CN109082140A - A kind of preparation method of compound high infrared reflection nano dye - Google Patents
A kind of preparation method of compound high infrared reflection nano dye Download PDFInfo
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- CN109082140A CN109082140A CN201810975319.4A CN201810975319A CN109082140A CN 109082140 A CN109082140 A CN 109082140A CN 201810975319 A CN201810975319 A CN 201810975319A CN 109082140 A CN109082140 A CN 109082140A
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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
- C09C1/22—Compounds of iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a kind of preparation method of compound high infrared reflection nano dye, specifically: 1) by P123 and deionized water disperse in suitable dehydrated alcohol progress magnetic stirring；2) LaFeO is added after completely dissolution to P1233, and whipping temp is set, butyl titanate is added in blender temperature after stablizing, ammonium hydroxide is added dropwise to adjust pH value；3) it is cleaned for several times with water and ethyl alcohol respectively after the reaction was completed, until impurity removal is complete, upper solution clarification, centrifugation is precipitated；4) precipitating obtained in step 3) is dried, is put into furnace and calcines after the completion of dry, it is ground to obtain compound high infrared reflection nano dye.In short, combining LaFeO with the compound high infrared reflection nano dye of the method for the present invention preparation gained3And TiO2Excellent performance, have it is nontoxic, colorability is strong, infrared reflectivity is high, good chemical stability.
Description
Technical field
The present invention relates to the pigment technologies such as building, ceramics, weaving fields, are specifically related to a kind of compound high infrared reflection
The preparation method of nano dye.
Background technique
In recent years, pigment is widely used in the fields such as building, ceramics, weaving.People also get over the performance requirement of pigment
Come higher.Traditional inorganic pigment is white and light color mostly, be easy to cause white light pollution to cut containing toxic component, makes to environment
The demand of all trades and professions is had been unable to meet at the pigment of pollution, and traditional single performance, so preparing novel receive now
Meter level Subnano-class material replaces the pigment of traditional single performance to be the hot spot of current Material Field research.Therefore seek green
The synthetic method of color obtains that size is small, good dispersion, fire resistance are good, good corrosion resistance, saturation under relatively mild environment
Spend, the compound high infrared reflection nano dye of even particle size distribution it is imperative.
Common TiO2It is a kind of heat-insulated pigment of high infrared reflection, it is fluffy white powder, and shielding ultraviolet rays effect is strong,
There are good dispersibility and durability.But since own appearance is white, so white pollution is easily caused, also certain
The retina of people has been injured in degree.
Application No. is 201510060090.8 patent applications to disclose a kind of high infrared reflection nano dye.Although the face
Material has the advantages that good thermal stability, good light stability, high infrared reflection rate are high, but its required raw material type is various, causes
Complex for operation step in preparation process, large-scale production is difficult to ensure quality, is unfavorable for industrial production.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of compound high infrared reflection nanometer of inorganic-inorganic
The preparation method of pigment, by active TiO2With pigment LaFeO3It carries out compound, has synthesized high infrared reflection ring at a lower temperature
Protect inorganic pigment.
The technical scheme is that a kind of preparation method of compound high infrared reflection nano dye, including walk as follows
It is rapid:
1) progress magnetic stirring in suitable dehydrated alcohol is dispersed by surfactant and deionized water；
2) LaFeO is added after completely dissolution to surfactant3, and whipping temp is set, blender temperature adds after stablizing
Enter butyl titanate, ammonium hydroxide is added dropwise to adjust pH value, reacts 3~4h；
3) it is cleaned for several times with water and ethyl alcohol respectively after the reaction was completed, until impurity removal is complete, upper solution clarification is centrifuged
It is precipitated；
4) obtained be deposited at 70 DEG C~80 DEG C in step 3) is dried, is put into 400 in furnace after the completion of dry
DEG C~500 DEG C of 1~3h of calcining, ground is to obtain compound high infrared reflection nano dye.
Further, after the step 4) grinding, at 34~47 DEG C, by obtained pigment and coalescing agent according to 2:(2
~5) 2~3h, and additional alternating magnetic field, central magnetic field 2400Gs, the alternative frequency of alternating magnetic field are impregnated in mass ratio mixing
10Hz；Mixing and attachment of the coalescing agent to precipitating can be improved by additional alternating magnetic field under this condition, helped by film forming
The immersion treatment of agent, can be improved the storage stability of compound high infrared reflection nano dye, and improve the pigment at
Film properties.
