CN100427392C - Rare earth particle and montmorillonite nano composite materials and process for preparing same - Google Patents
Rare earth particle and montmorillonite nano composite materials and process for preparing same Download PDFInfo
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- CN100427392C CN100427392C CNB2006100426870A CN200610042687A CN100427392C CN 100427392 C CN100427392 C CN 100427392C CN B2006100426870 A CNB2006100426870 A CN B2006100426870A CN 200610042687 A CN200610042687 A CN 200610042687A CN 100427392 C CN100427392 C CN 100427392C
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Abstract
The present invention discloses a rare earth particle / montmorillonite nanometer composite material and a preparation method thereof. In the method, surface active agent emulsion is self-assembled so as to obtained a molded plate, a polymer monomer is used as an oil phase, and a rare earth ionized water solution is used as a water phases; the oil phase and the water phase are mixed with each other so as to form the micro emulsion of reverse micelle of rear earth nanometer particles, and the rear earth particles are enabled to uniformly disperse in the oil phases to form a thermodynamic stable emulsion system; the emulsion is intercalated among slice layers of organic montmorillonite, an initiator is added to the emulsion, and in-situ polymerization is directly carried out to the polymer monomer; then, microwave radiation is carried out so that the polymer is decomposed into CO2 and H2O so as to obtain a rare earth particle /MMT nanometer composite material. The rare earth particle / montmorillonite nanometer composite material is characterized in that the thicknesses of the slice layers of the montmorillonite is approximately 30 to 50 nm, the average particle diameter of the rare earth nanometer particles is about 25 nm, and the rare earth nanometer particles have large interface areas. Interfaces of the rare earth particles and montmorillonite bases have ideal bonding performance, so the problem of the agglomeration of the nanometer particles is effectively solved, and physical chemical properties of composite materials are greatly improved.
Description
Technical field
The present invention relates to a kind of nano composite material, particularly a kind of rare earth ion/Nano composite material of montmorillonite based on polynite; The present invention also relates to a kind of method of utilizing the emulsion intercalation microwave method to prepare rare earth ion/Nano composite material of montmorillonite simultaneously.
Background technology
Polynite because aboundresources, inexpensive, have preferably that performances such as swelling property, cementability, adsorptivity, oilness and cationic exchange can be used as caking agent, absorption agent, weighting agent, catalyzer, washing composition, thickening material etc., be widely used in fields such as industrial or agricultural, medicine and environmental improvement, be called as " clay ", " omnipotent clay ", " lived mineral " with thousand kinds of purposes.
In recent years, the research of polynite intercalation compound is developed, and makes polynite have higher practicality.Because polynite singularity is widely used as the filler of thermal resistance polymer composites and conducting polymer composite material.Filler content is high more within the specific limits, and performance of composites is good more, but the mechanical property of material descends to some extent, and particularly toughness of material can obviously descend.An effective way that improves composite property is evenly to be filled in polymkeric substance with nano level inorganic particulate, can improve its thermal property, electric property and mechanical property, but adopt traditional blend method, be difficult to make the homodisperse on the filler acquisition nanometer level.Because the chemical structure and the physical aspect of filler and polymkeric substance differ bigger, at present, the interfacial energy that the interface modification technology is difficult to change fully between filler and polymeric matrix reduces interfacial tension, realizes nano level homodisperse and bonding interface.Therefore matrix material does not reach the molecular dispersion level, and only belongs to the microcosmic mixing material, has influenced the improvement of the due toughness of material, rigidity, thermotolerance and electric property.Improved approach is each phase homodisperse and form matrix material.Owing to there is very strong bonding force between montmorillonite layer, be easy to generate montmorillonite layer and assemble, cause the ununiformity of compound system middle-weight rare earths particle, exceed nano level, no longer be nano composite material, thereby influence performance of composites greatly.Can not be dispersed in the montmorillonite layer with nano level and influence matrix material in order to solve prior art middle-weight rare earths particle.In the polymerization process of matrix material, rely on tensio-active agent to form microemulsion, the isotropy of spontaneous formation, Thermodynamically stable, appearance transparent or translucent colloid emulsion, produce reverse micelle " pond reacting field ", this " microreactor " space can synthesis nano particulate, need not to carry out organically-modified and redispersion in presoma to inorganic nano-particle, directly intercalation carries out the body in-situ polymerization, carry out microwave radiation then and make rare earth ion/MMT nano composite material, both overcome rare earth ion homodisperse difficult problem in montmorillonite layer, simplified technology again.Have only montmorillonite layer and rare earth ion that strong interaction is arranged, and reach the dispersion of nanoscale, just the synergetic property of the two effectively may be brought into play, make it to become combination ideally, the good nano composite material of obtained performance.
