CN108299678A - A kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension - Google Patents
A kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension Download PDFInfo
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- CN108299678A CN108299678A CN201810113204.4A CN201810113204A CN108299678A CN 108299678 A CN108299678 A CN 108299678A CN 201810113204 A CN201810113204 A CN 201810113204A CN 108299678 A CN108299678 A CN 108299678A
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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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The present invention relates to delustering agent fields, disclose a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension, the present invention is ground with ultrasound treatment patterns instead of tradition machinery, and the titanium dioxide bulky grain separated is disintegrated under the action of ultrasonic wave into little particle, the advantage is that：Treatment effeciency is high, energy consumption is lower, generally only needs 5 ~ 30min of processing to be equivalent to the effect of grinding 2h, therefore can more preferably meet the needs of large-scale production；Ultrasonication is handled small to the destruction of titanium dioxide surface modification coating relative to mechanical lapping simultaneously, is influenced on the color value of product small.
Description
Technical field
The present invention relates to delustering agent field more particularly to a kind of preparation sides of polymer TITANIUM DIOXIDE DELUSTRANT suspension
Method.
Background technology
Titanium dioxide is widely used as a kind of delustering agent in polymer production, is usually by titanium dioxide and to gather
It closes monomer or its aqueous solution presses a certain concentration after mixing, delustring polymer is obtained after being sent into the aggregated reaction of polyplant.
To ensure that polymer quality, the grain size for not requiring nothing more than titanium dioxide meet the requirements, and there is good dispersibility and stablize
Property, so grain size titanium dioxide bigger than normal is filtered out in tio_2 suspension process for preparation, while to improve titanium dioxide
Utilization rate, the grain size that filters out titanium dioxide bigger than normal reuse again after postorder processing makes grain size reduce.In the prior art,
In order to improve dispersability of titanium dioxide, it is generally used the mode of grinding.
As the Chinese patent of Patent No. CN104313722A disclose it is a kind of it is centrifugal prepare tio_2 suspension
Method, including the preparation of caprolactam water solution, the preparation of tio_2 suspension, the centrifugation of tio_2 suspension,
The allotment of tio_2 suspension and the recycling of thick titanium dioxide, the recycling of disclosed thick titanium dioxide is by thick two
Titanium oxide is pumped into ball mill by conveying, and compounding system is reentered by the thick titanium dioxide of grinding, to reach recycling profit
Purpose.
But since ball mill grinding is entirely so that titanium dioxide bulky grain is disintegrated by mechanicals efforts, grinding efficiency is low,
Milling time is up to several hours, high energy consumption.What is more important simultaneously, to improve dispersed TITANIUM DIOXIDE DELUSTRANT powder life
All can be inorganic or organically-modified to surface progress when production, so that its surface is covered inorganic or organic matter, grinding for a long time makes surface change
Property coating destroyed, slurries form and aspect be deteriorated, may influence whether the color value b. values of polymer.Team of the present invention finds this
After problem, bulky grain titanium dioxide reuse efficiency is isolated to improve, while ensureing the form and aspect of slurries again, it is necessary to develop one
Kind new, more preferably technical solution solves above-mentioned technical problem.
Invention content
In order to solve the above technical problem, the present invention provides a kind of polymer systems of TITANIUM DIOXIDE DELUSTRANT suspension
Preparation Method, the present invention is ground with ultrasound treatment patterns instead of tradition machinery, by the titanium dioxide bulky grain separated in ultrasound
Disintegrate into little particle under the action of wave, the advantage is that：Treatment effeciency is high, energy consumption is lower, generally only needs 5 ~ 30min of processing just
It is equivalent to the effect of grinding 2h, therefore can more preferably meet the needs of large-scale production；Ultrasonication is relative to mechanical grinding simultaneously
Mill processing is small to the destruction of titanium dioxide surface modification coating, is influenced on the color value of product small.
The specific technical solution of the present invention is：A kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension, packet
Include following steps：
Titania powder and polymerized monomer or its aqueous solution are mixed to form suspension in a mixer；The suspension is passed through
The centrifugal treating for crossing centrifuge isolates the larger titanium dioxide of grain size, and the suspension of grain size qualification is delivered to blend tank, warp
Concentration is spare after allocating to normal concentration；The larger suspension of the grain size isolated from centrifuge is set using ultrasonication
It returns in mixer and remixes after standby processing, recycle according to this.