Further, the coalescing agent the preparation method comprises the following steps:
S1: it is complete that 7~10 parts of Lauryl Alcohol ester, 4~6 parts of polyoxyethylene carboxylate, acrylic acid are chosen according to parts by weight
6~9 parts of fluothane base ester, 0.3~0.5 part of hexamethylene diisocyanate, 1~2 part of cumyl peroxide, methyl ethyl ketone peroxide
0.8~1.5 part, 0.5~0.8 part of activated carbon powder, 5~7 parts of ethyl alcohol, 3~4 parts of propylene glycol, 1~2 part of nano titanium dioxide powder；
S2: by Lauryl Alcohol ester, polyoxyethylene carboxylate, perfluoroalkyl acrylate, hexamethylene diisocyanate
After mixing at 23~31 DEG C, it is added dropwise cumyl peroxide after being heated to 64~78 DEG C, 800~1000rpm stirring 5~
After 7min, then room temperature is down to the rate of 2 DEG C/min, forms mixture A, for use；
S3: ethyl alcohol, propylene glycol and methyl ethyl ketone peroxide are mixed, and control temperature at 35~45 DEG C, and additional microwave power
3~5min of microwave treatment of 180~300W, microwave frequency 2150MHz form mixture B, for use；By it is additional under this condition
Microwave can effectively improve ethyl alcohol, propylene glycol and methyl ethyl ketone peroxide degree of mixing, and then improve the performance of coalescing agent；
S4: being added the deionized water of its 0.5 times of weight after the mixture B of the mixture A of step S2 and step S3 is mixed,
After mixing, it adds activated carbon powder and nano titanium dioxide powder carries out high-pressure pulse electric, ultrasonic in combination dispersion, 25
High-pressure pulse electric is carried out at~40 DEG C and handles 15~30min, during which 2~3 DEG C and applies ultrasonic place every heating in 3~5 minutes
1~2min is managed, obtains coalescing agent, the ultrasound condition after high-pressure pulse electric, ultrasonic in combination dispersion are as follows: ultrasonic power is
150~260W, supersonic frequency are 20~70kHz, the high-voltage pulse electric field condition are as follows: 20~55KV/cm of electric field strength, pulse
Number 2~7.The degree of mixing that mixture A and mixture B can be significantly improved by high-pressure pulse electric, ultrasonic in combination dispersion, leads to
It crosses and adds active powdered carbon under the ratio and the performance of coalescing agent can be enhanced in nano titanium dioxide powder；Pass through our legal system
Standby coalescing agent can significantly improve weatherability, scrub resistance, the stability etc. of compound high infrared reflection nano dye
Deng.
Further, surfactant described in step 1) is preferably P123.
Further, it is 8 that ammonium hydroxide is added dropwise in step 2) and adjusts pH value, reacts 3h.
Further, the drying condition in step 4) specifically: 80 DEG C of dry 1h, calcination condition are as follows: 500 DEG C of temperature calcinings
1h。
Further, LaFeO described in step 2)3It is obtained through following methods: the beaker for being placed with deionized water is placed in
In constant temperature blender with magnetic force, magnetic stirring apparatus temperature is adjusted to 60 ± 10 DEG C；When magnetic stirring apparatus temperature is raised to and is stabilized to 60
At ± 10 DEG C, glycine is dissolved in deionized water, is after completely dissolution added sequentially to ferric nitrate, lanthanum nitrate to glycine molten
In liquid, it is stirred for 120 ± 10min after completely dissolution；After stirred, above-mentioned mixed solution is poured into evaporating dish, general-purpose is placed on
120 ± 10 DEG C of heating stirrings on electric furnace, the loose powder of self-propagating combustion reaction generation occurs for solution in the process, will be fluffy
Powder be put into agate mortar and grind, gained powder is obtained in 600~900 DEG C of temperature lower calcinations after milled.
Further, LaFeO described in step 2)3Preparation process in, the lanthanum nitrate and ferric nitrate of addition are distinguished
In terms of La, Fe, glycine mole is 2 times of the sum of La, Fe mole.
Further, calcination temperature is 700~800 DEG C.
Further, calcination temperature is 750 DEG C.LaFeO3Preparation process in matrix calcined at 600 DEG C and 700 DEG C
Not exclusively, as the temperature rises, impurity peaks disappear, and baseline tends to be steady, and peak shape tends to sharply, and crystallinity is become better and better.800
900 DEG C of characteristic peaks are higher DEG C compared with 900 DEG C, and peak type is more sharp, but we still select from the aspect of energy saving
Select opposite lower 750~800 DEG C of calcination temperature.
Further, the step 2) is stirred by pigment preparation facilities, and the pigment preparation facilities includes
Main body, main shaft, stirring disk, feeding device, support plate and feed liquid mouth boss；End face center is equipped with feed inlet in the main body, main
Body bottom surface center is equipped with discharge port, and the main shaft is located at body interior center, and main shaft upper end passes through top surface on motor and main body
Connection, there are two the stirring disk is set, two stirring disks are equidistantly located on main shaft from top to bottom, and the support plate is equipped with four
It is a, it is located at the middle part all around of body side, is equipped with sliding rail among support plate, the feeding device is located on support plate
End, the feed liquid mouth boss are located at support plate lower end；
The stirring disk circumference distal end is equipped with groove, and the groove is built-in with weighted spherical ball, stirs top surface on turntable
Multiple stirring main lobves are equidistantly equipped with bottom surface, it is secondary to be equidistantly equipped with multiple stirrings on the stirring main lobe left and right side
Leaf, stirring disk are embedded in main shaft by swinging fixture block, and the swing fixture block is used to make to stir disk and swings up and down and laterally limit
Position；
There are two the feed liquid mouth boss is set, it is located at the left and right ends that rail lower end is slided on support plate, feed liquid mouth boss
It is equipped with feed liquid mouth, the feed liquid mouth periphery is equipped with sealed elastic ring；
It is equipped among the feeding device medial surface and sliding rail is matched is elastically engaged slot, it is described to be elastically engaged slot or so
Two sides are equipped with the feed liquid interface with feed liquid mouth location matches, and the feed liquid interface periphery is equipped with and sealed elastic ring position
The sealed groove matched, end face center is equipped with adding mouth on feeding device.The present apparatus by stir disk effect make its with
It can also be swung up and down by the cooperation of weighted spherical ball and groove while main axis, utilize stirring main lobe and stirring accessory lobes
It is more fully stirred, while feeding device, the cooperation for sliding rail and feed liquid mouth boss, is made by the docking of two feed liquid mouths
Solution enters feeding device and washes away additive, ensure that the accurate of additive capacity, avoids the residual of addition, and match by elasticity
The leakproofness that slot, sealed elastic ring and sealed groove guarantee feed liquid interface and feed liquid mouth when docking is closed, in short, apparatus of the present invention make
With simplicity, mixing effect is good, easy can realize the accurate of additive capacity.
