochemistry bond rather than simply mix.
The preparation method of nano metal/polymer composites has a lot, as irradiation chemosynthesis, high-energy ball milling method, sol-gel method, dispersion copolymerization method, graft process, blending method etc.Ultrasonic technique, as a kind of novel synthetic technology, has unique effect in nano particle preparation.Ultrasonic polymerization is a kind of novel and polymerization process that efficiency is higher.Ultrasonic polymerization utilizes hyperacoustic " cavitation effect " exactly, 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, eliminate partial concn irregular, improve reaction efficiency, accelerate mass transfer and heat transfer process between interface, 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 is mainly to adopt emulsion polymerisation process, solution polymerization process is compared it, and water not in solution polymerization process, does not have sewage handling problem; In production, do not add additive, 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 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 fresh few, adopting the work of ultrasonic solution polymerization synthesis of nano iron/polymer composites is only a beginning, needs to study further deeply.
Summary of the invention
In order to overcome the deficiency of the synchronization extent of nano metal reduction and polymer polymerizing, the object of the invention is to adopt a kind of new synthetic technology, i.e. the method for Nanoscale Iron polymer composites is prepared in ultrasonic initiation solution polymerization.
The operation steps that the present invention specifically prepares Nanoscale Iron polymer composites is as follows:
The concrete operation step that Nanoscale Iron polymer composites is prepared in ultrasonic initiation solution polymerization 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, by mixing solutions ultrasonic radiation under nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 55～65min, ultrasonic power 550～650W, obtains reacting rear solution;
(2) after reaction, add 250～300ml anhydrous methanol to precipitate in solution, filter and be precipitated thing, by throw out washing, vacuum drying and grind, obtained Nanoscale Iron polymer composites; Nanoscale Iron polymer composites is dark gray powder shape.
The monomer that the present invention selects is simpler, is easy to polymerization; Wherein polystyrene, because having rigidity phenyl ring and flexible alkyl, has certain intensity and thermal characteristics, and good fluidity; Polymethylmethacrylate has the good transparency, but the defect 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, mobility is better, applies more extensive.
Nanoscale Iron particle diameter is little, very easily reunites, thereby has reduced reactive behavior.In addition, nano iron particles in air easily oxidation, also for it use and transportation is made troubles; Modally prevent that Nanoscale Iron from reuniting and the method for oxidation is at the coated one deck organic macromolecule in Nanoscale Iron surface or loaded on carrier.Nanoscale Iron polymer composites is along with the sharply decline of particle diameter, volume effect, surface effects, quantum size effect and macro quanta tunnel effect etc. cause nanoparticle to have good electricity, thermal and magnetic, light characteristic and catalytic etc., as can be for magnetic recording material, electromagnetic wave absorbent material, catalyzer and underground water and soil remediation etc., this makes its prospect that 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 polymkeric substance.Solution itself just has fabulous dispersiveness, and utilizes hyperacoustic cavitation effect, can eliminate partial concn irregular, 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 is also a kind of widely used metallic element, it is combined with organic monomer and while making nano composite material, should notes the anti-oxidation processing of iron, in experimentation, need always nitrogen injection endlessly, and ultrasonic power, time and ultrasonic gap are all on synthetic impact to some extent.The present invention's solution polymerization under ultrasound condition, a step has directly been synthesized Nanoscale Iron polymer composites, and this is a kind of method of green, energy-conservation environmental protection again relatively.
Accompanying drawing explanation
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, Tianjin Bo Di Chemical Co., Ltd.; Vinylbenzene, analytical pure, Shantou City Xi Long Chemical Co., Ltd.;
(2) solvent: toluene, analytical pure, Shanghai Su Yi chemical reagent company limited;
(3) initiator: Diisopropyl azodicarboxylate, chemical pure, upper seamount Pu Chemical Co., Ltd.;
(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, Wuxi City Ya Sheng Chemical Co., Ltd..
Embodiment 1:
The concrete operation step that Nanoscale Iron polymer composites is prepared in ultrasonic initiation solution polymerization 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 beaker, be thoroughly mixed to form homodisperse mixing solutions, the beaker that mixing solutions is housed is put into ultrasonic apparatus ultrasonic radiation under nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 60min, ultrasonic power 650W; Obtain reacting rear solution;
(2) after reaction, add 300ml anhydrous methanol to precipitate in solution, filter and be precipitated thing, by throw out washing, vacuum drying and grind, obtained Nanoscale Iron polymer composites, polymer composites is 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 beaker, be thoroughly mixed to form homodisperse mixing solutions, the beaker that mixing solutions is housed is put into ultrasonic apparatus ultrasonic radiation under nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 60min, ultrasonic power 650W; Obtain reacting rear solution;
(2) after reaction, add 300ml anhydrous methanol to precipitate in solution, filter and be precipitated thing, by throw out washing, vacuum drying and grind, obtained Nanoscale Iron polymer composites, polymer composites is grey black pressed powder;
(3) by VECTOR 33 Fourier transform infrared spectrometer (FT-IR), Nanoscale Iron polymer composites powder is carried out to infrared spectrum characterization, infrared spectrogram (see figure 1) from gained: 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 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 beaker, be thoroughly mixed to form homodisperse mixing solutions, the beaker that mixing solutions is housed is put into ultrasonic apparatus ultrasonic radiation under nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 60min, ultrasonic power 650W; Obtain reacting rear solution;
(2) after reaction, add 300ml anhydrous methanol to precipitate in solution, filter and be precipitated thing, by throw out washing, vacuum drying and grind, obtained Nanoscale Iron polymer composites, polymer composites is grey black pressed powder;
(3) with DX-2000 type X-ray diffractometer (XRD), Nanoscale Iron polymer composites powder is carried out to XRD sign, known from gained XRD figure (see figure 2): product, really to have the existence of iron, owing to adding in nano material, the amount of iron trichloride is very few, the diffraction peak of iron is not sharp-pointed, but in matrix material, proof has iron to exist.
Claims (1)
1. the method for Nanoscale Iron polymer composites is prepared in ultrasonic initiation solution polymerization, 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, by mixing solutions ultrasonic radiation under nitrogen protection condition, set ultrasonic grating constant: ultrasonic 1s, gap 1s, ultrasonic time 55～65min, ultrasonic power 550～650W, obtains reacting rear solution;
(2) after reaction, add 250～300ml anhydrous methanol to precipitate in solution, filter and be precipitated thing, by throw out washing, vacuum drying and grind, obtained Nanoscale Iron polymer composites; Nanoscale Iron polymer composites is dark gray powder shape.
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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 |