CN1377921A - Process for preparing nano CaCO3/SiO2 core-shell structure particle - Google Patents
Process for preparing nano CaCO3/SiO2 core-shell structure particle Download PDFInfo
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Abstract
The present invention relates to the preparation of nano CaCo3/SiO2 core-shell structure particle and its organic hybrid. Under the action of acid matter, silicate in water suspension of sodium silicate containing nano calcium carbonate is hydrolyzed and condensated to produce sol deposited onto the surface of nano calcium carbonate to form nano CaCO3/SiO2 composite particle in core-shell structure. During the preparation of the composite particle, lipophilic revulsant and organic activator may be added so as to obtain nano CaCO3/SiO2 composite particle with organic hybridized surface. The nano CaCO3/SiO2 composite particle has SiO2 shell jointed via chemical bond to the surface of CaCO3 particle, and the organic modified is jointed to the surface of nano CaCO3/SiO2 composite particle also via chemical bond.
Description
Technical field
The present invention relates to a kind of nanometer CaCO
3/ SiO
2The preparation method of nucleocapsid structure composite particles and organic hybrid thing thereof.
Background technology
CaCO commonly used in industry such as coating, rubber, plastics and papermaking
3As weighting agent, its purpose mainly is to reduce the cost of material.The development of nanosecond science and technology makes nano level CaCO
3The a large amount of appearance, and the continuous progress of nanometer composite technology makes nanometer CaCO
3Being used for traditional industries such as plastics, rubber becomes possibility, and it acts on except that reducing cost, and bibliographical information nanometer CaCO is also arranged
3Also can play and strengthen toughness reinforcing effect.Nanometer CaCO
3Be used for coatings industry as loading pigment,, the bigger zinc sulfide white of density in the system had living space steric effect and plays the anti-settling effect though have exquisiteness, even, high, the good in optical property of whiteness; The paint film whiteness increases in system lacquer back, the gloss height, and opacifying power such as does not but reduce at advantage, but studies carefully its essential nanometer CaCO
3Still use as inert pigment.How at CaCO
3On the basis of nanoscale super-refinement advantage, also have some function when reducing cost, then not only can widen nanometer CaCO
3The application space, and when substituting the higher auxiliary agents such as titanium dioxide, silicon-dioxide and iron oxide red of price, material property is not reduced as pigment.
In the at present relevant Research on Surface Modification of inorganic powder material (comprising nano material), mainly based on organic coating modification research, comprise tensio-active agent processings, coupling agent technology, plasma technique, radiation grafting technology, introduce azo, peroxide, mistake ester etc. by esterification, hydroxylating at powder surface and have the free yl graft polymerization modification technology of functional group of trigger monomer polymerization and redox technology etc.; The inorganic coating modification research on relevant inorganic powder material, especially nano-powder material surface is then less, and is mostly with nano-TiO
2It is main that the surface of particle coats research, relevant nanometer CaCO
3The inorganic coating modification research on surface is also still at the experimental stage.The used technology of organic coating modification on inorganic powder material (comprising nano-calcium carbonate) surface is generally dry process and wet processing.Though dry process can be coated on powder surface with organic modifiers, there is the surface to coat between uneven, organic modifiers and the powder surface to be the shortcoming of aspect such as physical force form in it, and flying upward of inorganic powder easily sucked by human body in the course of processing; Inorganic powder need be at first prepared in wet processing, and then inorganic powder is dispersed in the appropriate solvent, and technical process is complicated, and processing cost increases, and the use of organic solvent also can cause the pollution of environment.Along with the raising of people's living standard and the enhancing of environmental protection consciousness; common inorganic powder surface organic active treatment process can not satisfy the needs of people to aspects such as economy, health and environment protection, thereby seeking a kind of safe, reliable and effective inorganic powder, especially nano powder surface, to modify the method for handling be to need the problem that solves at present in a hurry.And about nano-calcium carbonate surface coated silica and and the method for organism in-situ hybridization also do not have relevant report at present.