The working method of pigment preparation facilities of the present invention are as follows: deionized water is added in main body by feed inlet, by surface
Activating agent, dehydrated alcohol, LaFeO3, butyl titanate be separately added into four feeding devices, opening device, first by surface-active
Agent, dehydrated alcohol feeding device press at feed liquid mouth boss, feed liquid mouth and feed liquid interface docking, while sealed elastic ring,
Sealed groove occlusion sealing, makes deionized water generate spin by stirring action, keeps two feed liquid cause for gossip existing and body interior
Convection current, after completely dissolution to surfactant, by pressure LaFeO3Feeding device, and whipping temp is set, temperature to be mixed
Degree settles out the feeding device of pressing butyl titanate, adjusts pH value ammonium hydroxide is added dropwise by feed inlet, stirs after reacting 3-4h
It completes；Period stirs disk by swinging fixture block characteristic, rotates it with main shaft, while passing through weighted spherical ball and groove
Effect make stir disk swing up and down, pass through stirring main lobe and stirring accessory lobes improve mixing effect.
The beneficial effects of the present invention are:
(1) of the invention by LaFeO3Pigment and TiO2It is compound, by the synergistic effect of the two, the advantage of the two is performed to
Most preferably, LaFeO is synthesized3/TiO2Nano combined pigment.The compound high infrared reflection nano dye of gained of the invention combines
LaFeO3And TiO2Excellent performance has many advantages, such as rich in color, high infrared reflection rate, nontoxic.
(2) coalescing agent prepared by the present invention can significantly improve the weather-proof of compound high infrared reflection nano dye
Property, scrub resistance, stability etc.；Mixing and attachment of the coalescing agent to precipitating can be improved by additional alternating magnetic field, mention
The storage stability of high compound high infrared reflection nano dye, and improve the filming performance of the pigment.
(3) pigment preparation facilities of the invention makes it may be used also while with main axis by stirring the effect of disk
It is swung up and down by the cooperation of weighted spherical ball and groove, is more fully stirred using stirring main lobe and stirring accessory lobes,
Ensure that the accurate of additive capacity simultaneously, avoid the residual of addition, for the present apparatus using easy, mixing effect is good, can simplicity mention
The accuracy of high additive capacity.
In short, preparation method of the present invention is simple, raw material are easy to get, and synthesis temperature is low, and simple process is controllable, and it is raw to be suitable for scale
It produces.
Detailed description of the invention
Fig. 1 is the LaFeO calcined at 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C3XRD diagram.
Fig. 2 is to calcine LaFeO at 700 DEG C, 750 DEG C, 800 DEG C3XRD diagram.
Fig. 3 is the LaFeO prepared under different pH value3/TiO2XRD diagram and LaFeO3The XRD diagram of matrix.
Fig. 4 is the LaFeO prepared with different surfaces activating agent3/TiO2XRD diagram.
Fig. 5 is the LaFeO prepared under different pH value3/TiO2SEM figure: (a) pH=7 (b) pH=8 (c) pH=9.
Fig. 6 is the LaFeO prepared with different surfaces surfactant3/TiO2SEM figure: (a) P123 (b) PVP (c) Qula
Logical x-100.
Fig. 7 is the appearance diagram of preparation facilities of the present invention.
Fig. 8 is preparation facilities schematic diagram of internal structure of the present invention.
Fig. 9 is present invention stirring disk top view.
Figure 10 is feeding device structural schematic diagram of the present invention.
Wherein, 1- main body, 11- feed inlet, 12- discharge port, 2- main shaft, 21- motor, 3- stirring disk, 31- groove,
32- weighted spherical ball, 33- stirring main lobe, 34- stirring accessory lobes, 35- swing fixture block, 4- feeding device, 41- feed liquid interface, 42- sealing
Groove, 43- are elastically engaged slot, 44- adding mouth, 5- support plate, 51- sliding rail, 6- feed liquid mouth boss, 61- feed liquid mouth, 62- sealing
Elastic ring.
Specific embodiment
Embodiment 1
LaFeO3Preparation method:
The beaker for being placed with the deionized water of 150ml is placed in constant temperature blender with magnetic force first, by magnetic stirring apparatus temperature
It is adjusted to 60 DEG C.When magnetic stirring apparatus temperature is raised to and is stabilized to 60 DEG C, the glycine of 3.002g is dissolved in deionized water, to
4.04g ferric nitrate, 4.33g lanthanum nitrate are added sequentially in solution by glycine after completely dissolution, are stirred for 2h after completely dissolution.