The present invention selects ultrasonic disperse mode instead of traditional grinding distribution, although on the surface like a kind of only letter
Single replacement（Ultrasonic disperse is also widely used in other field）, it appears that there is no what special features.But it can by analysis
Know, the present invention replaces grinding distribution not to be only to improve that dispersion efficiency is so simple, and concrete reason is as follows with ultrasonic disperse：
Ball mill grinding is entirely so that titanium dioxide bulky grain is disintegrated by mechanicals efforts, and the diameter of particle after grinding becomes smaller,
It can solve the problems, such as that powder is easy to reunite in state of the art substantially.But the present inventor is by studying for a long period of time
It was found that：Ball mill grinding is entirely so that titanium dioxide bulky grain is disintegrated by mechanicals efforts, and grinding efficiency is low, and milling time is up to
Several hours, high energy consumption.What is more important simultaneously, all can be to table when to improve dispersed TITANIUM DIOXIDE DELUSTRANT power production
Face carry out it is inorganic or organically-modified, make its surface cover inorganic or organic matter, for a long time grinding make surface be modified coating by
It destroys, slurries form and aspect, which are deteriorated, to black（It is possible that being surface coated organic matter or inorganic matter in long-time mechanical lapping and high temperature
It is lower to be aoxidized or occurred other chemical changes）, and the color value b values of polymer are eventually affected, cause product appearance drop etc..
For the above situation, those skilled in the art and it is unaware that this point at present, also there are no phase in the prior art
Report is closed, therefore there is no enough motivations to remove dispersing mode to be replaced by those skilled in the art, because current In the view of them
Research dispersion enough solution technical problem.After finding this problem between team of the present invention is accidental, to avoid titanium dioxide
It is destroyed after the grinding of titanium surface coating layer through a long time, and then is induced to the black of slurries, and then influence the color of polymer
Value, selection replace traditional grinding, the principle of ultrasonication to be ultrasonic wave " irradiation " slurries and generate sky with ultrasonication
To change effect, huge impact force and microjet are generated to titanium dioxide, under its effect, surface energy is weakened nano-powder, from
And realize to the peptizaiton of nano-powder, titanium dioxide surface clad is not for the mechanical lapping that compares, when supersound process
The extent of the destruction being subject to is small, so slurry color is not in black situation.It follows that replacing mechanical grinding with ultrasonic disperse
Mill, achieves unexpected technique effect to a certain extent.
Preferably, the grain size of the suspension of the grain size qualification is 1 μm or less.
Preferably, in the suspension titanium dioxide a concentration of 10 ~ 50wt%.
Preferably, excusing from death frequency is 20-100KHz, ultrasonic time is 5min ~ 30min.
Preferably, the normal concentration is 10 ~ 25wt%.
Preferably, the polymer and polymerized monomer or its aqueous solution are selected from following combination：
A, polymer is polyethylene terephthalate, and polymerized monomer is ethylene glycol；
B, polymer is polyamide, and polymerized monomer aqueous solution is the aqueous solution of amide or amidic-salt；
C, polymer is polycaprolactam, and polymerized monomer aqueous solution is caprolactam water solution；
D, polymer is polyhexamethylene adipamide, and polymerized monomer aqueous solution is the aqueous solution of adipic acid hexamethylene diamine salt；
E, polymer is polyadipate pentanediamine, and polymerized monomer aqueous solution is the aqueous solution of adipic acid pentanediamine salt.
One of optionally, the titania powder is modified by surface：
（1）Titania powder is scattered in deionized water and is stirred, is heated, adjusts pH, then be slowly added dropwise into aluminum sulfate solution,
PH is adjusted with dilute sulfuric acid simultaneously, continues stirring curing after dripping, is dried after washing to neutrality, unformed alumina-coated is made
Titanium dioxide powder；
（2）By step（1）Powder obtained and ultrasonic disperse after water, polyethylene glycol, dispersant, obtain after washing, drying
Modifying titanium dioxide.
The present invention has successively coated unformed aluminium oxide and polyethylene glycol to titanium dioxide surface, and surface is modified, can
Improve its dispersibility and interface compatibility in suspension and melt, it is made to be not easy to reunite.
In step（1）In, first using aluminum sulfate as presoma, unformed alumina-coated is carried out to titanium dioxide surface,
Since unformed aluminium oxide has higher specific surface area, and a large amount of hydroxyl is contained on surface, it is easier to graft reaction occur.
