CN114345311B - Super-hydrophobic fluorocarbon chain modified titanium dioxide and preparation method and application thereof - Google Patents
Super-hydrophobic fluorocarbon chain modified titanium dioxide and preparation method and application thereof Download PDFInfo
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- CN114345311B CN114345311B CN202111649752.7A CN202111649752A CN114345311B CN 114345311 B CN114345311 B CN 114345311B CN 202111649752 A CN202111649752 A CN 202111649752A CN 114345311 B CN114345311 B CN 114345311B
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 26
- -1 fluorocarbon chain modified titanium dioxide Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000005457 ice water Substances 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 claims description 5
- COWKRCCNQSQUGJ-UHFFFAOYSA-N 1,1,2,2,3-pentafluoropropan-1-ol Chemical compound OC(F)(F)C(F)(F)CF COWKRCCNQSQUGJ-UHFFFAOYSA-N 0.000 claims description 3
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 3
- PMWGIVRHUIAIII-UHFFFAOYSA-N 2,2-difluoropropanoic acid Chemical compound CC(F)(F)C(O)=O PMWGIVRHUIAIII-UHFFFAOYSA-N 0.000 claims description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000110 cooling liquid Substances 0.000 claims description 3
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims description 3
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical class FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 3
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 13
- 238000004334 fluoridation Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a super-hydrophobic fluorocarbon chain modified titanium dioxide and a preparation method and application thereof, wherein a titanium source compound is slowly dripped into ice water under the condition of stirring at room temperature, then a fluorine source compound is added, stirring and mixing are carried out at room temperature, stirring and reacting are carried out for 1-8h at 80-150 ℃, the reaction liquid is respectively washed by hydrofluoroether and deionized water until the chloride ion content in the washing liquid is less than 20ppm, and the obtained mixture is centrifuged, deposited and dried to obtain fluorocarbon chain modified TiO 2 And (3) nanoparticles. The invention prepares the super-hydrophobic fluorocarbon chain modified TiO 2 The step of nano particles is simple, and the product yield is high (up to more than 95 percent); prepared fluorocarbon chain modified TiO 2 The nano particles have superhydrophobicity, and have good application prospects in self-cleaning and oil-water separation, and particularly in preparation of fluorinated liquid nano fluid.
Description
Field of the art
The invention relates to the field of hydrophobic material preparation, in particular to a superhydrophobic fluorocarbon chain modified TiO 2 Nanoparticle and its preparation method and application are provided.
(II) background art
Titanium dioxide is an important multifunctional inorganic functional material, and is safe and nontoxic due to good transparency, high whiteness and high brightness, and is widely applied to various fields. However, unmodified titanium dioxide has a large specific surface area and high surface energy, shows strong polarity and hydrophilicity and oleophobicity, causes the titanium dioxide to be easily agglomerated in an organic system to generate precipitation, and seriously affects the service performance, so that the titanium dioxide needs to be modified to improve the compatibility, the dispersibility and the hydrophobicity of the titanium dioxide in a medium.
Fluorinated liquid cooling media (hydrofluorocarbon HFCs, hydrofluoroether HFEs, and perfluorinated amines and perfluoropolyethers) are considered to be desirable alternatives to cooling liquids, but have lower heat transfer coefficients. Cakmak et al studied the volume fraction and temperature vs. rGO-Fe 3 O 4 -TiO 2 The effect of the thermal conductivity of the ethylene glycol ternary mixed nanofluid is that the thermal conductivity of the ethylene glycol ternary mixed nanofluid is increased by 13.3% when the volume fraction is 0.25% and the temperature is 60 ℃ compared with that of pure ethylene glycol. The heat transfer coefficient of the nanometer fluid can be improved by adding nanometer particles into the fluoridation liquid to prepare stable and uniform nanometer fluid. However, the fluorinated solution contains a large number of C-F bonds, has a strong inertness, does not have good compatibility with inorganic nanoparticles, and, in addition, most of the TiO 2 The density of the particles is greater than that of the fluorinated liquid, so that the coagulation phenomenon easily occurs when the nanoparticles are added to the fluorinated liquid. Thus, tiO 2 The nano particles can be modified to be dispersed in the fluorinated liquid to prepare the fluorinated liquid nano fluid. The inorganic particles are well dispersed in the fluorinated solution, and besides the particle size, the particles are surface modified to achieve good compatibility with the fluorinated solution.
