CN107400380A - The special titanium dioxide process of high gloss paint - Google Patents
The special titanium dioxide process of high gloss paint Download PDFInfo
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- CN107400380A CN107400380A CN201710579744.7A CN201710579744A CN107400380A CN 107400380 A CN107400380 A CN 107400380A CN 201710579744 A CN201710579744 A CN 201710579744A CN 107400380 A CN107400380 A CN 107400380A
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- titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The present invention relates to the special titanium dioxide process of high gloss paint, the titanium dioxide process is：(1) using industrial titanium dioxide as raw material, mesoporous TiO 2 is prepared；(2) mesoporous TiO 2 is placed in alkaline solution, adds alumina silicate and cladding processing is carried out to mesoporous TiO 2；(3) organic fluoride surface treatment is carried out to mesoporous TiO 2 of the step (2) by cladding processing.After titanium dioxide prepared by the inventive method adds high gloss paint, the performance of high gloss paint is improved.Both original premium properties of high gloss paint had been maintained, has added the resistance to chemical corrosion and Water-proof and oil-proof, antifouling property of high gloss paint again.On the other hand, the present invention by epoxy resin with fluorination surface treatment, method is simple, easy to control, it is cost-effective and to experimental facilities requirement.
Description
Technical field
The present invention relates to titanium dioxide, the in particular special titanium dioxide process of high gloss paint.
Background technology
Paint is widely used in the life of people and industrial production, plays the work of protection, decoration, mark and other specific uses
With being the indispensable material in the world today.The species that existing market is painted is various, wherein high lac varnish is with its excellent gloss
Property is favored by everybody.Traditional high lac varnish be using acrylic resin or polyurethane as base-material, be aided with various pigment, solvent,
Additive is refined to be formed, although its paint film toughness and wear-resisting, heat-resisting, resistance to persistence, glossiness are all relatively good, it is anti-
Water, grease proofing, antifouling NBC protective performance and resistance to chemical corrosion are relatively poor, and this largely limits high lac varnish
Application, while shorten the service life of high lac varnish.
Patent CN201210107834.3 patent applications disclose a kind of preparation technology of fluorine-containing high lac varnish, and step is：1、
Under nitrogen protection, by perfluoro hexyl ethyl propylene acid esters, acrylic acid, methacrylic acid, methyl methacrylate, acrylic acid fourth
Ester, mixed in xylene solvent, 30min is stirred at room temperature, add peroxidized t-butyl perbenzoate initiator, be copolymerized instead
Should, fluorine resin is made；2nd, ground after fluorine resin is mixed with inorganic pigment, add diluent, add dispersant, defoamer
And levelling agent, fluorine-containing high lac varnish is made.The raw materials technology is fully easy to get, and cost is cheap, and obtained product has good light
Damp degree and excellent UV resistant performance, and Water-proof and oil-proof, antifouling property are good.
In view of this, the present invention is proposed.
The content of the invention
The problems of for solution in the prior art, the invention provides the special titanium dioxide process of high gloss paint
And preparation method thereof.
In order to solve the above problems, the present invention adopts the following technical scheme that：
The special titanium dioxide process of high gloss paint, the titanium dioxide process are：(1) using industrial titanium dioxide as
Raw material, prepare mesoporous TiO 2；(2) mesoporous TiO 2 is prepared into slurry with deionized water, and adds alkaline solution regulation
PH value is 9~9.5, disperses, stirs and adds alumina silicate, and hydrochloric acid is added dropwise, and it is 7.5~8.5 to control pH value, and keeping temperature 90~
100 DEG C, continue 2~4h of stirring, filtering, washing, dry, obtain inorganic coating mesoporous TiO 2；(3) step (2) is passed through
The mesoporous TiO 2 of cladding processing carries out organic fluoride surface treatment.
Preferably, step (1) is specially：Concentrated alkali solution will be added in industrial titanium dioxide first, make industrial titanium dioxide complete
Dissolving, stirring make it fully react, and the solution obtained is scattered in deionized water, and stirring obtains mixed liquor；To mixed under stirring
Close and concentrated acid is added dropwise in liquid, the volume ratio of concentrated acid and mixed liquor is 6：1, stirring reaction 30 minutes；Obtained solution is placed in high pressure
Reacted 6 hours in 180 DEG C in hydrothermal reaction kettle, mesoporous TiO 2 is made.
Preferably, the concentrated acid is 38% hydrochloric acid.
Preferably, the ratio between molal weight of hydroxide ion in the alumina silicate and alkaline solution of the step (2) is 1：7
~10.
Preferably, step (2) reaction temperature is 90~100 DEG C, and mixing time is 2~4h.
Preferably, the alkaline solution is NaOH solution.
Preferably, the titanium dioxide that processing is coated by step (2) is cladding completely.
Preferably, step (3) is specially：By epoxy resin, crossed with coupling agent treatment the step of (2) prepare titanium dioxide
Processing is separately dried, epoxy resin is placed in supercritical fluid kettle, adjusts pressure and temperature in kettle so that delivery of fluorine/nitrogen
Pressure and temperature reaches critical point；The material being dispersed with stirring in supercritical fluid kettle so that epoxy resin fusion plastification；At addition
Titanium dioxide after reason, and overcritical delivery of fluorine/nitrogen fluid is passed through, 40~70min of stir process at a temperature of 90~130 DEG C；
Highly pressurised liquid is depressured, to below less than delivery of fluorine/nitrogen critical pressure, material is separated, spray, crush, sieved
Classification, obtains fluorinated epoxy resin titanium dioxide granule.
Preferably, the overcritical delivery of fluorine/nitrogen fluid fluorine/nitrogen volume ratio is 1：9~2：3.