Summary of the invention
The purpose of this invention is to provide a kind of rare earth ion/Nano composite material of montmorillonite;
Another object of the present invention provides a kind of method of utilizing the emulsion intercalation microwave technology to prepare rare earth ion/Nano composite material of montmorillonite.
Rare earth ion/Nano composite material of montmorillonite of the present invention is rare earth ion and montmorillonite layer homodisperse, combines closely; Wherein the particle diameter of rare earth ion is 20～30nm, and the thickness of montmorillonite layer is 30～50nm.
The pbw of described rare earth ion and polynite is: 1～20 part of rare-earth nanometer particles, 1～30 part of polynite.
Described rare-earth nanometer particles is the rare earth oxide particle.
The preparation method of rare earth ion/Nano composite material of montmorillonite of the present invention, be that a certain amount of polymer monomer is dissolved in the dispersion agent that is dissolved with tensio-active agent, stir to wherein adding a certain amount of rare earth salt aqueous solution, at room temperature ultra-sonic dispersion is 30～60 minutes, forms the reverse micelle emulsion again; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 60～80 ℃, magnetic agitation was disperseed intercalation 2～3 hours, add an amount of initiator subsequently and make the polymer monomer initiated polymerization, react after 15～30 hours and to add the acclimatization agent rare earth ion is precipitated fully, filter, wash vacuum drying; Be the microwave radiation 0.2～1.5 hour of 2000～2500MHz with frequency then, make polymer unwinds become CO
2And H
2O, microwave radiation is not obvious to rare earth ion crystallization influence, and resistant to elevated temperatures polynite remains unchanged, and makes rare earth ion/Nano composite material of montmorillonite.
The polymer monomer that present method adopts is any in aniline, methyl methacrylate, methyl acrylate, pyrroles or the O-Phenylene Diamine.
The tensio-active agent that present method adopts is anion surfactant, cats product or nonionogenic tenside; Wherein anion surfactant is sodium lauryl sulphate, sodium stearate or stearic acid; Cats product is a palmityl trimethyl ammonium chloride; Nonionogenic tenside is an alkylphenol polyoxyethylene.The add-on of tensio-active agent is 15～25% of a polymer monomer weight.
The existence of tensio-active agent prepares the rare-earth nanometer particles that is uniformly dispersed at self-assembly formation reverse micelle microemulsion on the one hand and plays an important role, again as the coating materials of polynite and rare-earth nanometer particles, improved oil phase and water consistency and avidity.Emulsion is the translucent colloidal dispersion system of isotropy, Thermodynamically stable, outward appearance that relies on the spontaneous formation of tensio-active agent." pond reacting field " in the emulsion is nano level, size is little and be evenly distributed, limited the growing space of nanoparticle effectively, make water and oil phase in reaction process, be uniformly dispersed, the rare earth ion of aqueous phase is with regard to being tied in the polymkeric substance and keep original homodisperse state when polymer monomer generation polymerization, carry out microwave radiation then and make rare earth ion/MMT nano composite material, solved the agglomeration traits of nanoparticle effectively, and reach the homodisperse of nanoscale, make nano composite material have the unapproachable premium properties of many employing traditional methods.