After stirred, above-mentioned mixed solution is poured into evaporating dish, 120 DEG C of heating, liquid on universal electric furnace is placed on and starts to expand rapidly,
Solution starts the vigorous combustion in evaporating dish later, releases largely pungent flue gas, generates fluffy powder at burning in the process,
Fluffy powder is put into agate mortar and is ground, by gained powder in 600 DEG C of temperature lower calcination 2h after milled, then it is ground at
It is powdered to get arrive LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
Progress magnetic stirring in 250ml dehydrated alcohol is dispersed by 0.6g P123 and 2ml deionized water, it is sufficiently molten to P123
0.05gLaFeO is added after solution3Matrix, setting whipping temp are 60 DEG C.2.5ml is added when being stable at 60 DEG C in device temperature to be mixed
Butyl titanate starts timing when butyl titanate sufficiently dissolves, it is allowed to react 3 hours.In the process, by the way that ammonium hydroxide tune is added dropwise
Whole pH=8.So that butyl titanate hydrolyzes and the TiO of generation2It is coated on cadmium ferrite surface.Number is cleaned with water and ethyl alcohol respectively later
Secondary, until impurity removal is complete, upper solution is clarified.Centrifugal process is precipitated, and is dried at 70 DEG C.It is put after the completion of dry
Enter 500 DEG C of calcining 1h in furnace, ground is to obtain compound high infrared reflection nano dye.
Embodiment 2
LaFeO3Preparation method:
Unlike the first embodiment, magnetic stirring apparatus temperature is adjusted to 50 DEG C；It is stirred for 130min after completely dissolution；It puts
110 DEG C of heating on universal electric furnace；Gained powder in 700 DEG C of temperature lower calcination 2h, then it is ground at powdered to get arriving
LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
Progress magnetic stirring in 250ml dehydrated alcohol is dispersed by 0.5gPVP and 2ml deionized water, is sufficiently dissolved to P123
After 0.05gLaFeO is added3Matrix, setting whipping temp are 60 DEG C.2.5ml titanium is added when being stable at 60 DEG C in device temperature to be mixed
Acid butyl ester starts timing when butyl titanate sufficiently dissolves, it is allowed to react 3.5 hours.In the process, by the way that ammonium hydroxide tune is added dropwise
Whole pH=8.So that butyl titanate hydrolyzes and the TiO of generation2It is coated on cadmium ferrite surface.Number is cleaned with water and ethyl alcohol respectively later
Secondary, until impurity removal is complete, upper solution is clarified.Centrifugal process is precipitated, and is dried at 75 DEG C.It is put after the completion of dry
Enter 450 DEG C of calcining 2h in furnace, ground is to obtain compound high infrared reflection nano dye.
Embodiment 3
LaFeO3Preparation method:
Unlike the first embodiment, magnetic stirring apparatus temperature is adjusted to 70 DEG C；It is stirred for 110min after completely dissolution；It puts
130 DEG C of heating on universal electric furnace；Gained powder in 800 DEG C of temperature lower calcination 2h, then it is ground at powdered to get arriving
LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
5ml Qula is led into x-100 and 2ml deionized water and is scattered in progress magnetic stirring in 250ml dehydrated alcohol, is filled to P123
0.05gLaFeO is added after dividing dissolution3Matrix, setting whipping temp are 60 DEG C.Addition when device temperature to be mixed is stable at 60 DEG C
2.5ml butyl titanate starts timing when butyl titanate sufficiently dissolves, it is allowed to react 4 hours.In the process, pass through dropwise addition
Ammonium hydroxide adjusts pH=8.So that butyl titanate hydrolyzes and the TiO of generation2It is coated on cadmium ferrite surface.Use water and ethyl alcohol respectively later
For several times, until impurity removal is complete, upper solution is clarified for cleaning.Centrifugal process is precipitated, and is dried at 80 DEG C.It has dried
400 DEG C of calcining 3h in furnace are put into after, ground is to obtain compound high infrared reflection nano dye.
Embodiment 4
LaFeO3Preparation method:
Unlike the first embodiment, gained powder is in 900 DEG C of temperature lower calcination 2h, then it is ground at powdered to get arriving
LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
Unlike the first embodiment, in the process, pH=7 is adjusted by the way that ammonium hydroxide is added dropwise.
Embodiment 5
LaFeO3Preparation method:
Unlike the first embodiment, gained powder is in 750 DEG C of temperature lower calcination 2h, then it is ground at powdered to get arriving
LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
Unlike the first embodiment, in the process, pH=9 is adjusted by the way that ammonium hydroxide is added dropwise.