Preferably, the overcritical delivery of fluorine/nitrogen fluid is the supercritical fluid under 5.21~10Mpa pressure.
Raw material of the present invention is industrial titanium dioxide, and industrial titanium dioxide is conveniently easy to get.The titanium dioxide system of the present invention
Preparation Method is using industrial titanium dioxide as raw material, applied in high gloss paint.Titanium dioxide one side conduct is added in high gloss paint
Pigment coloring, on the other hand remove pollutant using the photocatalytic activity of titanium dioxide., it is necessary to two when titanium dioxide is as pigment
Titanium oxide has good covering power；, can be by increasing the measures such as specific surface area modification when titanium dioxide is as photochemical catalyst
To improve its photocatalytic activity.
The first step of the present invention is prepared for mesoporous TiO 2, and the raw material selected by the present invention is cheap industrial titanium white
Powder, its character is secure, and easily obtains.Based on titanium dioxide, crystal structure dissociates under concentrated base environment, so as to create crystal weight
The principle of the condition of group, it is the principle that monocrystalline is formed based on hydro-thermal reaction that the present invention, which prepares mesoporous TiO 2, is made by concentrated base
Titanium dioxide crystal structure dissociates, and remixes acid solution and carries out hydro-thermal reaction, is gradually invaded during the course of the reaction using acid solution
Lose Crystallization micropore or meso-hole structure.Due to the corrosion function of acid solution, the outer of prepared titanium dioxide granule compares table
Area greatly increases, and adds titanium dioxide granule and extraneous contact area, improves photocatalytic activity.Prepared by the step is situated between
During porous titanium dioxide, using industrial titanium dioxide as raw material, crystal structure is dissociated by alkaline solution, acid solution is in crystallization process
Final product is made in the principle of etched crystal, the external surface area for increasing titanium dioxide granule.This method reactant easily obtains,
It is simple to operate.
But because photocatalytic activity is high, in use can the organic principle that contacts of catalytic degradation, cause mesoporous
Titanium dioxide surface nanoscale hole hole fails with organic basic combine, and makes coating generation loss of gloss and powder of detached etc. low again, sternly
The various performance and used lifes of product are reduced again.Therefore, TiO 2 particles are surface-treated using film-coating technique, i.e.,
Make barrier in one layer of good material of photochemistry inertia of TiO 2 particles Surface coating, lived so as to reduce the photochemistry of titanium dioxide
Property, be advantageous to improve the performances such as weather resisteant, dispersiveness, gloss and the covering power of TiO 2 particles.Silica can improve two
The weatherability of titanium oxide, aluminum oxide can reduce the photochemical activity of titanium dioxide, improve the dispersiveness of titanium dioxide and cover
The performances such as power, in the prior art generally use silicate, aluminate to titanium dioxide carry out silica, aluminum oxide cladding, and
Coating both materials and then needing two steps to be handled can just complete.The present invention passes through in the scattered alkalescence of mesoporous TiO 2
Alumina silicate is added in solution, inorganic coating is carried out to mesoporous TiO 2.Alumina silicate reacts with alkaline solution, because of relative quantity not
Together, three kinds of silicate, aluminate and aluminium hydroxide materials are can obtain, add acid regulation PH, and control temperature and reaction time,
Filtered, washing, dry, the mixed layer of last layer silica, aluminum oxide finally can be all coated in titanium dioxide surface.It is preferred that
, the alkaline solution is excessive relative to alumina silicate, and alumina silicate reacts to obtain sodium metasilicate, sodium aluminate solution with alkaline solution, after
It is continuous to add acid regulation PH, and temperature and reaction time are controlled, filtered, washing, dry, finally in mesoporous TiO 2 particle
Last layer silica, the mixed layer of aluminum oxide are coated on outer surface, and silica can improve the weatherability of titanium dioxide, oxidation
Aluminium can improve the dispersiveness and the performance such as covering power of titanium dioxide, from there through alumina silicate under alkaline environment to titanium dioxide
Coated, improve the weatherability, dispersiveness and covering power of titanium dioxide.Have in the prior art direct in titanium dioxide surface
Coating alumina silicate film layer is to improve the high lockedin air space of product and high whiteness.But the present invention is different from prior art, nothing of the present invention
Though the raw material in the processing of machine cladding is alumina silicate, final clad is not silicic acid aluminum membranous layer simple in the prior art, and is led to
Cross the mechanism of alumina silicate and alkali reaction, step processing just completes silica and aluminum oxide while coated, directly in titanium dioxide
Surface forms one layer of silica, the mixed layer of aluminum oxide, and method is simple, and resultant effect is good.Reacted in the present invention by controlling
The mesoporous TiO 2 that the amount of thing and reaction time are coated completely.Mesoporous TiO 2 now remains Jie on surface
Hole, but inner silica titanium is kept completely separate with the external world, and just the catalytic organism around it will not be degraded.By dioxy in the step
Change titanium, which is placed in alkaline environment to add in alumina silicate progress inorganic coating, with the first step to prepare, uses concentrated base in mesoporous TiO 2
(10mol/L) dissociates industrial titanium dioxide crystal different.It is the cladding of manufacture alkalescence in the step though all employ alkali process
Environment, and the alkaline solution concentration is low；Time of the mesoporous TiO 2 individually in the alkaline environment is short simultaneously, only scattered
1 minute, alumina silicate is just added, therefore, alkaline environment has faint anti-to the mesoporous TiO 2 prepared in this step
Should.On the other hand, the faint reaction that alkali occurs with titanium dioxide granule surface in the step, reaction generation soluble-salt, meeting
A small amount of micropore is manufactured on titanium dioxide granule surface, so as to increase the external surface area of titanium dioxide, this is that the first step is manufactured to be situated between
The reinforcement of porous titanium dioxide.