In step（2）In, polyethylene glycol is further coated to titanium dioxide surface, after coating polyethylene glycol, in process
The steric hindrance of titanium dioxide in a liquid can be reduced, it is more preferable with the compatibility of other organic components, it is easier to disperse.
Preferably, step（1）In, titania powder be scattered in deionized water after a concentration of 10-20wt%, sulphur
A concentration of 5-15wt% of sour aluminum solutions, a concentration of 5-20wt% of dilute sulfuric acid control unformed alumina-coated layer and titanium dioxide
The mass ratio of titanium powder is 1-5:100；In addition, initial pH is adjusted to 10-12, reaction temperature is adjusted to 60-90 DEG C, and aluminum sulfate is molten
Drop adds rear pH and is adjusted to 5-7, and the curing time is 2-4 h.
Preferably, step（2）In, the mass ratio of the powder and polyethylene glycol is 40-100:1, the addition of dispersant
Amount is the 0.5-2.5 ‰ of powder quality, and dispersant is charge modifiers.
Preferably, step（1）With（2）In, drying mode is vacuum drying, and temperature is 50-90 DEG C, and drying time is
12-24h。
It is compared with the prior art, the beneficial effects of the invention are as follows：It is handled with ultrasonic device and is contained through what centrifuge was separated
Bulky grain titanium dioxide slurries only need 5 ~ 30min, and tradition machinery milled processed at least needs 2h, treatment effeciency to improve 4 ~ 24
Times, large-scale production needs can be met.Secondly ultrasonic device processing is compared with mechanical lapping, to titanium dioxide surface clad
Destroy small, slurries coloration can more be kept, and the long rear slurry of tradition machinery milling time is black, finally influences whether polymer
Coloration.After titanium dioxide is surface-modified, dispersibility is stronger, after being mixed with monomer solution with polymerized monomer, is convenient for shape
At the slurries of more stable uniform.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Reference numeral is：Mixer 1, centrifuge 2, blend tank 3, ultrasonic processor 4.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Total embodiment：
Titania powder and polymerized monomer or its aqueous solution are mixed to form to the suspension of a concentration of 10-50wt% in a mixer
Liquid；The centrifugal treating that the suspension is passed through to centrifuge, isolates the larger titanium dioxide of grain size, by grain size qualification（Grain size
It is 1 μm or less）Suspension be delivered to blend tank, allocated to normal concentration through concentration（10~25wt%）It is spare afterwards；It will be from centrifugation
The larger suspension of grain size that machine is isolated is handled using ultrasonic processing equipment（Excusing from death frequency is 20-100KHz, when ultrasonic
Between be 5min ~ 30min）It returns in mixer and remixes afterwards, recycle according to this.
Wherein, the polymer and polymerized monomer or its aqueous solution are selected from following combination：
A, polymer is polyethylene terephthalate, and polymerized monomer is ethylene glycol；
B, polymer is polyamide, and polymerized monomer aqueous solution is the aqueous solution of amide or amidic-salt；
C, polymer is polycaprolactam, and polymerized monomer aqueous solution is caprolactam water solution；
D, polymer is polyhexamethylene adipamide, and polymerized monomer aqueous solution is the aqueous solution of adipic acid hexamethylene diamine salt；
E, polymer is polyadipate pentanediamine, and polymerized monomer aqueous solution is the aqueous solution of adipic acid pentanediamine salt.
Optionally, the titania powder is modified by surface：
（1）Titania powder is scattered in deionized water and is stirred, is heated, adjusts pH, then be slowly added dropwise into aluminum sulfate solution,
PH is adjusted with dilute sulfuric acid simultaneously, continues stirring curing after dripping, is dried after washing to neutrality, unformed alumina-coated is made
Titanium dioxide powder.Wherein, a concentration of 10-20wt% after titania powder is scattered in deionized water, aluminum sulfate solution
A concentration of 5-15wt%, a concentration of 5-20wt% of dilute sulfuric acid, control unformed alumina-coated layer and titania powder
Mass ratio is 1-5:100；In addition, initial pH is adjusted to 10-12, reaction temperature is adjusted to 60-90 DEG C, and aluminum sulfate solution drips
PH is adjusted to 5-7 afterwards, and the curing time is 2-4 h.
（2）By step（1）Powder obtained and ultrasonic disperse after water, polyethylene glycol, dispersant, after washing, drying
Obtain modifying titanium dioxide.The mass ratio of the powder and polyethylene glycol is 40-100:1, the additive amount of dispersant is powder matter
The 0.5-2.5 ‰ of amount, dispersant are charge modifiers.