The dispersion medium that the present invention adopts is trichloromethane, water or ethanol.The amount of dispersion medium is 4～10 times of polymer monomer quality.The effect of dispersion medium is to promote the dispersion of polynite in polymer monomer.Dispersion medium is decided according to monomer, rare earth ion, initiator.Good dispersion medium should make polynite and rare-earth nanometer particles disperse easily and have good miscibility with monomer and initiator, and the composite property of preparing is good.
The rare-earth salts that the present invention adopts is the nitrate or the muriate of soluble ree; Wherein the add-on of rare-earth salts is 1～20% of a polymer monomer quality.
The organo montmorillonite that the present invention adopts is to be organic modifiers with cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride or octadecyl trimethylammonium bromide, carries out natural montmorillonite organically-modified and gets; The add-on of organo montmorillonite is 1～30% of a polymer monomer quality.
The method of modifying of organo montmorillonite is: a certain amount of properties-correcting agent is placed water, add appropriate hydrochloric acid and regulate the protonated solution of formation; The polynite that to purify in right amount places water again, in 40～60 ℃ water bath with thermostatic control, leave standstill behind stirring heating 30～60min, form the polynite aqueous dispersions, then above-mentioned protonated solution is dropwise joined in the polynite aqueous dispersions, and with vibration of ultrasonic wave 3～4 hours, again through suction filtration and be washed with water to no bromide anion and chlorion, at last under 70～90 ℃, through vacuum-drying, grind, sieve after, products therefrom is an organo montmorillonite.The lamella of this organo montmorillonite is evenly dispersed in the organic modifiers matrix, the thickness of lamella is 40～50nm, sheet interlayer spacing is 3～15nm, and this special structure of organo montmorillonite is for the nanofeature for preparing rare earth ion/Nano composite material of montmorillonite provides basis.
The initiator that the present invention adopts is Diisopropyl azodicarboxylate, ammonium persulphate or p-methyl benzenesulfonic acid iron; The add-on of initiator is 0.1～320% of a polymer monomer quality, determines according to polymer monomer.
The precipitation agent that the present invention adopts is a sodium hydroxide.
The present invention compared with prior art has the following advantages:
1, rare earth ion/Nano composite material of montmorillonite of the present invention, make the thickness of montmorillonite layer be approximately 30～50nm, can find out significantly that the polynite after expanding is keeping peeling off phenomenon on original laminate structure basis, formed regular nano composite material, the median size of rare-earth nanometer particles is about 25nm, has very large interfacial area, rare earth ion and polynite basal body interface have the ideal adhesiveproperties, can eliminate two material thermal expansivity and not match and immiscible problem, make that the physicochemical property of matrix material is well improved.
2, preparation method of the present invention is template with the tensio-active agent, the formation of rare-earth nanometer particles and the preparation of matrix material are carried out synchronously, and water and oil phase are uniformly dispersed in reaction process, when in the emulsion during monomer generation polymerization rare earth ion with regard to being tied in the polymkeric substance and keep original homodisperse state, carry out microwave radiation for some time polymer unwinds CO in microwave then
2And H
2O, microwave radiation is not obvious to rare earth ion crystallization influence, and resistant to elevated temperatures polynite remains unchanged, solved the agglomeration traits of nanoparticle effectively, and reach the homodisperse of nanoscale, thereby effective simplification the Composite Preparation program, shortened preparation time.Method of the present invention is simple to operate, the production efficiency height, and cost is low, and is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is that rare earth ion of the present invention/Nano composite material of montmorillonite forms synoptic diagram
Fig. 2 is rare earth ion of the present invention/Nano composite material of montmorillonite SEM photo
Fig. 3 is the XRD figure of rare earth ion/Nano composite material of montmorillonite of the present invention
(a) is that composite amplifies 6.2 * 10 among Fig. 24SEM photo doubly can be clear that to cover and take off The rare-earth nanometer particles that disperses on the structure of soil and the lamella; (b) be the SEM photo figure of one of them lamella, Can clearly see equally and disperse equably rare-earth nanometer particles on the montmorillonite layer. Can estimate from figure (a) The thickness of calculating montmorillonite layer is approximately 30～50nm, and is bigger than the thickness of former MMT lamella, this be because of Be the CO that produces during polymer unwinds on the montmorillonite layer2And H2O causes the swollen shape of imvite. By figure (a) Can find out significantly that montmorillonite layer has kept its original layer structure substantially, rare earth ion has all inserted Its interlayer forms regular rare earth ion/MMT nano composite material, can find out rare earth ion and illiteracy Take off native lamella in conjunction with closely, should have suction-operated between them. Can see significantly that by figure (b) rare earth receives The distribution of rice corpuscles between montmorillonite layer is more even, and small size, and average grain diameter is at 25nm About, can think that thus the nano particle of composite is in reverse micelle microemulsion " pond reacting field " Carry out, emulsion " microreactor " size is little and be evenly distributed, so that water and oil phase divide in course of reaction Loose evenly, the inorganic phase rare-earth nanometer particles keeps with regard to being tied in the organism when organism generation polymerization Originally homodisperse state has limited reunion and the growth of nano particle. And in microwave polymer unwinds Become CO2And H2O, resistant to elevated temperatures rare earth ion and imvite remain unchanged, and have effectively solved nanoparticle The agglomeration traits of son makes rare earth ion/MMT nano composite material.