After the mesoporous and cladding for carrying out early stage is handled, obtained titanium dioxide has the knot being combined with organic matter
Structure, further to its organic surface treatment to improve the anti-corrosion of titanium dioxide and grease proofing antifouling waterproof ability.Traditional high lac varnish
It is using acrylic resin or polyurethane as base-material, is aided with various pigment, solvent, additive and refines and form.The present invention utilizes epoxy
There is resin good antiseptic property, fluoro-containing group can assign the superiority such as coating solvent resistant, chemically stable, more low-surface-energy
Can, the pollutant such as water, oil is difficult to be attached on surface, so as to have good resistance to soiling.But although fluorinated epoxy resin is because of its carbon
Fluorine atom is closely arranged in around resin backbone, and surface tension, friction factor, refractive index are low, have excellent corrosion resistant
Corrosion, wearability, heat resistance, hydrophobicity, moisture-proof, dielectricity, stain resistance, anti-flammability, durability.But fluorinated epoxy resin
It is expensive, the adhesive of specific use, such as space flight solar panel, optical fiber is only applied at present.Therefore this hair
The bright mesoporous titanium dioxide of inorganic clad surface completely that first two steps are prepared carries out epoxy resin cladding, and it is carried out
Fluorination treatment, obtain excellent properties possessed by fluorinated epoxy resin.But because fluorine gas activity is high, dangerous greatly and inconvenient straight
The fluorination reaction for being actually used in organic matter is connect, and the dissolubility of fluorine is poor, because typically being carried out in reaction in two phase surfaces；Again because of fluorination
React for exothermic reaction, easily form focus in reaction surface so as to accelerate the progress of side reaction.In order to reduce side reaction
Occur, and control course of reaction, fluorine gas is diluted by using inert gas (such as nitrogen or argon gas), so that fluorination reaction is easily controlled
Make and improve fluorination first selecting property.Therefore carry out using delivery of fluorine/nitrogen mixed gas during fluorination treatment in the present invention, and control fluorine
Gas/nitrogen institute volume ratio is no more than 3：2 are tested.Carrying out epoxy resin to it using supercritical liq method in step processing has
Machine surface and fluorination treatment.Fluorine is fully contacted with reactant, thus can increase internal-response, reduce possibility caused by focus,
Reduce the generation of side reaction.The mixed gas of delivery of fluorine/nitrogen is prepared into supercritical fluid by the present invention, is surpassed in the delivery of fluorine/nitrogen
In the environment of critical fluids, fluorination treatment is carried out to the titanium dioxide and epoxy resin composition previously prepared.In shooting flow
In the environment of body, by peptizaiton, the mesoporous TiO 2 of epoxy resin and inorganic coating is combined closely, and with fluorine fluid
Fully and it is in close contact, reaches the purpose of fluorination.This method reduces reaction temperature and shortens the reaction time, after the completion of reaction,
As long as the gas of Supercritical Conditions is recovered into normal pressure, through spraying, granulating can obtain final products.
The critical pressure of fluorine gas is 5.21MPa in the present invention, and critical-temperature is -128.85 DEG C；The critical pressure of nitrogen is
3.39MPa, critical-temperature are -147 DEG C, thus when using supercritical fluid method, as long as temperature is higher than -128.85 DEG C, pressure
Required supercritical fluid environment can be created more than 5.21MPa, in order to reduce the requirement to equipment, preferential overcritical fluorine
Gas/nitrogen fluid is the supercritical fluid under 5.21~10Mpa pressure；At this moment fluorine gas and the physical property of nitrogen has liquid property concurrently
With gas property.It is substantially still a kind of gaseous state, but is different from general gas flow, is a kind of dense gaseous state.Its density ratio
General gas flow wants big two orders of magnitude, close with liquid.Its ratio of viscosities liquid is small, but diffusion velocity is faster (about 10- than liquid
100 times), so having preferable mobility and transfer performance.Its dielectric constant drastically changes with pressure, as dielectric constant increases
Big to be advantageous to dissolve the big material of some polarity, the supercritical fluid, almost without surface tension, therefore is easy to ooze just like gas
Enter into porous tissue various paint fillers, reach the effect of thorough dispersion mixing.During using this method, shooting flow is set
Temperature is 90 DEG C~150 DEG C in body kettle.The condition of preparation is this method reduce, shortens preparation time, so as to save the energy, is carried
High throughput rate.
On the basis of early stage prepares the mesoporous TiO 2 of inorganic coating, organic process is carried out, on the one hand enhances two
The compatibility of titan oxide particles and organic matter, and the connection function with organic matter is enhanced by surface mesoporous structure.The opposing party
Face, protect organic matter not influenceed and degraded by photocatalytic activity, and improve the weatherability of titanium dioxide simultaneously.
Each step is step by step progressive above, and titanium dioxide is modified；To obtain the best titanium dioxide of relative performance, between its order
Exist non-adjustable transsexual, and each step is indispensable；Using relatively suitable the step of preparation method of the present invention and between step
Titanium dioxide made from sequence can obtain significant beneficial effect；This is to change sequence of steps in preparation method of the present invention, or is subtracted
Small wherein step institute is irrealizable.
Beneficial effect
After titanium dioxide prepared by the inventive method adds high gloss paint, the performance of high gloss paint is improved.Both kept
Original premium properties of high gloss paint, the resistance to chemical corrosion and Water-proof and oil-proof, soil resistance of high gloss paint are added again
Energy.On the other hand, for the present invention by epoxy resin and the surface treatment of fluorination, method is simple, easy to control, cost-effective and to reality
Test equipment requirement.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in the present invention, the required accompanying drawing used in embodiment will be made below
Simply introduce, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for the general of this area
For logical technical staff, on the premise of not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the diafiltration device of the special titanium dioxide process of high gloss paint of the present invention.