Embodiment 6
LaFeO3Preparation method:
Unlike the first embodiment, gained powder is in 750 DEG C of temperature lower calcination 2h, then it is ground at powdered to get arriving
LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
Unlike the first embodiment, after grinding, at 34 DEG C, by obtained pigment and coalescing agent according to the quality of 2:3
2h, and additional alternating magnetic field, central magnetic field 2400Gs, the alternative frequency 10Hz of alternating magnetic field are impregnated than mixing；It is somebody's turn to do by additional
Under the conditions of alternating magnetic field coalescing agent can be improved can by the immersion treatment of coalescing agent to the mixing and attachment of precipitating
To improve the storage stability of compound high infrared reflection nano dye, and improve the filming performance of the pigment.
Coalescing agent the preparation method comprises the following steps:
S1: 7 parts of Lauryl Alcohol ester, 4 parts of polyoxyethylene carboxylate, perfluoroalkyl acrylate are chosen according to parts by weight
6 parts, 0.3 part of hexamethylene diisocyanate, 1 part of cumyl peroxide, 0.8 part of methyl ethyl ketone peroxide, activated carbon powder 0.5
Part, 5 parts of ethyl alcohol, 3 parts of propylene glycol, 1 part of nano titanium dioxide powder；
S2: by Lauryl Alcohol ester, polyoxyethylene carboxylate, perfluoroalkyl acrylate, hexamethylene diisocyanate
After mixing at 23 DEG C, be added dropwise cumyl peroxide after being heated to 64 DEG C, after 800rpm stirs 5min, then with 2 DEG C/
The rate of min is down to room temperature, forms mixture A, for use；
S3: ethyl alcohol, propylene glycol and methyl ethyl ketone peroxide are mixed, and control temperature at 35 DEG C, and additional microwave power 180W,
The microwave treatment 3min of microwave frequency 2150MHz forms mixture B, for use；It can be effective by additional microwave under this condition
Ethyl alcohol, propylene glycol and methyl ethyl ketone peroxide degree of mixing are improved, and then improves the performance of coalescing agent；
S4: being added the deionized water of its 0.5 times of weight after the mixture B of the mixture A of step S2 and step S3 is mixed,
After mixing, it adds activated carbon powder and nano titanium dioxide powder carries out high-pressure pulse electric, ultrasonic in combination dispersion, 25
At DEG C carry out high-pressure pulse electric handle 15min, during which every 3 minutes heating 2-3 DEG C and apply ultrasonic treatment 1min, high-tension pulse
Coalescing agent, ultrasound condition are obtained after rushing electric field, ultrasonic in combination dispersion are as follows: ultrasonic power 150W, supersonic frequency 20kHz,
High-voltage pulse electric field condition are as follows: electric field strength 20KV/cm, umber of pulse 2.By high-pressure pulse electric, ultrasonic in combination dispersion can
To significantly improve the degree of mixing of mixture A and mixture B, by adding active powdered carbon and nanometer titanium dioxide titanium valve under the ratio
The performance of coalescing agent can be enhanced in end；The coalescing agent prepared by this method, it is anti-can to significantly improve compound high IR
Penetrate the weatherability of nano dye, scrub resistance, stability etc..
Embodiment 7
LaFeO3Preparation method:
Unlike the first embodiment, gained powder is in 750 DEG C of temperature lower calcination 2h, then it is ground at powdered to get arriving
LaFeO3It is nanocrystalline.
The preparation method of compound high infrared reflection nano dye:
Unlike the first embodiment, after grinding, at 41 DEG C, precipitating and coalescing agent are mixed according to the mass ratio of 2:4
Impregnate 2.5h, and additional alternating magnetic field, central magnetic field 2400Gs, the alternative frequency 10Hz of alternating magnetic field.
Coalescing agent the preparation method comprises the following steps:
S1: 9 parts of Lauryl Alcohol ester, 5 parts of polyoxyethylene carboxylate, perfluoroalkyl acrylate are chosen according to parts by weight
7 parts, 0.4 part of hexamethylene diisocyanate, 2 parts of cumyl peroxide, 1.2 parts of methyl ethyl ketone peroxide, activated carbon powder 0.7
Part, 6 parts of ethyl alcohol, 3 parts of propylene glycol, 2 parts of nano titanium dioxide powder；
S2: by Lauryl Alcohol ester, polyoxyethylene carboxylate, perfluoroalkyl acrylate, hexamethylene diisocyanate
After mixing at 27 DEG C, be added dropwise cumyl peroxide after being heated to 73 DEG C, after 950rpm stirs 6min, then with 2 DEG C/
The rate of min is down to room temperature, forms mixture A, for use；
S3: ethyl alcohol, propylene glycol and methyl ethyl ketone peroxide are mixed, and control temperature at 39 DEG C, and additional microwave power 270W,
The microwave treatment 4min of microwave frequency 2150MHz forms mixture B, for use；It can be effective by additional microwave under this condition
Ethyl alcohol, propylene glycol and methyl ethyl ketone peroxide degree of mixing are improved, and then improves the performance of coalescing agent；
S4: being added the deionized water of its 0.5 times of weight after the mixture B of the mixture A of step S2 and step S3 is mixed,
After mixing, it adds activated carbon powder and nano titanium dioxide powder carries out high-pressure pulse electric, ultrasonic in combination dispersion, 35
At DEG C carry out high-pressure pulse electric handle 20min, during which every 4 minutes heating 3 DEG C and apply ultrasonic treatment 2min, high-voltage pulse
Coalescing agent, ultrasound condition are obtained after electric field, ultrasonic in combination dispersion are as follows: ultrasonic power 240W, supersonic frequency 50kHz are high
Press condition of pulse electric field are as follows: electric field strength 45KV/cm, umber of pulse 6.