Summary of the invention
The objective of the invention is at nanometer CaCO
3Surface coated Si O
2Thereby prepare nano-calcium carbonate/silica dioxide composite particles, and in same system, nano-calcium carbonate/silica dioxide composite particles is carried out the original position organic hybrid, realize organic modification the composite particles surface with nucleocapsid structure.
The present invention adopts and contains the water glass waterborne suspension of nano-calcium carbonate under the acidic substance effect, thereby the reaction of silicate generation hydrolysis-condensation generates the colloidal sol precipitator method that colloidal sol is deposited on the nano-calcium carbonate surface, prepares the nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure; By in the composite particles preparation process, adding lipophilicity inductor and organic modifiers, obtain the nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure of surface organic matter hydridization.
The concrete technology of the inventive method is as follows:
(1) have the preparation of the nano-calcium carbonate/silica dioxide composite particles of nucleocapsid structure: will without the nano-calcium carbonate suspension of any finishing after filtration, carrying out washing treatment is with ion remaining in the system of removing; The powerful stirring down joins washed nano-calcium carbonate in the sodium silicate aqueous solution that concentration is 5%～70% (being generally 15%～45%), and ultrasonic dispersing is handled the back and continued to stir more than 2 hours; Reaction system is put into 70～85 ℃ water-bath, and dripping concentration with 0.5ml/min～35ml/min speed is the H of 0.5mol/L～5.5mol/L
2SO
4Dilute solution, control stir speed (S.S.) 2000～6000 commentaries on classics/min, and the pH value of regulation system is 5～10, ageing 2～5 hours; Reaction product through cooling, filter, promptly obtain having after washing and the 120 ℃ of drying treatment nano-calcium carbonate/silica dioxide composite particles of nucleocapsid structure.
(2) preparation of the nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure of surface organic matter hydridization: adding lipophilicity inductor ethylene glycol or volume ratio are 1: 1 ethylene glycol and ethanol in the system in above-mentioned (1) after ultrasonication, add R-SiX after ageing 1-4 hour
3Class organic modifiers, 15min-90min after product through cooling, filter, promptly obtain after washing and the 120 ℃ of drying treatment nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure of surface organic matter hydridization; Said organic modifiers R-SiX
3In R be meant can with organic resin reaction or dissolved methacrylic ester, amino or vinyl mutually, X is meant methoxyl group, oxyethyl group or the halogen that easily is hydrolyzed.
The mass concentration of used nano-calcium carbonate generally is 5%～65% in the aforesaid method (1), and the mean sizes of nano-calcium carbonate is 15～100nm.The concentration of used organic modifiers is generally 0.5%～15% of composite particles total mass number in the method (2); Used organic modifiers is one or both in γ-(methacryloxypropyl) Trimethoxy silane (KH-570), vinyltriethoxysilane (A-151), N-(β amido ethyl)-γ-aminocarbonyl propyl Trimethoxy silane (KH-792) and the γ-An Jibingjisanyiyangjiguiwan (KH-550); The concentration of lipophilicity inductor be in the system water quality 5%～30%.
The present invention adopts silicon source and the dispersion medium of water glass aqueous solution as the modification of nano-calcium carbonate surface inorganic, guarantees particle dispersive stability and homogeneity thereby can form electrostatic double layer on the Nano particles of calcium carbonate surface; Nano-calcium carbonate surface coated silica both can improve the performance (as surface property, thermal characteristics) of nano-calcium carbonate, can make particle surface contain the higher silanol base functional group of a large amount of reactive behavioies again, for the organic active modification is laid a good foundation; And because the preparation and the organic hybrid modification of composite particles are all finished in same water-based system, both can overcome the shortcoming that is easily sucked of flying upward of powder in the dry process technology, can avoid again in the wet processing process the introducing of the investment of equipment and organic solvent pollution that environment caused by human body.