Reference
Diafiltration device 6；Central controller 600；Slideway 611；Electronic sliding block 612；Extension sleeve 613；Connecting rod 614；Cross
Filter frame 615；Filter plate 616；Collecting tank 62；Filtrate receiver 621；Drying chamber 622；Material collection groove 623；Clear water pipeline 63；First is clear
Penstock 631；Spray thrower 632；Second Clean water valve 633；Material pipeline 64；Material valve 641；Waste-solution line 66；Waist valve
Door 661.
Embodiment
The present invention can be explained in more detail by the following examples, the open purpose of the present invention is intended to the protection present invention
In the range of all changes and improvements, the invention is not limited in the following examples.
Comparative example
A kind of preparation technology of fluorine-containing high lac varnish is disclosed in patent CN201210107834.3 patent applications, it is specific real
It is as follows to apply one of mode：
Under nitrogen protection, to equipped with mechanical agitation, temperature measuring point, condenser pipe four-hole bottle in, add 40g perfluoro hexyl second
Base acrylate, 120g acrylic acid, 70g methacrylic acids, 100g methyl methacrylates, 150g butyl acrylates, 500g bis-
Toluene solvant, 30min is stirred at room temperature, adds 20g peroxidized t-butyl perbenzoate initiators, be slowly heated to 80~90 DEG C and draw
Hair reaction, polymerisation 5h, obtains 1000g fluorine resins.
2h is ground through SG types three-roll grinder after 550g fluorine resins are mixed with 250g blue inorganic pigments, makes its fineness
Reach 20 μm, 100g butyl acetate diluents are added under 600rpm stirring at low speed, after rotating speed is adjusted into 1200rpm, continue to add
Enter 20g sodium polyacrylate disperants, 30g epoxy peanut oil silica ether straight chain aliphatic hydrocarbons emulsion defoamers and the acetone of 50g bis-
Alcohol levelling agent, 30min is stirred, make it well mixed, the fluorine-containing high lac varnish of blueness is made.
Experimental example 1
Prepare mesoporous TiO 2：
1) the industrial titanium dioxide of 50 parts by weight is taken, adds 10mol/L NaOH solution, stirring makes industrial titanium dioxide completely molten
Solution, it is 1 according to the volume ratio of solution and deionized water：5, deionized water is added, is well mixed；Quality is added dropwise into above-mentioned solution
Fraction is 38% concentrated hydrochloric acid, and it is 6 that the volume of concentrated hydrochloric acid and solution, which passes through,：1, it is added dropwise, continues reaction 30 minutes；
2) above-mentioned solution is placed in high-pressure hydrothermal reaction kettle, in 180 DEG C of temperature, reacts 6h, gained sediment spend from
Sub- water washing 2 times, absolute ethyl alcohol are washed 1 time, and porous titanium dioxide is produced after drying process.
Titanium dioxide specific surface area increase prepared by this experimental example 1, its photocatalytic activity are greatly improved.Experimental example
2
Prepare inorganic coating mesoporous TiO 2：
This experimental example 2 is on the basis of experimental example 1, and the titanium dioxide prepared to experimental example 1 is further handled, to improve
The covering power of titanium dioxide high gloss paint is added, so as to obtain the special titanium dioxide of high gloss paint of more dominance energy.The present embodiment
Choose experimental example 1 and prepare mesoporous TiO 2 as raw material, progress following step 3) processing.
Step 3)：Mesoporous TiO 2 in the step 2) of experimental example 1 is configured to oar material with deionized water, it is molten to add NaOH
Liquid makes oar material pH value be 9~9.5, ultrasonic disperse 1 minute；Stir and be slowly added to alumina silicate fine powder, alumina silicate and NaOH's rubs
Your mass ratio is 1：7；The hydrochloric acid that mass fraction is 38% is added dropwise, it is 7.5~8.5 to control pH value, and 100 DEG C of keeping temperature,
Continue to stir 4h, filtering, washing, dry, obtain inorganic coating mesoporous TiO 2.
The acid for the regulation pH value that step 3) adds is identical with the acid in step 3) in this experimental example 2, reduces raw material type,
Decrease the introducing of other materials.
That inorganic coating is carried out in the presence of NaOH by alumina silicate in this experimental example step 3), and alumina silicate with
NaOH relative quantity is different, and reaction product is different, so as to influence whether clad ratio, for this reason, it is necessary to be rubbed to alumina silicate and NaOH
You are limited mass ratio, to reach required complete covered effect.
Take the alumina silicate of equivalent and the NaOH solution of same concentrations, control the amount of NaOH solution with adjust alumina silicate with
The ratio between NaOH molal weights, the method in taking steps 3) coat to titanium dioxide is made in the experimental example 1 of equivalent.To protect
Card participates in the amount equivalent of the alumina silicate of cladding, and alumina silicate can be completely dissolved in NaOH, then alumina silicate and NaOH molal weight it
Than cannot be greater than 1：2.Change reaction temperature and mixing time simultaneously, finally obtain the titanium dioxide of different clad ratios.It reacts
Condition and final clad ratio are as shown in table 1.