Patent application CN 113184902A modified TiO with stearic acid 2 Has certain hydrophobicity, but the dispersibility in the fluoridation liquid is still poor; patent application CN105602412A adopts silane coupling agent to modify TiO 2 The composition has a certain hydrophobic effect, but the dispersion in the fluoridized liquid still does not reach the ideal effect; preparation of modified TiO from self-made fluorosilicones in patent application CN 113044878A 2 The method has better superhydrophobicity, but belongs to a post-modification mode, and in addition, the preparation path of fluorosilicone is complex, so that the method is not beneficial to industrialization. Therefore, the search for simple preparation of super-hydrophobic and superfine titanium dioxide nano particles has great significance.
The titanium dioxide modified by the fluorocarbon chain has reduced surface free energy, and has good superhydrophobicity on the basis of the original fatty acid modification due to the introduction of fluorine element, so that the fluorine-containing nanometer fluid can be applied to various occasions, has good application prospects in the aspects of self-cleaning and oil-water separation, and particularly has good application prospects in the aspect of preparing fluorinated liquid nanometer fluid.
(III) summary of the invention
The invention aims to provide a superhydrophobic fluorocarbon chain modified TiO 2 Nanoparticle and preparation method and application thereof, and solves the problem of modifying TiO by most of organic matters at present 2 The super-hydrophobic effect is poor.
The technical scheme adopted by the invention is as follows:
the invention provides a super-hydrophobic fluorocarbon chain modified TiO 2 Nanoparticles, the fluorocarbon chain modified TiO 2 The nanoparticle is prepared as follows: slowly dripping a titanium source compound into ice water at room temperature (25-30 ℃) under stirring, adding a fluorine source compound, stirring and uniformly mixing at room temperature (preferably stirring for 60 min), stirring and reacting for 1-8h at 80-150 ℃, respectively washing the reaction liquid with hydrofluoroether and deionized water until the chloride ion content in the washing liquid is less than 20ppm, centrifuging, precipitating and drying to obtain the fluorocarbon chain modified TiO 2 A nanoparticle; the titanium source compound is one of titanium tetrachloride or tetrabutyl titanate; the fluorine source compound is fluorocarbonic acid (R) f -COOH), acyl fluoride (R) f -COF) or fluorocarbon alcohol (R) f -OH)Species, wherein R is f C2-C6 fluoroalkyl which is C2-C6 straight chain alkyl containing fluorine or C2-C6 fluoroalkyl containing oxygen heteroatom, specifically comprises one of 2, 2-difluoropropionic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, hexafluoropropylene oxide dimer, heptafluorobutyric acid, trifluoroethanol or pentafluoropropanol.
Preferably, the ratio of the amount of the titanium source compound to the amount of the fluorine source compound substance is 1:1-4, preferably 1:1-2; the volume ratio of the titanium source compound to the ice water is 1:1-5, preferably 1:1-3.
Preferably, the addition rate of the titanium source compound and the fluorine source compound is 2 to 7 s/drop, preferably 4 to 6 s/drop.
Preferably, the stirring speeds are each 400 to 700r/min, more preferably 500 to 600r/min.
Preferably, the hydrofluoroether is one of HFE-347, HFE-6512, HFE-449 or HFE-458.
Preferably, the reaction is carried out at 90-130℃for 3-6h.
Preferably, the centrifugal rotational speed is 4000 to 7000r/min, more preferably 5000 to 6000r/min.
Preferably, the drying is at 60-180deg.C for 10-24h, more preferably at 80-150deg.C for 12-20h.
The super-hydrophobic fluorocarbon chain modified TiO prepared by the method of the invention 2 The particle size of the nano particles is 10-20nm, and the nano particles can be used for self-cleaning and oil-water separation, and especially can be applied to nano fluid.
The invention also provides the fluorocarbon chain modified TiO 2 Application of nano particles in preparation of fluorine-containing coolant additive, wherein the application refers to fluorocarbon chain modified TiO 2 The nano particles are added into the fluorine-containing cooling liquid in the mass concentration of 0.1-0.5% for improving the heat transfer performance of the fluorine-containing cooling liquid.
Compared with the prior art, the method has the beneficial effects that: the invention prepares the super-hydrophobic fluorocarbon chain modified TiO 2 The step of nano particles is simple, and the product yield is high (up to more than 95 percent); prepared fluorocarbon chain modified TiO 2 The nanometer particles (5-20 nm) have super-hydrophobicity, and are self-cleaning and oil-water separationThe method has good application prospect in separation, in particular to the preparation of fluorinated liquid nano-fluid.