Show that by TG, FTIR, TEM, XPS and X-ray diffraction analysis the nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure and the surperficial organic hybrid thing particle thereof of the inventive method preparation are of a size of nanometer scale, homogeneous grain diameter; And thereby coated with silica has nucleocapsid structure at the inorganic coating layer of nano-sized carbon calcium particle surface formation, silica shell is not to be coated on the Nano particles of calcium carbonate by the simple physics effect, but is keyed to the Nano particles of calcium carbonate surface by chemical b `.By in system, introducing suitable and an amount of lipophilicity inductor and organic modifiers, when preparation has the nano-calcium carbonate/silica dioxide composite particles of nucleocapsid structure, make nano-calcium carbonate/silica dioxide composite particles surface organic again, still there is the absorption peak of organic modifiers in its IR spectrogram in product after repeatedly washing and filtration treatment, show that organic modifiers is chemically bonded on nano-calcium carbonate/silica dioxide composite particles surface.
The present invention selects and control of process parameters by reagent, in same system, both can prepare nano-calcium carbonate/silica dioxide composite particles, make the composite particles surface organic when improving nano-calcium carbonate performance (as surface property, thermal decomposition performance), because the coated with silica layer is contained on the nano-calcium carbonate surface, can widen the application space of nano-calcium carbonate in traditional industry fields such as rubber, plastics, coating.The present invention adopts the water-based dispersion suspension liquid of nano-calcium carbonate, the inorganic modification on nano-calcium carbonate surface and organic active are handled and are finished stage by stage in same system, not only can reduce the investment of equipment and reagent aspect, also can avoid pollution that environment is caused, so the present invention have great social significance and application prospects.
The invention will be further described below by way of embodiments and drawings.
Description of drawings
Fig. 1 is nanometer CaCO
3The TEM photo;
Fig. 2 is nanometer CaCO
3/ SiO
2The TEM photo of composite particles;
Fig. 3 is CaCO
3Surperficial XPS before and after coating, wherein curve 1 is pure nanometer CaCO
3, curve 2 is nanometer CaCO
3/ SiO
2Composite particles;
Fig. 4 is CaCO
3/ SiO
2In Ca2pXPS spectrum;
Fig. 5 is CaCO
3/ SiO
2Middle Si2pXPS spectrum.
Embodiment
Will without the nano-calcium carbonate suspension of any finishing after filtration, carrying out washing treatment is with ion remaining in the system of removing; Powerful stir that down washed nano-calcium carbonate to be joined concentration be that ultrasonic dispersing is handled the back and continued to stir 2 hours in 15% the sodium silicate aqueous solution; Reaction system is put into 75～80 ℃ water-bath, and dripping concentration with 25ml/min speed is the H of 1mol/L
2SO
4Dilute solution, control stir speed (S.S.) 4000 commentaries on classics/min, and the pH value of regulation system is 9.5, ageing 4 hours; Reaction product through cooling, filter, promptly obtain having after washing and the 120 ℃ of drying treatment nano-calcium carbonate/silica dioxide composite particles of nucleocapsid structure.Its size, composition, structure and performance characterization are as follows: the size of composite particles and surface topography
From accompanying drawing 1 pure nanometer CaCO
3The electromicroscopic photograph of particle as can be seen, nanometer CaCO before the coated with silica modification
3Particle is cube, is arranged in chain, and size is 40～60nm, and particle surface is smooth; And nanometer CaCO in the accompanying drawing 2
3/ SiO
2The size of composite particles does not have considerable change, and it is irregular that shape begins to become, based on cubes, and the very small particles almost spherical, the surface has cellular flocculence thing to exist.The surface composition of composite particles and structure:
To pure nanometer CaCO
3With nanometer CaCO
3/ SiO
2Composite particles is made XPS surface analysis of components, the results are shown in accompanying drawing 3.As can be seen, pure nanometer CaCO
3Have only C peak, O peak and Ca peak, and nanometer CaCO
3/ SiO
2Complex body the Si peak also occurred near 103eV except C peak, O peak and Ca peak are arranged.XPS surface atom composition quantitative analysis results (seeing Table 1) shows nanometer CaCO
3/ SiO
2The mol ratio of elements Si/Ca is 3.25 in the complex body, and the Si/Ca mol ratio that Theoretical Calculation and TG analyze is 0.13, and 3.25 much smaller than XPS analysis illustrates the nanometer CaCO that the present invention is prepared
3/ SiO
2The SiO that the colloidal sol precipitation generates in the complex body
2Be not simply with physical blending mode and nanometer CaCO
3Coexistence, but be coated on nanometer CaCO
3The surface forms the composite particles with nucleocapsid structure.Because electron beam need penetrate SiO during the ratio analysis of XPS surface-element
2Coating layer just can be got to CaCO
3, nanometer CaCO
3/ SiO
2The relative content of C and Ca element and pure nanometer CaCO in the complex body
3More many than little, this is the prepared nanometer CaCO of indirect proof the present invention also
3/ SiO
2Complex body has nucleocapsid structure.