Step（1）With（2）In, drying mode is vacuum drying, and temperature is 40-60 DEG C, drying time 12-24h.
Embodiment 1
As shown in Figure 1, titanium dioxide and caprolactam containing 45wt% it is water-soluble the preparation of mixer 1 containing titanium dioxide be about 12wt% or
The slurries of 22wt%, its median is 0.589 μm after testing, and after the processing of centrifuge 2, small particle titanium dioxide provides liquid and enters
Blend tank 3 send polyplant to use, titanium dioxide containing bulky grain after centrifugal treating after concentration is adjusted to 12% or 22%（Middle position
Grain size is 0. 632 μm）Slurries enter ultrasonic processor 4（Ultrasonic oscillation instrument）After being 53 KHz frequency processings 10min with frequency
Titanium dioxide grain size median is 0.537 μm, and slurries form and aspect are unchanged before and after slurries send blend tank Treatment for Reuse back to.
Embodiment 2
The aqueous solution of TITANIUM DIOXIDE DELUSTRANT powder and the adipic acid hexamethylene diamine salt containing 75wt% is mixed into the slurry of 10wt% or 20 wt %
Liquid, after centrifuge processing, small particle titanium dioxide money liquid enters smart distribution tank, is sent after concentration is adjusted to 10 wt % or 20 wt %
Polyplant uses, and titanium dioxide slurries containing bulky grain enter ultrasonic wave separating apparatus with frequency for 20KHz frequencies after centrifugal treating
Processing 15min rear slurries send preparing tank reuse back to.Titanium dioxide median is 0. to ultrasonic disperse instrument before and after the processing after testing
593 μm, 0.564 μm, slurries form and aspect are unchanged before and after the processing.
Embodiment 3
TITANIUM DIOXIDE DELUSTRANT powder is mixed into the slurries of 50wt% with hexylene glycol, after centrifuge processing, small particle titanium dioxide money
Liquid enters smart distribution tank, is adjusted to 10 wt% through concentration and polyplant is sent to use, titanium dioxide slurries containing bulky grain after centrifugal treating
Preparing tank reuse is sent back to for 20KHz frequency processing 15min rear slurries with frequency into ultrasonic wave separating apparatus.Ultrasonic disperse after testing
Instrument before and after the processing titanium dioxide median be 0. 509 μm, 0.433 μm before and after the processing slurries form and aspect it is unchanged.
Embodiment 4
TITANIUM DIOXIDE DELUSTRANT powder is mixed into the slurries of 15 wt % with the aqueous solution containing 70 wt % adipic acid pentanediamine salt, from
After scheming processing, small particle titanium dioxide money liquid enters smart distribution tank, is adjusted to 12 wt % through concentration and polyplant is sent to use, from
Titanium dioxide slurries containing bulky grain enter ultrasonic wave separating apparatus with frequency for 53KHz frequency processing 10min rear slurries after heart processing
Send preparing tank reuse back to.Titanium dioxide median is 0. 642 μm, 0.593 μm to ultrasonic disperse instrument before and after the processing after testing, place
The front and back slurries form and aspect of reason are unchanged.
Embodiment 5
Titania powder is mixed with the caprolactam water solution that mass fraction is 45wt% in mixer 1, is made 22wt%'s
Tio_2 suspension, for suspension after the separation of centrifuge 2, the titanium dioxide of grain size qualification enters blend tank 3 through essence with laggard
Enter lower process to use, the tio_2 suspension containing bulky grain isolated enters ultrasonic oscillation instrument processing 30min, through laser grain
Titanium dioxide median is respectively 0.651 μm, 0.498 μm before and after spending tester detection ultrasonication, before and after the processing slurries
Form and aspect are unchanged.
Wherein, the titania powder is modified by surface：
（1）Titania powder is scattered in deionized water and is stirred, its a concentration of 15wt% is made, is heated to 75 DEG C, adjust pH to
11, then the aluminum sulfate solution into a concentration of 10wt% is slowly added dropwise, while adjusting pH to 6, drop with the dilute sulfuric acid of a concentration of 12wt%
Continue stirring curing 3h after adding, is dried in vacuo after washing to neutrality（50 DEG C, 18h）, the two of unformed alumina-coated are made
Titanium oxide powder, the mass ratio for finally controlling unformed alumina-coated layer and titania powder is 3:100.