Among Fig. 3, be the XRD figure of MMT (a), (b) be Pr2O
3The XRD of/MMT nano composite material Figure (c) is the XRD figure of polymer/rare earth ion/MMT nano composite material. According to the Bragg equation 2dsin θ=n λ as can be known, angle corresponding to diffraction maximum reduces, the interlamellar spacing of imvite increases. Among Fig. 3 (c) with (a) compare as can be known, polymer/rare earth ion/MMT nano composite material ° is located corresponding diffraction in 2 θ=7.2 The peak disappears with respect to the diffraction maximum of simple MMT, covers and ° locate to have occurred this explanation of diffraction maximum in 2 θ=2.1 Take off native sheet interlayer spacing and further increase, polymer has inserted the interlayer of imvite. (a), (b) and (c) phase among Fig. 3 Than as can be known, (b) ° locate to have occurred diffraction maximum in 2 θ=2.6, show rare earth ion/MMT nanometer composite layer Spacing is less than the interlamellar spacing of polymer/rare earth ion/MMT nano composite material, and greater than the interlayer of MMT Distance, compare with (a) (b) and (c) in 2 θ=12.5 ° and 2 θ=27.6 ° locate new diffraction maximum all to have occurred, illiteracy is described Take off and inserted simultaneously rare earth ion in the soil, the intensity of diffraction maximum illustrates more by force the rare earth ion in this composite Crystallization is better. Above analytic explanation polymer unwinds in microwave becomes CO2And H2O is so that interlamellar spacing to some extent Reduce, microwave is not obvious to rare earth ion crystallization impact, and resistant to elevated temperatures imvite remains unchanged, rare earth Particle has inserted between cheating engaging layer, has effectively solved the agglomeration traits of nano particle, makes rare earth ion / MMT nano composite material.
Embodiment
Embodiment 1,100 parts of aniline, 15 parts of sodium lauryl sulphate joined in 400 parts the water and stir; Rare earth Nd with 20 parts
2O
3Be dissolved in the NdCl that hydrochloric acid is mixed with 0.1mol/L
3The aqueous solution, and join in the above-mentioned mixing solutions, at room temperature ultra-sonic dispersion is 30 minutes, forms the reverse micelle emulsion.With 1 part of weight through purify, organically-modified polynite places water, leaves standstill behind 40～60 ℃ of homothermic stirred in water bath heating 30～60min, forms the polynite aqueous dispersions; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 60 ℃, and magnetic agitation was disperseed intercalation 2 hours.Cooling subsequently moves to reactant in the ice-water bath about 2 ℃ and dropwise to add 100 parts of ammonium sulfate initiators, makes the polymer monomer initiated polymerization, react after 15 hours, add the NaOH solution of 0.3mol/L, rare earth ion is precipitated fully, filter, wash vacuum drying; Be the microwave radiation 0.2 hour of 2000MHz with frequency then, make polymer unwinds become CO
2And H
2O makes Nd
2O
3/ MMT nano composite material.