Table 1 nanometer CaCO
3Surperficial composition relative content before and after coating
Percentage(％)
C O Ca Si Si/Ca
CaCOr 53.12 38.83 8.05 0 0
CaCO
3/SiO
2?34.75 47.13 4.26 13.84 3.25
Nanometer CaCO in the accompanying drawing 4
3/ SiO
2Ca2p in the complex body
1/2And Ca2p
3/2The electron binding energy of track is respectively 350.7eV and the pure CaCO of 347.2eV.
3Middle Ca2p
1/2And 2p
3/2Its theoretical value of electron binding energy on the track be respectively 350.3eV and 346.8eV (Liu Shihong, the king is when foolish, Pan Chenghuang writes, X-ray photoelectron spectroscopic analysis, Science Press, 1988, P312).Nanometer CaCO
3/ SiO
2Ca2p orbital electron bound energy is than pure CaCO in the complex body
3In Ca2p orbital electron bound energy exceed 0.4eV, show that the Si element is to be incorporated into CaCO with the valence bond form in the complex body
3The surface has formed the Si-O-Ca key.This conclusion also can be at Si2p and nanometer CaCO
3Surface coated Si O
2Obtain proof in the XPS spectrum of the O1s orbital electron of front and back.
Pure SiO
2The bound energy of middle Si2p orbital electron is positioned at 103eV～103.6eV scope, nanometer CaCO in the accompanying drawing 5
3/ SiO
2The bound energy peak of Si2p orbital electron also appears in complex body in this scope; And the peak shape broadening has tangible conditions of streaking and is attended by acromion in low bound energy direction, and the chemical configuration form that Si element in the compound system is described is more than pure SiO
2, closing the form except containing the Si-O-Si bond, the bound energy of Si2p orbital electron is close near its electron binding energy value of acromion that occurs the 102eV position and the silicate, proves that the Si element in the compound system also exists the Si-O-Ca bond to close form.
Pure nanometer CaCO
3The bound energy of O1s orbital electron be 531.55eV.Pure SiO
2The bound energy of the O1s orbital electron of water of constitution is respectively 532.9eV and 532.4～532.7eV according to the literature in the Si-O-Si key and in the system.Nanometer CaCO
3/ SiO
2The bound energy peak of O1s orbital electron is than pure CaCO in the complex body
3The O1s peak width, and confirming to truly have in the system Si-O-Ca key indirectly in the obvious broadening of low bound energy direction.The thermal characteristics of composite particles:
In the TG curve before and after the nano-calcium carbonate coating modification, pure nanometer CaCO
3Slightly weightless before 600 ℃, this is because powder is sloughed the moisture content of surface adsorption causes, with the rising of temperature, because the lime carbonate thermolysis discharges CO
2Gas, curve have a tangible weightless step between 620～720 ℃, rate of weight loss is 57.05%.And nanometer CaCO
3/ SiO
2In the composite granule, the SiO of its surface coating layer
2Be in hydration status, be subjected to that the TG curve has two tangible weightless steps in the thermal process between 480～600 ℃ and 600～725 ℃, wherein in 480～600 ℃ of scopes and weightlessness before this be because SiO
2.xH
2Due to the O dehydrating condensation.Adopt the Freeman-Carroll method to carry out dynamic analysis to the TG curve data, try to achieve nanometer CaCO
3/ SiO
2The thermal degradation activation energy of composite particles is 209.9KJ/mol.K, and pure nanometer CaCO
3Thermal degradation activation energy be 166.3KJ/mol.K.The surface properties of composite particles:
By measure sample at N
2Absorption under the atmosphere and desorption curvilinear motion can be understood between surface properties, hole distribution and the sample and the adsorbate of sample for information about interactional.Nanometer CaCO
3/ SiO
2The sorption isotherm of composite particles after 120 ℃ of processing belongs to secondary adsorption, adsorption curve rises slowly and is protruding state to the adsorptive capacity axle when relative pressure is low, show that when adsorbate adsorbed, the heat of adsorption of the first layer was bigger than the condensation heat between the adsorbate on sorbent material.At relative pressure (p/p
0) greater than 0.6 o'clock, the capillary condensation phenomenon began to become significantly, make polymolecular layer physical adsorption balance be destroyed and cause adsorptive capacity sharply to increase.Just occur the phenomenon that adsorptive capacity enlarges markedly by the shape of sorption hysteresis circle (belong to category-A lag behind circle) and relative pressure when big and can infer that the composite particles surface contains pore, and mostly be macropore and neutral hole.Pure nanometer CaCO
3The BET specific surface area be 24.7m
2/ g, and nanometer CaCO
3/ SiO
2The specific surface area of composite particles is 38.4m
2/ g has increased about about 55%.