It is stirred in the preparation process of compound high infrared reflection nano dye by pigment preparation facilities, is such as schemed
Shown in 1 and 2, pigment preparation facilities includes main body 1, main shaft 2, stirring disk 3, feeding device 4, support plate 5 and feed liquid mouth boss 6；
End face center is equipped with feed inlet 11 in main body 1, and 1 bottom surface center of main body is equipped with discharge port 12, and main shaft 2 is located in 1 inside of main body
The heart, 2 upper end of main shaft are connect by motor 21 with top surface in main body 1, are stirred there are two disk 3 sets, two stirring disks 3 on to
It is equidistantly located on main shaft 1 down, there are four support plate 5 is set, is located at the middle part all around of 1 side of main body, is set among support plate 5
There is sliding rail 51, feeding device 4 is located at 5 upper end of support plate, and feed liquid mouth boss 6 is located at 5 lower end of support plate；
As shown in figure 3, stirring 3 circumference of disk distal end is equipped with groove 31, groove 31 is built-in with weighted spherical ball 32, and stirring turns
Top surface and bottom surface are equidistantly equipped with multiple stirring main lobves 33 on disk 3, stir on 33 left and right side of main lobe equidistantly equipped with more
A stirring accessory lobes 34, stirring disk 3 swing fixture block 35 for making and stir about 3 disk by swinging fixture block 35 in main shaft 2
Swing and cross spacing；
As shown in Figure 1, the left and right ends that 51 lower end of rail is slided on support plate 5 are located at there are two feed liquid mouth boss 6 sets,
Feed liquid mouth boss 6 is equipped with feed liquid mouth 61, and 61 periphery of feed liquid mouth is equipped with sealed elastic ring 62；
As shown in figure 4, being equipped among feeding device 4 medial surface, rail 51 is matched is elastically engaged slot 43 with sliding, and elasticity is matched
The feed liquid interface 41 being equipped at left and right sides of slot 43 with 61 location matches of feed liquid mouth is closed, 41 periphery of feed liquid interface is equipped with and sealing
The sealed groove 42 of 62 location matches of elastic ring, end face center is equipped with adding mouth 44 on feeding device 4.
The working method of above-mentioned pigment preparation facilities are as follows: deionized water is added in main body 1 by feed inlet 11, by surface
Activating agent, dehydrated alcohol, LaFeO3, butyl titanate be separately added into four feeding devices 4, opening device, first by surface-active
Agent, dehydrated alcohol feeding device 4 press at feed liquid mouth boss 6, feed liquid mouth 61 and feed liquid interface 41 dock, while sealing bullet
Property ring 62, sealed groove 42 occlusion sealing, make deionized water by stirring action generate spin, make two feed liquid mouth 61 realization
After completely dissolution to surfactant pressure LaFeO is pressed with the convection current inside main body 13Feeding device 4, and be arranged stirring temperature
Degree, temperature to be mixed settle out the feeding device 4 of pressing butyl titanate, adjust pH value ammonium hydroxide is added dropwise by feed inlet 11,
Completion is stirred after reacting 3-4h；Period stirs disk 3 by swinging 35 characteristic of fixture block, rotates it with main shaft 2, simultaneously
So that stirring disk 3 is swung up and down by the effect of weighted spherical ball 32 and groove 31, passes through stirring main lobe 33 and stirring accessory lobes
34 improve mixing effect.
XRD test
LaFeO is obtained by calcining precursor powder3Nanocrystalline, Fig. 1 is at 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C respectively
LaFeO3Nanocrystalline XRD diagram picture.It is opened caning be found that after XRD diagram and standard graph card JCPDSNO.74-2203 comparison from 600 DEG C
Beginning, there have been the characteristic peaks of cadmium ferrite.600 DEG C and 700 DEG C all there are impurity peaks, by XRD diagram and standard graph card respectively with
JCPDS NO.22-641 and JCPDS NO.2-915 are it was found that impurity peaks are La2O3And Fe2O3Characteristic peak, this illustrates matrix
It is calcined at 600 DEG C and 700 DEG C incomplete.As the temperature rises, impurity peaks disappear, and baseline tends to be steady, and peak shape tends to point
Sharp, crystallinity is become better and better.800 DEG C compared with 900 DEG C 900 DEG C characteristic peaks it is higher, peak type is more sharp, but from energy saving
From the aspect of we still select opposite lower 800 DEG C of calcination temperature.
As shown in Figure 2,750 DEG C of calcination temperature equally eliminates the impurity being mixed in cadmium ferrite, has obtained good crystallinity
Cadmium ferrite it is nanocrystalline, the nano particle diameter obtained since peak value is higher is bigger, and for pigment, granularity is smaller, particle
Specific surface area is bigger, and specific surface energy is higher, and material scatter is better in addition, easily forms uniform coating in use, and attached
Put forth effort strong, evenness.In order to next to matrix cladding lay a good foundation, we determined that 750 DEG C for self- propagating fire
Burning method prepares the more excellent temperature of ferrous acid lanthanum pigment.