(IV) description of the drawings
FIG. 1 is a modified TiO prepared in example 1 2 Is a FT-IR spectrum of (2).
FIG. 2 is a fluorocarbon chain modified TiO prepared in example 1 2 Is a XRD pattern of (C).
FIG. 3 is a fluorocarbon chain modified TiO prepared in example 1 2 A resolution of 100nm, b resolution of 20nm, both a and b scanning sites being identical; c. d has a resolution of 20nm, and the two scanning sites are different.
FIG. 4 is a fluorocarbon chain modified TiO prepared in example 1 2 Contact angle test of (2).
FIG. 5 is a fluorocarbon chain modified TiO prepared in example 1 2 A is a dispersion diagram of fluorocarbon chain modified TiO prepared in example 1 in a fluorinated solution 2 Dispersion in fluorinated liquid, b is unmodified TiO 2 Dispersion pattern in fluorinated liquid.
(fifth) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto: the room temperature is 25-30 ℃.
Example 1
1. Fluorocarbon chain modified TiO 2 Nanoparticles
10ml of titanium tetrachloride and 30ml of ice water were taken out by a measuring cylinder. Dropwise adding 10ml (0.09 mol) of titanium tetrachloride into 30ml of ice water at a speed of 2 s/drop in a beaker under the stirring condition of room temperature and a rotating speed of 700r/min, dropwise adding 28.5g (0.09 mol) of hexafluoropropylene oxide dimer at a speed of 2 s/drop, stirring for 60min at 700r/min, transferring the reaction solution into a stainless steel reaction kettle, heating to 100 ℃ for reaction for 3h, taking out, washing with hydrofluoroether HFE-347 (1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether) and deionized water for 5 times respectively to remove chloride ions on the surface, measuring the concentration of the chloride ions in the washing solution to be 15ppm by a chloride ion content measuring instrument (model TDCL-225, manufactured by the company of the first and development of technology, beijing) and centrifuging at a rotating speed of 7000r/min, and drying the obtained solid at 120 DEG CDrying for 18h, grinding for 30min by an agate mortar to obtain white fluorocarbon chain modified TiO 2 32.7g of nanoparticle powder with a mass yield of 95.8%.
2. Structural identification
(1) And (3) infrared spectrum detection: detecting the fluorocarbon chain modified TiO prepared in the step 1 by using an infrared spectrometer (ARL iSpark 8860, siemens) 2 The molecular structure and elemental composition of the nanoparticle powder sample are shown in FIG. 1, and FIG. 1 shows that fluorocarbon groups have been successfully grafted to TiO 2 And (3) upper part.
(2) X-ray diffraction detection: adopting an X-ray diffractometer (XRD-6100, shimadzu) to prepare the fluorocarbon chain modified TiO in the step 1 2 XRD testing was performed on the powder nanoparticle samples, and the results are shown in FIG. 2. FIG. 2 shows modified TiO 2 The crystal form is anatase, and is consistent with the standard card JCPDS-21-1272.
(3) Scanning electron microscope detection: using scanning electron microscopy (SEM, SUPRA) TM 55, chuiss Germany) to the fluorocarbon chain modified TiO prepared in step 1 2 The nanoparticle powder samples were tested and the results are shown in figure 3. FIG. 3 shows TiO 2 The microstructure of the polymer is a nano lamellar structure, the grain diameter is smaller, and the grain diameter is between 10 and 20 nm.
(4) Contact angle test: adopting a contact angle tester (JY-PHA, manufactured by the Bode test detection instrument Co., ltd.) to prepare the fluorocarbon chain modified TiO in the step 1 2 The nanoparticle powder sample is tested, the contact angle test angle is 156.3 degrees, the result is shown in figure 4, and the result shows that the fluorocarbon chain modified TiO 2 The nanoparticle powder has good superhydrophobicity.
3. Fluorocarbon chain modified TiO 2 Dispersibility in fluorinated liquids
0.01g of the fluorocarbon chain modified TiO prepared in the step 1 is respectively treated 2 Nanoparticle powder and unmodified TiO 2 Powder, 10g of hexafluoropropylene trimer (purity 99%, available from North America, zhejiang) was added (fluorocarbon chain modified TiO) 2 The dispersion mass concentration is 0.1 percent), after ultrasonic dispersion is carried out for 1h at 40kHz, the dispersion is kept at room temperature for 0, 5, 10 and 15d, the results are shown in table 1, and a graph of the dispersion for 30min is shown in fig. 5.