（2）By step（1）Ultrasonic disperse after powder obtained is mixed with water, polyethylene glycol, calgon washs, is true
Sky is dry（50 DEG C, 18h）After obtain modifying titanium dioxide.Wherein, the mass ratio of the powder and polyethylene glycol is 80:1, dispersion
The additive amount of agent is the 1.5 ‰ of powder quality.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention
Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example
The protection domain of case.
Claims (10)
1. a kind of polymer preparation method of TITANIUM DIOXIDE DELUSTRANT suspension, it is characterised in that include the following steps：
Titania powder and polymerized monomer or its aqueous solution are mixed to form suspension in a mixer；The suspension is passed through
The centrifugal treating for crossing centrifuge isolates the larger titanium dioxide of grain size, and the suspension of grain size qualification is delivered to blend tank, warp
Concentration is spare after allocating to normal concentration；The larger suspension of the grain size isolated from centrifuge is set using ultrasonication
It returns in mixer and remixes after standby processing, recycle according to this.
2. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as described in claim 1, which is characterized in that
The grain size of the suspension of the grain size qualification is 1 μm or less.
3. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as described in claim 1, which is characterized in that
A concentration of 10 ~ 50wt% of titanium dioxide in the suspension.
4. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as described in claim 1, which is characterized in that
Excusing from death frequency is 20-100KHz, and ultrasonic time is 5min ~ 30min.
5. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as described in claim 1, which is characterized in that
The normal concentration is 10 ~ 25wt%.
6. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as described in claim 1, which is characterized in that
The polymer and polymerized monomer or its aqueous solution are selected from following combination：
A, polymer is polyethylene terephthalate, and polymerized monomer is ethylene glycol；
B, polymer is polyamide, and polymerized monomer aqueous solution is the aqueous solution of amide or amidic-salt；
C, polymer is polycaprolactam, and polymerized monomer aqueous solution is caprolactam water solution；
D, polymer is polyhexamethylene adipamide, and polymerized monomer aqueous solution is the aqueous solution of adipic acid hexamethylene diamine salt；
E, polymer is polyadipate pentanediamine, and polymerized monomer aqueous solution is the aqueous solution of adipic acid pentanediamine salt.
7. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as described in claim 1, which is characterized in that
The titania powder is modified by surface：
（1）Titania powder is scattered in deionized water and is stirred, is heated, adjusts pH, then be slowly added dropwise into aluminum sulfate solution,
PH is adjusted with dilute sulfuric acid simultaneously, continues stirring curing after dripping, is dried after washing to neutrality, unformed alumina-coated is made
Titanium dioxide powder；
（2）By step（1）Powder obtained and ultrasonic disperse after water, polyethylene glycol, dispersant, obtain after washing, drying
Modifying titanium dioxide.
8. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as claimed in claim 7, which is characterized in that
Step（1）In, titania powder be scattered in deionized water after a concentration of 10-20wt%, a concentration of 5- of aluminum sulfate solution
15wt%, a concentration of 5-20wt% of dilute sulfuric acid, the mass ratio for controlling unformed alumina-coated layer and titania powder is 1-
5:100；In addition, initial pH is adjusted to 10-12, reaction temperature is adjusted to 60-90 DEG C, and aluminum sulfate solution drips rear pH and is adjusted to
5-7, curing time are 2-4 h.
9. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as claimed in claim 7, which is characterized in that
Step（2）In, the mass ratio of the powder and polyethylene glycol is 40-100:1, the additive amount of dispersant is the 0.5- of powder quality
2.5 ‰, dispersant is charge modifiers.
10. a kind of preparation method of polymer TITANIUM DIOXIDE DELUSTRANT suspension as claimed in claim 7, feature exist
In step（1）With（2）In, drying mode is vacuum drying, and temperature is 50-90 DEG C, drying time 12-24h.
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| CN109880172A (en) * | 2019-03-18 | 2019-06-14 | 湖南师范大学 | A kind of aluminate coupling agent modified titanium dioxide and its preparation method and a kind of full-dull nylon 6 polymer and its preparation method |
| CN109943892A (en) * | 2019-03-01 | 2019-06-28 | 江苏三联新材料有限公司 | A kind of super fine denier directly spins the production technology of full-dull polyester filament |
| CN115478332A (en) * | 2022-10-08 | 2022-12-16 | 广西金茂钛业有限公司 | A method for preparing liquid nano titanium dioxide matting agent |
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| CN115478332A (en) * | 2022-10-08 | 2022-12-16 | 广西金茂钛业有限公司 | A method for preparing liquid nano titanium dioxide matting agent |
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