In the preparation process of embodiment 1 nuclear shell structured nano-lime carbonate/silica dioxide composite particles, system adds the lipophilicity inductor ethylene glycol of water quality 18% after ultrasonication, add 5% organic modifiers KH-570 after 1.5 hours in ageing, all the other conditions are constant, the 60min after product through cooling, filter, promptly obtain after washing and the 120 ℃ of drying treatment nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure of surface organic matter hydridization.Its IR characterizes as follows:
3000～2850cm
-1Absorption peak in the scope is the 1717cm as a result that absorbs owing to the c h bond stretching vibration on alkane, the alkene
-1And 1629cm
-1The stretching vibration absorption peak of C=O key and C=C key appears respectively in the place; 1512cm
-1Be CH
2The scissoring vibration and the CH of base
3The unsymmetrically formation vibration absorption band of base, 1395cm
-1The absorption peak at place is CH
2Symmetrical deformation vibration; 1305cm
-1The place is the antisymmetric stretching vibration of Si-C base; The absorption peak of the antisymmetric stretching vibration of C-C-O-C key and Si-O base appears at 1280～1000cm
-1In the scope; The c h bond flexural vibration absorption peak of vinyl is at 937cm
-1Near the appearance; 867cm
-1The place is that the symmetrical stretching vibration of Si-O-C key absorbs; 800cm
-1The weak absorption peak that the place occurs is CH
2Rocking vibration absorption band in the plane of base.
Embodiment 3
In the preparation process of embodiment 1 composite particles, system adds the ethylene glycol of water quality 15% and 15% ethanol after ultrasonication, add 15% organic modifiers A-151,90min discharging after 3 hours in ageing, all the other conditions are constant, and products therefrom IR spectrum analysis is as follows:
3000～2850cm
-1Absorption peak in the scope is the result who absorbs owing to the c h bond stretching vibration on alkane, the alkene; 1628cm
-1The place is that the stretching vibration of C=C key absorbs; CH
2The scissoring vibration and the CH of base
3The unsymmetrically formation vibration of base is absorbed in 1510～1400cm
-1The place; 1297cm
-1The absorption peak at place is that the stretching vibration of Si-O base absorbs; The antisymmetric stretching vibration absorption peak of Si-C base appears at 1200～1050cm
-1In the scope; 867cm
-1The place is that the symmetrical stretching vibration of Si-O-C key absorbs; 783cm
-1The weak absorption peak at place is CH
2Rocking vibration absorption band in the plane of base.
Embodiment 4
In the preparation process of embodiment 1 composite particles, system adds the ethylene glycol of water quality 5% after ultrasonication, adds 8% organic modifiers KH-792 after 2 hours in ageing, the 30min discharging, and all the other conditions are constant, and products therefrom IR spectrum analysis is as follows:
3000～2850cm
-1Absorption peak in the scope is because the result that the c h bond stretching vibration on the alkane absorbs; 1600～1480cm
-1Absorption peak in the scope is because primary amino NH
2, secondary amino group NH and CH
2The scissoring vibration and the CH of base
3The unsymmetrically formation vibration absorption band of base, 1390cm
-1The absorption peak at place is CH
2Symmetrical deformation vibration; C-N key, C-N-C key and Si-O base absorption peak appear at 1100～1000cm
-1In the scope; 867cm
-1The place is that the symmetrical stretching vibration of Si-O-C key absorbs; 783cm
-1The weak absorption peak that the place occurs is CH
2Rocking vibration absorption band in the plane of base.