The reaction condition of the inorganic coating of table 1 and clad ratio corresponding table
As can be seen from Table 1, when equivalent alumina silicate participates in coating, temperature of plate is identical with the time, alumina silicate and NaOH
The ratio between molal weight it is smaller, clad ratio is bigger.The ratio between alumina silicate and NaOH molal weight is certain, and temperature of plate is constant, bag
Cover time growth, clad ratio increase；The ratio between alumina silicate and NaOH molal weight is certain, and the cladding time is constant, temperature of plate liter
Height, clad ratio increase.The present invention needs to prepare the titanium dioxide of higher clad ratio, to avoid titanium dioxide in itself to organic around
The degraded of thing, therefore select higher temperature and longer mixing time.In view of the titanium dioxide effect coated completely is best, it is preferred that
The ratio between molal weight during experiment by controlling alumina silicate and NaOH is less than 1：7~10, in 90~100 DEG C of 2~4h of stirring reaction,
Under the experiment condition, the titanium dioxide coated completely can be obtained.The mesoporous TiO 2 coated completely, it can effectively shield dioxy
Change the photocatalytic activity of titanium, avoid degraded of the titanium dioxide to organic matter around in itself.Carried out for follow-up organic surface treatment
Prepare.By statistical calculations, result has statistical significance thereon (P is less than 0.01)；But data above value is obtained, to be done
Parallel test.
Generally use silicate, aluminate carry out the cladding of silica, aluminum oxide to titanium dioxide in the prior art, and want
Coating both materials and then needing two steps to be handled can just complete.Also have in the prior art and directly coated in titanium dioxide surface
Silicic acid aluminum membranous layer is to improve the high lockedin air space of product and high whiteness.This experimental example of this experimental example is different from prior art, step
3) though raw material is alumina silicate in, final clad is not silicic acid aluminum membranous layer simple in the prior art, and by alumina silicate with
The mechanism of alkali reaction, step processing just complete silica and aluminum oxide while coated, directly in titanium dioxide surface formation one
Layer silica, the mixed layer of aluminum oxide, method is simple, and the resultant effect such as weatherability, dispersiveness and covering power is good, in next step
Processing prepare, and for final products performance make basis.
Embodiment 1
The present embodiment is on the basis of experimental example 2, and the titanium dioxide prepared to experimental example 2 is further handled, so as to obtain
Obtain the special titanium dioxide of high gloss paint of more dominance energy.Prepared under the present embodiment selection 2 same experiment condition of experimental example complete
The titanium dioxide of cladding carries out following step 4 as raw material) -5) processing.
4) epoxy resin is placed in vacuum drying chamber 24h and removes air and moisture, and by the TiO of above-mentioned preparation2
Grain is placed in vacuum drying chamber after being handled with silane coupler dries 10h at a temperature of 180 DEG C；
5) epoxy resin after drying process is placed in supercritical fluid kettle, design temperature is 130 DEG C, utilizes shooting flow
Heating element heater in body kettle be heated to constant temperature 3 minutes after the temperature of setting, while starts shearing elements and carry out shearing and go to
Velocity of rotation is 100 revs/min so that the abundant fusion plastification of resin.Then dried TiO2Particle is placed in shooting flow
In body kettle, and it is passed through a certain proportion of overcritical delivery of fluorine/nitrogen fluid (body of the fluorine gas and nitrogen that pressure is 5.21MPa
Product is than being 1：9), wherein, the volume ratio of titanium dioxide and epoxy resin is 10：3, the volume of supercritical fluid and titanium dioxide
Volume ratio is controlled 6：1.Ultrasonic disperse and stirring by 5 minutes, titanium dioxide granule are fully mixed with epoxy resin fused mass
Close, overcritical delivery of fluorine/nitrogen is diffused rapidly in the organic matter matrix of fusion plastification, and the viscosity of organic-compound system reduces, freely
Volume increases, and multiphase polymer is sufficiently mixed with TiO 2 particles；Continue to stir 70min.Stop heating and stirring, and turn
Normal pressure is depressured to pressure relief valve is opened, supercritical gas foaming nucleation, a large amount of abscesses is internally formed in polymeric matrix, steeps
Further homogenising polymer multiphase body and titanium dioxide it is expected the mixing of particle in the forming process of hole, continue to be passed through overcritical fluorine gas/
Nitrogen fluid causes the organic matter of fusion plastification to be cooled to glass transition temperature, abundant glass transition temperature is cooled to
Mixed Polymer Blends body and nano-particle be passed through classification kettle in sprayed, granulating, classified filtering obtain powder.
Embodiment 2
The present embodiment is on the basis of experimental example 2, and the titanium dioxide prepared to experimental example 2 is further handled, so as to obtain
Obtain the special titanium dioxide of high gloss paint of more dominance energy.Prepared under the present embodiment selection 2 same experiment condition of experimental example complete
The titanium dioxide of cladding is to be prepared under the same terms and method with titanium dioxide selected in embodiment 1, except that
Following step 4) -5) processing.
4) epoxy resin is placed in vacuum drying chamber 24h and removes air and moisture, and by the TiO of above-mentioned preparation2
Grain is placed in vacuum drying chamber after being handled with silane coupler dries 10h at a temperature of 180 DEG C；
5) epoxy resin after drying process is placed in supercritical fluid kettle, design temperature is 110 DEG C, utilizes shooting flow
Heating element heater in body kettle be heated to constant temperature 3 minutes after the temperature of setting, while starts shearing elements and carry out shearing and go to
Velocity of rotation is 100 revs/min so that the abundant fusion plastification of resin.Then dried TiO2Particle is placed in shooting flow
In body kettle, and it is passed through a certain proportion of overcritical delivery of fluorine/nitrogen fluid (volume ratio of the fluorine gas and nitrogen that pressure is 7MPa
For 3：7), wherein, the volume ratio of titanium dioxide and epoxy resin is 10：3, the volume of supercritical fluid and the volume of titanium dioxide
Than controlling 4：1.Ultrasonic disperse and stirring by 5 minutes, titanium dioxide granule are sufficiently mixed with epoxy resin fused mass, are surpassed
Critical delivery of fluorine/nitrogen is diffused rapidly in the organic matter matrix of fusion plastification, and the viscosity of organic-compound system reduces, and free volume increases
Greatly, multiphase polymer is made to be sufficiently mixed with TiO 2 particles；Continue to stir 55min.Stop heating and stirring, and go to opening
Pressure relief valve is depressured to normal pressure, supercritical gas foaming nucleation, is internally formed a large amount of abscesses in polymeric matrix, abscess is formed
During further homogenising polymer multiphase body and titanium dioxide it is expected the mixing of particle, continue to be passed through overcritical delivery of fluorine/nitrogen stream
Body causes the organic matter of fusion plastification to be cooled to glass transition temperature, being cooled to after glass transition temperature is sufficiently mixed
Polymer Blends body and nano-particle be passed through classification kettle in sprayed, granulating, classified filtering obtain powder.