Embodiment 2,100 parts of methyl methacrylates, 18 parts of sodium stearate joined in 500 parts the trichloromethane and stir; Rare earth Nd with 15 parts
2O
3Be dissolved in the EuCl that hydrochloric acid is mixed with 0.1mol/L
3The aqueous solution, and join in the above-mentioned mixing solutions, at room temperature ultra-sonic dispersion is 35 minutes, forms the reverse micelle emulsion; Place water with 6 parts through purification, organically-modified polynite, behind 40～60 ℃ of homothermic stirred in water bath heating 30～60min, leave standstill, form the polynite aqueous dispersions; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 65 ℃, magnetic agitation was disperseed intercalation 2.5 hours, add 0.001 part of Diisopropyl azodicarboxylate subsequently, make the polymer monomer initiated polymerization, react the NaOH solution that adds 0.3mol/L after 18 hours, rare earth ion is precipitated fully, filter, wash vacuum drying; Be the microwave radiation 0.5 hour of 2200MHz with frequency then, make polymer unwinds become CO
2And H
2O makes Nd
2O
3/ Nano composite material of montmorillonite.
Embodiment 3,100 parts of methyl acrylates, 20 parts of stearic acid joined in 700 parts the ethanol and stir; Rare earth La with 10 parts
2O
3Be dissolved in the LaCl that hydrochloric acid is mixed with 0.1mol/L
3The aqueous solution, and join in the above-mentioned mixing solutions, at room temperature ultra-sonic dispersion is 40 minutes, forms the reverse micelle emulsion; Place water with 12 parts through purifying and carrying out organically-modified polynite, behind 40～60 ℃ of homothermic stirred in water bath heating 30～60min, leave standstill, form the polynite aqueous dispersions; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 70 ℃, magnetic agitation was disperseed intercalation 3 hours, adding 1 part of Diisopropyl azodicarboxylate subsequently is initiator, make the polymer monomer initiated polymerization, react the NaOH solution that adds 0.3mol/L after 20 hours, rare earth ion is precipitated fully, filter, wash vacuum drying; Be the microwave radiation 0.7 hour of 2100MHz with frequency then, make polymer unwinds become CO
2And H
2O makes La
2O
3/ Nano composite material of montmorillonite.
Embodiment 4,100 parts of pyrroles, 22 parts of palmityl trimethyl ammonium chlorides joined in 900 parts the trichloromethane and stir; Rare-earth salts Pr with 5 parts
2(CO
3)
3Be dissolved in nitric acid and be mixed with 0.1mol/LPr (NO
3)
3The aqueous solution, and join in the above-mentioned mixing solutions, at room temperature ultra-sonic dispersion is 45 minutes, forms the reverse micelle emulsion; Place water with 25 parts through purifying and carrying out organically-modified polynite, behind 40～60 ℃ of homothermic stirred in water bath heating 30～60min, leave standstill, form the polynite aqueous dispersions; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 75 ℃, and magnetic agitation was disperseed intercalation 2.5 hours.Cooling subsequently moves to reactant in the ice-water bath about 2 ℃, dropwise adds 150 parts of p-methyl benzenesulfonic acid iron initiators, makes the polymer monomer initiated polymerization, react the NaOH precipitation agent that adds 50 weight parts after 25 hours, filters, washs vacuum drying; Be the microwave radiation 1 hour of 2300MHz with frequency then, make polymer unwinds become CO
2And H
2O makes Pr
2O
3/ Nano composite material of montmorillonite.