Fig. 3 is the product X RD image of different pH value.The matrix that temperature is 750 DEG C, remaining is compound rear LaFeO3/TiO2。
, it can be seen that LaFeO from figure3The diffraction maximum of matrix is narrow and sharp, and crystal structure is good.LaFeO after compound3/TiO2
Crystal, since pH=7 image, all there is TiO in every curve2(△ is labeled as TiO to characteristic peak2Characteristic peak) illustrate TiO2?
Through being successfully coated on LaFeO3On matrix.Explanation the method can be successfully prepared out LaFeO3/TiO2Nano combined face
Material.LaFeO in the image of pH=7, pH=8, pH=93Characteristic peaks have apparent decrease, this is because TiO2It wraps
LaFeO3Generated result.LaFeO in the image of pH=93Peak value it is extremely low compared with matrix, illustrate to be likely to be TiO2
Layer package it is too thick, in this way since our obtained composite pigments be very likely TiO2What is shown is white rather than color
Color.Specific covered effect needs further to analyze by SEM.
Fig. 4 is the XRD analysis figure of different surfaces activating agent product.Different surfactants has experiment as we know from the figure
Different influences: wherein there is apparent TiO using the sample that PVP and P123 is coated2(△ is labeled as TiO to characteristic peak2Characteristic peak),
Show TiO2Successfully it has been compounded in LaFeO3On matrix；And there is no very big compared with matrix for the sample for using Qula to lead to
, there is not TiO in difference2Characteristic peak.And PVP uses the sample TiO of P123 compared with P1232Characteristic peak it is higher, peak
Type is more sharp.This explanation uses the covered effect of PVP more preferable under square one using P123 ratio.
SEM test
Structured testing is carried out to product by scanning electron microscope, Fig. 5 is the SEM image for preparing product at various ph values, from
Image can be seen that pH value to TiO2Covered effect influences more obvious.Wherein figure a and figure c dispersibility are poor, there is a large amount of reunions
Phenomenon, figure c become apparent；And scheme b dispersibility preferably, there is apparent near-spherical particle to occur, partial size is in 30nm or so.Particle table
Face is coarse, and there are many small protrusions on surface, and from the point of view of XRD, these kicks are exactly the TiO in cladding2.To which preferable ph is
8。
Fig. 6 is the SEM image that product is prepared with different surfaces activating agent, from image it can be seen that different surfaces activating agent pair
TiO2Covered effect influences more obvious, wherein the product dispersibility of figure a is preferably, near-spherical is presented, uniform in size, surface is thick
Rough, there are many little particle protrusions on surface, illustrates that these these little particles on surface are exactly in cladding in conjunction with XRD characteristic peak
TiO2.And scheme b and figure c dispersibility it is poor, size is uneven.To which preferred surfactant is preferably P123.
Coloration test
The data of table 1 are the colorimetric analysis result of the sample of different pH value.It is concluded that pH=based on the analysis results
The sample of pigment L* (lightness) highest produced when 9, pH=7 and pH=8 also have good brightness.PH=7 and pH=8 sample
Partially red (a* high), the inclined yellow (b* high) of pH=9 sample.According to the trend of today's society, the pigment of this pink colour should compare
It is welcome.
Table 1LaFeO3/TiO2Nano combined pigment color coordinate diagram
Mechanism of the invention is as follows:
LaFeO3Matrix is a kind of structure with extensive chemical stability, not soluble in water, ethyl alcohol is not dissolved in, insoluble in acid.
And TiO2It is a kind of heat-insulated pigment of high infrared reflection, it is single the disadvantage is that due to its white appearance, it is easy to cause white light pollution, hurt
The retina of victimization.Therefore, the two is effectively combined, the high infrared reflection insulating color face of the compound high comprehensive performance out of energy
Material.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (10)
1. a kind of preparation method of compound high infrared reflection nano dye, which comprises the steps of:
1) progress magnetic stirring in suitable dehydrated alcohol is dispersed by surfactant and deionized water；
2) LaFeO is added after completely dissolution to surfactant3, and whipping temp is set, metatitanic acid is added after stablizing in blender temperature
Butyl ester is added dropwise ammonium hydroxide to adjust pH value, reacts 3~4h；
3) it is cleaned for several times with water and ethyl alcohol respectively after the reaction was completed, until impurity removal is complete, upper solution clarification, centrifugation is obtained
Precipitating；
4) obtained be deposited at 70 DEG C~80 DEG C in step 3) is dried, be put into furnace after the completion of dry 400 DEG C~
500 DEG C of 1~3h of calcining, ground is to obtain compound high infrared reflection nano dye.
2. a kind of preparation method of compound high infrared reflection nano dye according to claim 1, which is characterized in that institute
State step 4) grinding after, at 34~47 DEG C, by obtained pigment and coalescing agent according to 2:(2~5) mass ratio mix leaching
Steep 2~3h, and additional alternating magnetic field, central magnetic field 2400Gs, the alternative frequency 10Hz of alternating magnetic field.
3. a kind of preparation method of compound high infrared reflection nano dye according to claim 1, which is characterized in that step
Rapid 2) the middle ammonium hydroxide adjusting pH value that is added dropwise is 8, reacts 3h.