Embodiment 3
The present embodiment is on the basis of experimental example 2, and the titanium dioxide prepared to experimental example 2 is further handled, so as to obtain
Obtain the special titanium dioxide of high gloss paint of more dominance energy.Prepared under the present embodiment selection 2 same experiment condition of experimental example complete
The titanium dioxide of cladding is to be prepared under the same terms and method with titanium dioxide selected in embodiment 1 and embodiment 2, institute
Unlike following step 4) -5) and processing.
4) epoxy resin is placed in vacuum drying chamber 24h and removes air and moisture, and by the TiO of above-mentioned preparation2
Grain is placed in vacuum drying chamber after being handled with silane coupler dries 10h at a temperature of 180 DEG C；
5) epoxy resin after drying process is placed in supercritical fluid kettle, design temperature is 90 DEG C, utilizes shooting flow
Heating element heater in body kettle be heated to constant temperature 3 minutes after the temperature of setting, while starts shearing elements and carry out shearing and go to
Velocity of rotation is 100 revs/min so that the abundant fusion plastification of resin.Then dried TiO2Particle is placed in shooting flow
In body kettle, and it is passed through a certain proportion of overcritical delivery of fluorine/nitrogen fluid (volume of the fluorine gas and nitrogen that pressure is 10MPa
Than for 5：5), wherein, the volume ratio of titanium dioxide and epoxy resin is 10：3, the volume of supercritical fluid and the body of titanium dioxide
Product is than control 10：1.Ultrasonic disperse and stirring by 5 minutes, titanium dioxide granule are fully mixed with epoxy resin fused mass
Close, overcritical delivery of fluorine/nitrogen is diffused rapidly in the organic matter matrix of fusion plastification, and the viscosity of organic-compound system reduces, freely
Volume increases, and multiphase polymer is sufficiently mixed with TiO 2 particles；Continue to stir 40min.Stop heating and stirring, and turn
Normal pressure is depressured to pressure relief valve is opened, supercritical gas foaming nucleation, a large amount of abscesses is internally formed in polymeric matrix, steeps
The mixing of further homogenising polymer multiphase body and TiO 2 particles, continues to be passed through overcritical fluorine gas/nitrogen in the forming process of hole
Air-flow body causes the organic matter of fusion plastification to be cooled to glass transition temperature, fully mixed glass transition temperature is cooled to
Polymer Blends body and nano-particle after conjunction be passed through classification kettle in sprayed, granulating, classified filtering obtain powder.
Overcritical delivery of fluorine/nitrogen fluid minimum pressure in the step 4) of embodiment 1- embodiments 3 is 5.21Mpa, preferably
For 5.21~10Mpa, the pressure using delivery of fluorine/nitrogen fluid is small, and the requirement to equipment is small, and the temperature required for preparing is relatively
Low, sufficient reaction time is short.
It is different by the ratio of a certain proportion of overcritical delivery of fluorine/nitrogen fluid in step 5), affect the journey of fluorination
Degree, and degree of fluorination directly affects the performance of final product.It is necessary to be defined the ratio of delivery of fluorine/nitrogen for this, from
And suitable fluorination effect is obtained, reach the purpose efficiently produced.But because fluorine gas activity is high, dangerous greatly and inconvenient directly real
Border is used for the fluorination reaction of organic matter, and fluorination reaction is exothermic reaction, in order to control course of reaction, by using inert gas
(such as nitrogen or argon gas) dilutes fluorine gas, so that fluorination reaction is easily controlled and improves fluorination first selecting property.Therefore in the present invention
Carry out using delivery of fluorine/nitrogen mixed gas during fluorination treatment, and control fluorine gas/nitrogen institute volume ratio to be no more than 3：2 are tested.Will
Under the experiment condition of embodiment 2, change delivery of fluorine/nitrogen than obtained target product titanium dioxide.
The experiment condition of embodiment 1 will be chosen, set different delivery of fluorine/nitrogen ratios, in embodiment 1 other parameters phase
Titanium dioxide is made with conditions of, high gloss paint is prepared with the same method of comparative example, wherein in the comparative example first step not
Fluorine hexyl ethyl propylene acid esters is added, directly prepares not fluorine-containing resin.With prepared in the present invention in comparative example second step
Titanium dioxide replace comparative example in original inorganic pigment, other same comparative examples of method, be prepared containing different delivery of fluorine/nitrogen
The high gloss paint of the titanium dioxide prepared under environment.The following performance and method of obtained high gloss paint are measured：
By obtained high gloss paint and diformazan benzene diluter in mass ratio 9:After 1 is well mixed, standing removes bubble, with without sky
Gas high-pressure spray gun is sprayed on stainless steel surface, and coating layer thickness is 150 μm, is tested according to coating property, detection performance project is such as
Table 2, specific performance testing result such as table 3：
The detection performance project of table 2 and standard
Specific performance testing result when the different fluorine nitrogen of table 3 are than processing
After the titanium dioxide that as can be seen from Table 3 prepared by the inventive method adds high gloss paint, the ratio of different delivery of fluorine/nitrogen
The addition of the titanium dioxide of example processing produces different influences to the performance of high gloss paint.It is in delivery of fluorine/nitrogen ratio as shown in Table 3
1：9~2：When 3, obtained titanium dioxide, which adds its glossiness, weatherability, Salt corrosion corrosion and waterproof and oilproof in high gloss paint, to be prevented
Dirty ability all shows fabulous, has very excellent combination property.Both the premium properties of high gloss paint had been maintained, has added height again
Resistance to chemical corrosion and Water-proof and oil-proof, the antifouling property of gloss paint.By statistical calculations, result has statistics thereon
Meaning (P is less than 0.01)；But data above value is obtained, to do parallel test.