Embodiment 5,100 parts of O-Phenylene Diamines, 25 parts of alkylphenol polyoxyethylene joined in 1000 parts the ethanol and stir; Rare earth Eu with 1 part
2O
3Be dissolved in the aqueous solution that hydrochloric acid is mixed with 0.1mol/L, and join in the above-mentioned mixing solutions, at room temperature ultra-sonic dispersion is 30 minutes, forms the reverse micelle emulsion; Place water with 30 parts through purifying and carrying out organically-modified polynite, behind 40～60 ℃ of homothermic stirred in water bath heating 30～60min, leave standstill, form the polynite aqueous dispersions; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 60 ℃, and magnetic agitation was disperseed intercalation 2 hours.Cooling subsequently moves to reactant that dropwise to add 100 parts of persulfuric acid in the ice-water bath about 2 ℃ be initiator, makes the polymer monomer initiated polymerization, react the NaOH solution that adds 0.3mol/L after 15 hours, rare earth ion is precipitated fully, filter, wash vacuum drying; Be the microwave radiation 1.5 hours of 2500MHz with frequency then, make polymer unwinds become CO
2And H
2O makes Eu
2O
3/ MMT nano composite material.
Claims (10)
1, a kind of rare earth ion/Nano composite material of montmorillonite is characterized in that: the particle diameter of rare earth ion is 20～30nm, and the thickness of montmorillonite layer is 30～50nm, and rare earth ion and montmorillonite layer are uniformly dispersed and combine closely.
2, a kind of rare earth ion/Nano composite material of montmorillonite as claimed in claim 1, it is characterized in that: the pbw of described rare earth ion and polynite is: 1～20 part of rare-earth nanometer particles, 1～30 part of polynite.
3, a kind of rare earth ion/Nano composite material of montmorillonite as claimed in claim 1 is characterized in that: described rare-earth nanometer particles is the oxide compound of rare earth.
4, a kind of preparation method of rare earth ion/Nano composite material of montmorillonite, be that polymer monomer is dissolved in the dispersion agent that is dissolved with tensio-active agent, the aqueous solution to the rare-earth salts that wherein adds polymer monomer quality 1～20% stirs again, at room temperature ultra-sonic dispersion is 30～60 minutes, forms the reverse micelle emulsion; Then at N
2Protection dropwise joins the reverse micelle emulsion in the organo montmorillonite aqueous dispersions down, attemperation to 60～80 ℃, magnetic agitation was disperseed intercalation 2～3 hours, the initiator that adds polymer monomer quality 0.1～320% subsequently makes the polymer monomer initiated polymerization, react after 15～30 hours and to add precipitation agent rare earth ion is precipitated fully, filter, wash vacuum drying; Be the microwave radiation 0.2～1.5 hour of 2000～2500MHz with frequency then, make polymer unwinds become CO
2And H
2O makes rare earth ion/Nano composite material of montmorillonite; Described polymer monomer is any in aniline, methyl methacrylate, methyl acrylate, pyrroles or the O-Phenylene Diamine.
5, as the preparation method of rare earth ion/Nano composite material of montmorillonite as described in the claim 4, it is characterized in that: described tensio-active agent is anion surfactant, cats product or nonionogenic tenside.
6, as the preparation method of rare earth ion/Nano composite material of montmorillonite as described in the claim 4, it is characterized in that: described anion surfactant is sodium lauryl sulphate, sodium stearate or stearic acid; Described cats product is a palmityl trimethyl ammonium chloride; Described nonionogenic tenside is an alkylphenol polyoxyethylene; The add-on of tensio-active agent is 15～25% of a polymer monomer weight.
7, as the preparation method of rare earth ion/Nano composite material of montmorillonite as described in the claim 4, it is characterized in that: described dispersion agent is trichloromethane, water or ethanol; The add-on of dispersion agent is 4～10 times of polymer monomer quality.
8, as the preparation method of rare earth ion/Nano composite material of montmorillonite as described in the claim 4, it is characterized in that: described rare-earth salts is the nitrate or the muriate of soluble ree.
9, as the preparation method of rare earth ion/Nano composite material of montmorillonite as described in the claim 4, it is characterized in that: described initiator is Diisopropyl azodicarboxylate, ammonium persulphate or p-methyl benzenesulfonic acid iron.
10, as the preparation method of rare earth ion/Nano composite material of montmorillonite as described in the claim 4, it is characterized in that: described precipitation agent is a sodium hydroxide.
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