4. a kind of preparation method of compound high infrared reflection nano dye according to claim 1, which is characterized in that step
It is rapid 4) in drying condition specifically: 80 DEG C of dry 1h, calcination condition are as follows: 500 DEG C of calcining 1h of temperature.
5. a kind of preparation method of compound high infrared reflection nano dye according to claim 1, which is characterized in that step
It is rapid 2) described in LaFeO3It is obtained through following methods: the beaker for being placed with deionized water is placed in constant temperature blender with magnetic force, it will
Magnetic stirring apparatus temperature is adjusted to 60 ± 10 DEG C；It is when magnetic stirring apparatus temperature is raised to and is stabilized to 60 ± 10 DEG C, glycine is molten
In deionized water, ferric nitrate, lanthanum nitrate are added sequentially in solution after completely dissolution to glycine, stirred again after completely dissolution
Mix 120 ± 10min；After stirred, above-mentioned mixed solution is poured into evaporating dish, is placed on 120 ± 10 DEG C of heating on universal electric furnace
Stirring, the loose powder of self-propagating combustion reaction generation occurs for solution in the process, and gained powder is in 600~900 DEG C of temperature
Lower calcining obtains.
6. a kind of preparation method of compound high infrared reflection nano dye according to claim 5, which is characterized in that step
It is rapid 2) described in LaFeO3Preparation process in, the whipping temp of the magnetic stirring apparatus is 60 ± 10 DEG C.
7. a kind of preparation method of compound high infrared reflection nano dye according to claim 5, which is characterized in that step
It is rapid 2) described in LaFeO3Preparation process in, the lanthanum nitrate and ferric nitrate of addition are respectively in terms of La, Fe, glycine mole
It is 2 times of the sum of La, Fe mole.
8. a kind of preparation method of compound high infrared reflection nano dye according to claim 5, which is characterized in that forge
Burning temperature is 700~800 DEG C.
9. a kind of preparation method of compound high infrared reflection nano dye according to claim 5, which is characterized in that forge
Burning temperature is 750 DEG C.
10. a kind of preparation method of compound high infrared reflection nano dye according to claim 1, which is characterized in that
The step 2) is stirred by pigment preparation facilities, and the pigment preparation facilities includes main body (1), main shaft (2), stirs
Mix disk (3), feeding device (4), support plate (5) and feed liquid mouth boss (6)；End face center is equipped with feed inlet on the main body (1)
(11), main body (1) bottom surface center is equipped with discharge port (12), and the main shaft (2) is located at main body (1) inside center, on main shaft (2)
End is connect by motor (21) with top surface on main body (1), and there are two the stirring disk (3) sets, two stirring disks (3) are from upper
Equidistantly be located on main shaft (1) to lower, there are four the support plate (5) sets, be located at main body (1) side all around in
Portion, support plate (5) is intermediate to be equipped with sliding rail (51), and the feeding device (4) is located at support plate (5) upper end, the feed liquid mouth boss (6)
Positioned at support plate (5) lower end；
Stirring disk (3) the circumference distal end is equipped with groove (31), and the groove (31) is built-in with weighted spherical ball (32), stirring
Top surface and bottom surface are equidistantly equipped with multiple stirring main lobves (33) on turntable (3), on stirring main lobe (33) left and right side
Multiple stirring accessory lobes (34) are equidistantly equipped with, stirring disk (3) is by swinging fixture block (35) in main shaft (2), the swing
Fixture block (35) is swung up and down and cross spacing for making to stir disk (3)；
There are two the feed liquid mouth boss (6) sets, it is located at the left and right ends that rail (51) lower end is slided on support plate (5), feed liquid
Mouth boss (6) is equipped with feed liquid mouth (61), and feed liquid mouth (61) periphery is equipped with sealed elastic ring (62)；
It is equipped with that rail (51) are matched is elastically engaged slot (43) with sliding among feeding device (4) medial surface, the elasticity is matched
It closes and is equipped with feed liquid interface (41) with feed liquid mouth (61) location matches at left and right sides of slot (43), outside feed liquid interface (41) circumference
Side is equipped with the sealed groove (42) with sealed elastic ring (62) location matches, and end face center is equipped with adding mouth on feeding device (4)
(44)。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286705A (en) * | 2016-03-30 | 2017-10-24 | 长城汽车股份有限公司 | Nano inorganic composite pigment and preparation method thereof |
| CN108017936A (en) * | 2017-12-05 | 2018-05-11 | 华北水利水电大学 | A kind of preparation method of spherical compound ultra-fine yellow ceramic paint |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286705A (en) * | 2016-03-30 | 2017-10-24 | 长城汽车股份有限公司 | Nano inorganic composite pigment and preparation method thereof |
| CN108017936A (en) * | 2017-12-05 | 2018-05-11 | 华北水利水电大学 | A kind of preparation method of spherical compound ultra-fine yellow ceramic paint |
Non-Patent Citations (1)
| Title |
|---|
| R. DHINESH KUMAR等: ""Synthesis and characterization of LaFeO3/TiO2 nanocomposites for visible light photocatalytic activity"", 《JOURNAL OF PHYSICAL AND CHEMISTRY OF SOLIDS》 * |
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