Each step is step by step progressive above, and titanium dioxide is modified；To obtain the best titanium dioxide of relative performance, its
Exist non-adjustable transsexual between order, and each step is indispensable；Using the step of preparation method of the present invention and between step
Relative ranks made from titanium dioxide can obtain significant beneficial effect；This is that step is suitable in change preparation method of the present invention
Sequence, or reduction wherein step institute are irrealizable.
Filtering is eventually passed through in step 3) of the present invention, washs, be dried to obtain inorganic coating titanium dioxide, filtering at this, is washed
The technique wash, dried employs special diafiltration device 6.
Specifically, the diafiltration device 6 includes filtrate receiver 621, drying chamber 622, material collection groove 623；
The filtrate receiver 621 is connected with waste-solution line 66, and waste liquid valve 661 is provided with waste-solution line 66；
Clear water pipeline 63 is connected with the top of filtrate receiver 621, the second Clean water valve is provided with clear water pipeline 63
633；
The top of filtrate receiver 621 is provided with the discharge end of material pipeline 64, and material valve 641 is provided with material pipeline 64,
The charging of material pipeline 64 open can be set, also can be with the device discharging opening of inorganic coating processing titanium dioxide device in step 3)
It is connected；The top of filtrate receiver 621 is provided with spray thrower 632, and the discharge end of the spray thrower 632 and clear water pipeline 63 connects
Connect, the first Clean water valve 631 is provided with clear water pipeline 63, the feed end of clear water pipeline 63 is connected with water tank；Described first is clear
The Clean water valve 633 of penstock 631 and second is in charge of two branch roads.
The top of diafiltration area 61 is provided with slideway 611；
Electronic sliding block 612 is arranged in slideway 611, and is slid into the horizontal direction on filtrate receiver 621 along slideway 611
Any position in side, the top of drying chamber 622, the top of material collection groove 623；
Extension sleeve 613 is stretched in vertical direction, or is rotated along the axis of extension sleeve 613；The extension sleeve
613 are arranged on electronic sliding block 612；
Connecting rod 614 is connected with extension sleeve 613 and filter frame 615 respectively；
Filter frame 615 carries out the motion in vertical direction under the drive of extension sleeve 613, or along the axle of extension sleeve 613
Line is rotated, and the motion in horizontal direction is carried out under the drive of electronic sliding block 612, and the filter frame 615 is internally provided with filter plate
616。
Further, in order to realize Automated condtrol of the diafiltration device 6 in operation, reduce manpower in production into
This, improves production efficiency, and the diafiltration device 6 also includes central controller 600, first Clean water valve 631, described second
Clean water valve 633, material valve 641, waste liquid valve 661 are Perfected electromagnetic metering valve, are connected with central controller 600, in center
Under the control of controller 600 perform valve opening and closing action, electronic sliding block 612, extension sleeve 613 respectively with central controller 600
Connection, is moved under the control of central controller 600；Drying chamber 622 is connected with central controller 600, is controlled in center
The parameter such as the temperature of regulation drying chamber 622, air-flow, spray thrower 632 are connected with central controller 600 under the control of device 600 processed,
The spray angles of spray thrower 632 under the control of central controller 600.
Further, material collection groove 623 is connected with the charging aperture of the supercritical liq kettle in step 4), and by controlling
Whether device control feeds；Thus whole-course automation control can be realized.
Specific control process comprises the following steps：
A, central controller 600 controls electronic sliding block 612, extension sleeve 613 to move successively, filter frame 615 is in filter
The top of liquid bath 621, the lower section of the discharge end of material pipeline 64；
B, central controller 600 opens material valve 641 and waste liquid valve 661, passes through mixing of the filter plate 616 to titanium dioxide
Thing is filtered, and waste liquid enters collecting tank 62 through waste-solution line 66, and titanium dioxide is stayed on filter plate 616；
C, central controller 600 closes waste liquid valve 661, opens the second Clean water valve 633, makes to store in filtrate receiver 621
A certain amount of clear water, central controller 600 control extension sleeve 613 to move, filter frame 615 is in filtrate receiver 621, make titanium
White powder is immersed in clear water；Central controller 600 controls extension sleeve 613 to be pivoted during immersion；
After immersion, central controller 600 controls extension sleeve 613 to rotate and move up, and removes the spacing of liquid level one
From when, keep upper-lower position constant, but extension sleeve 613 still keeps rotating and positioned at the lower section of spray thrower 632；Then center control
The first Clean water valve 631 is opened in the control of device 600, and spray thrower 632 is opened and translation-angle spray clear water；It is now placed in filter frame
Titanium dioxide in 615 ceaselessly rotates and sprayed by the clear water of spray thrower 632 various angles, further to titanium dioxide
Cleaned.