Embodiment 5
In the preparation process of embodiment 1 composite particles, system adds the ethylene glycol of water quality 15% after ultrasonication, adds 2% organic modifiers KH-550 after 4 hours in ageing, the 50min discharging, and all the other conditions are constant, and products therefrom IR spectrum analysis is as follows:
3000～2850cm
-1Absorption peak in the scope is because the result that the c h bond stretching vibration on the alkane absorbs; 1620～1470cm
-1Absorption peak in the scope is because primary amino NH
2And CH
2The scissoring vibration and the CH of base
3The unsymmetrically formation vibration absorption band of base; C-N key and Si-O base absorption peak appear at 1180～1030cm
-1In the scope; 876cm
-1The place is that the symmetrical stretching vibration of Si-O-C key absorbs.
Claims (6)
1. nanometer CaCO
3/ SiO
2The preparation method of nucleocapsid structure composite particles is characterized in that: will without the nano-calcium carbonate suspension of any finishing after filtration, carrying out washing treatment is with ion remaining in the system of removing; Powerful stir that down washed nano-calcium carbonate to be joined concentration be that ultrasonic dispersing is handled the back and continued to stir more than 2 hours in 5%～70% the sodium silicate aqueous solution; Reaction system is put into 70～85 ℃ water-bath, and dripping concentration with 0.5ml/min～35ml/min speed is the H of 0.5mol/L～5.5mol/L
2SO
4Dilute solution, control stir speed (S.S.) 2000～6000 commentaries on classics/min, and the pH value of regulation system is 5～10, ageing 2～5 hours; Reaction product through cooling, filter, promptly obtain having after washing and the 120 ℃ of drying treatment nano-calcium carbonate/silica dioxide composite particles of nucleocapsid structure.
2. in accordance with the method for claim 1, it is characterized in that used sodium silicate aqueous solution concentration is 15%～45%.
3. in accordance with the method for claim 1, it is characterized in that in the system after ultrasonication adding lipophilicity inductor ethylene glycol or volume ratio and be 1: 1 ethylene glycol and ethanol, add R-SiX after 1～4 hour in ageing
3Class organic modifiers, 15min～90min after product through cooling, filter, promptly obtain after washing and the 120 ℃ of drying treatment nano-calcium carbonate/silica dioxide composite particles with nucleocapsid structure of surface organic matter hydridization; Said organic modifiers R-SiX
3In R be meant can with organic resin reaction or dissolved methacrylic ester, amino or vinyl mutually, X is meant methoxyl group, oxyethyl group or the halogen that easily is hydrolyzed.
4. according to the method described in the claim 3, the concentration that it is characterized in that used organic modifiers is 0.5%～15% of composite particles total mass number, the concentration of lipophilicity inductor be in the system water quality 5%～30%.
5. according to claim 3 or 4 described methods, it is characterized in that used organic modifiers R-SiX
3Be in γ-(methacryloxypropyl) Trimethoxy silane, vinyltriethoxysilane, N-(β amido ethyl)-γ-aminocarbonyl propyl Trimethoxy silane and the γ-An Jibingjisanyiyangjiguiwan one or both.
6. according to the described method of one of claim 1 to 4, the mass concentration that it is characterized in that used nano-calcium carbonate is 5%～65%, and the average dimension of used nano-calcium carbonate is 15～100nm.
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| WO2003097529A1 (en) * | 2002-03-20 | 2003-11-27 | Nanomaterials Technology Pte Ltd. | CaCO3/Si2O • nH2O NANOCOMPOSITE PARTICLES, Si2O • nH2O NANOMATERIAL AND METHOD OF PRODUCING THE SAME |
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