D, after cleaning, central controller 600 controls extension sleeve 613 and electronic sliding block 612 to move, and makes filter frame
615 in the top of drying chamber 622, the lower section of spray thrower 632；Central controller 600 opens waste liquid valve 661 simultaneously, by filtrate receiver
Waste liquid discharge in 621；
E, central controller 600 adjust drying chamber 622 in temperature, airflow direction and speed, keep extension sleeve 613 around
Axle is rotated, and titanium dioxide is dried；
F, after drying, central controller 600 controls extension sleeve 613 and electronic sliding block 612 to move, and makes filter frame
615 in material collection groove 623, to collect the titanium dioxide after inorganic coating.
Filtering, washing in present invention step 3) primarily described herein, drying device, described device can be with work of the present invention
Other each equipment of skill are connected, and to form the production line of series connection, the automation of processing line is realized by the operation of control device
Using.
Finally it is to be appreciated that above example is merely to illustrate technical scheme and not limited, although reference
Technical scheme is described in detail for preferred embodiment, it will be appreciated by those skilled in the art that can be to this hair
Bright technical scheme is modified or equivalent substitution, and without departing from the purpose and scope of the invention, it all should cover in this hair
Among bright protection domain.
Claims (10)
1. the special titanium dioxide process of high gloss paint, it is characterised in that：The titanium dioxide process is：(1) with work
Industry titanium dioxide is raw material, prepares mesoporous TiO 2；(2) mesoporous TiO 2 is prepared into slurry with deionized water, and adds alkali
Property solution regulation pH value be 9~9.5, disperse, stir and add alumina silicate, hydrochloric acid is added dropwise, control pH value as 7.5~8.5, and protect
80~100 DEG C of temperature is held, continues 1~4h of stirring, filtering, washing, dries, obtain inorganic coating mesoporous TiO 2；(3) to step
Suddenly the mesoporous TiO 2 of (2) by cladding processing carries out organic fluoride surface treatment.
2. titanium dioxide process according to claim 1, it is characterised in that：Step (1) is specially：First by industry
Concentrated alkali solution is added in titanium dioxide, is completely dissolved industrial titanium dioxide, stirring makes it fully react, and the solution obtained is scattered in
In deionized water, stirring obtains mixed liquor；It is added dropwise concentrated acid under stirring into mixed liquor, the volume ratio of concentrated acid and mixed liquor is 6：1,
Stirring reaction 30 minutes；Obtained solution is placed in high-pressure hydrothermal reaction kettle and reacted 6 hours in 180 DEG C, mesoporous dioxy is made
Change titanium.
3. titanium dioxide process according to claim 2, it is characterised in that：The concentrated acid is 38% hydrochloric acid.
4. titanium dioxide process according to claim 1, it is characterised in that：The alumina silicate and alkali of the step (2)
Property solution in the ratio between the molal weight of hydroxide ion be 1：7~10.
5. titanium dioxide process according to claim 4, it is characterised in that：Step (2) reaction temperature is 90
~100 DEG C, mixing time is 2~4h.
6. titanium dioxide process according to claim 5, it is characterised in that：The alkaline solution is NaOH solution.
7. titanium dioxide process according to claim 6, it is characterised in that：By the two of step (2) cladding processing
Titanium oxide is cladding completely.
8. titanium dioxide process according to claim 1, it is characterised in that：Step (3) is specially：By asphalt mixtures modified by epoxy resin
Titanium dioxide prepared by fat, the step of being crossed with coupling agent treatment (2) is separately dried processing, and epoxy resin is placed in into supercritical fluid
In kettle, pressure and temperature in kettle is adjusted so that the pressure and temperature of delivery of fluorine/nitrogen reaches critical point；It is dispersed with stirring shooting flow
Material in body kettle so that epoxy resin fusion plastification；Titanium dioxide after addition processing, and it is passed through overcritical delivery of fluorine/nitrogen
Fluid, 40~70min of stir process at a temperature of 90~130 DEG C；Highly pressurised liquid is depressured, faced to less than delivery of fluorine/nitrogen
Below boundary's pressure, material separated, sprayed, is crushed, crossing sieve classification, obtaining fluorinated epoxy resin titanium dioxide granule.
9. titanium dioxide process according to claim 7, it is characterised in that：The overcritical delivery of fluorine/nitrogen fluid
Fluorine/nitrogen volume ratio is 1：9~2：3.
10. titanium dioxide process according to claim 7, it is characterised in that：The overcritical delivery of fluorine/nitrogen fluid
For the supercritical fluid under 5.21~10Mpa pressure.
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| CN100999620A (en) * | 2006-12-20 | 2007-07-18 | 中国科学院山西煤炭化学研究所 | Process for coating surface of titanium white powder |
| CN101492575A (en) * | 2008-01-21 | 2009-07-29 | 河南佰利联化学股份有限公司 | Surface modified method for titanium dioxide for papermaking |
| CN106497147A (en) * | 2016-10-25 | 2017-03-15 | 锦州钛业有限公司 | A kind of preparation method with high covering power, high-weatherability and high whiteness TiO 2 pigment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1994021733A1 (en) * | 1993-03-15 | 1994-09-29 | Kompopigment Ltd. | Pigments having good scattering properties and process for the production thereof |
| CN1298430A (en) * | 1998-04-22 | 2001-06-06 | 昭和电工株式会社 | Particulate metal oxide with evenly fluorinated surface, process for producing the same, and use |
| CN100999620A (en) * | 2006-12-20 | 2007-07-18 | 中国科学院山西煤炭化学研究所 | Process for coating surface of titanium white powder |
| CN101492575A (en) * | 2008-01-21 | 2009-07-29 | 河南佰利联化学股份有限公司 | Surface modified method for titanium dioxide for papermaking |
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