FIG. 5 shows that with unmodified TiO 2 In contrast, fluorocarbon chain modified TiO 2 Has better dispersibility and stability in fluoridation liquid.
TABLE 1 TiO 2 Stabilization in fluorinated liquids
| Standing time/d | EXAMPLE 1 preparation of fluorocarbon chain modified TiO 2 | Unmodified TiO 2 |
| 0 | Good stability | Poor stability, and the bottom is concentrated |
| 5 | Good stability | Poor stability, and the bottom is concentrated |
| 10 | Good stability | Poor stability, and the bottom is concentrated |
| 15 | Good stability | Poor stability, and the bottom is concentrated |
The dispersibility test results in Table 1 and FIG. 5 show that the dispersibility of fluorocarbon chain modified titanium dioxide in fluorinated liquid is significantly better than that of unmodified titanium dioxide.
Example 2
3ml of tetrabutyl titanate and 3ml of ice water were taken out with a measuring cylinder. 3ml (0.009 mol) of tetrabutyl titanate is dripped into 10ml of ice water at a speed of 3 s/drop in a beaker under the stirring condition of room temperature and a rotating speed of 500r/min, 3.5g (0.036 mol) of difluoroacetic acid is dripped into the beaker at a speed of 3 s/drop, the reaction solution is transferred into a stainless steel reaction kettle after stirring for 60min at 500r/min, the temperature is raised to 150 ℃ for 2h, after being taken out, the mixture is washed for 5 times by using hydrofluoroether HFE-6512 (1H, 5H-octafluoropentyl-1, 2-tetrafluoroethyl ether) and deionized water respectively, the concentration of chloride ions is measured to be 16ppm by a chloride ion content tester, the obtained solid is centrifuged at a rotating speed of 5000r/min, dried for 24h at 80 ℃, and ground for 30min by using an agate mortar to obtain 1.4g of white fluorocarbon chain modified TiO 2 The mass yield of the nanoparticle powder is 95.6%.
The structure identification is carried out by adopting the method of the embodiment 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the contact angle is tested to be 150.2 degrees, and the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and in the case of a dispersion mass concentration of 0.2%, after standing for 10d, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Example 3
10ml of titanium tetrachloride and 20ml of ice water were taken out by a measuring cylinder. Dropwise adding 10ml (0.09 mol) of titanium tetrachloride into 25ml of ice water at a speed of 4 s/drop in a beaker under stirring at a speed of 600r/min at room temperature, adding 17.3g (0.18 mol) of 2, 2-difluoropropionic acid at a speed of 4 s/drop, stirring at 600r/min for 60min, transferring the reaction solution into a stainless steel reaction kettle, heating to 80 ℃ for reaction for 8h, taking out, washing with hydrofluoroether HFE-6512 and deionized water for 6 times to remove impurities on the surface, measuring the concentration of chloride ions to be 12ppm by a chloride ion content tester, centrifuging at a speed of 7000r/min by a centrifuge, drying the obtained solid at 150 ℃ for 20h, and grinding by agateBowl milling for 30min to obtain 15.7g white fluorocarbon chain modified TiO 2 The mass yield of the nanoparticle powder is 96.6%.
The structure identification is carried out by adopting the method of the embodiment 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the average particle size is between 10 and 20nm, and the contact angle test hydrophobic angle is 151.2 degrees, which shows that the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and at a dispersion mass concentration of 0.1%, after standing for 10d, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Example 4
12ml of tetrabutyl titanate and 20ml of ice water were taken out with a measuring cylinder. Under the stirring condition of room temperature and 700r/min, 12ml (0.035 mol) of tetrabutyl titanate is dripped into 20ml of ice water at the speed of 5 s/drop, 17.9g (0.11 mol) of pentafluoropropionic acid is dripped into the beaker at the speed of 5 s/drop, after the stirring of 700r/min for 60min, the reaction solution is transferred into a stainless steel reaction kettle to be heated to 90 ℃ for reaction for 1H, after being taken out, the mixture is respectively washed by hydrofluoroether HFE-449 (C5H 3F 9O) and deionized water for 3 times to remove impurities on the surface, after the chloride ion concentration is measured to be 18ppm by a chloride ion content tester, the obtained solid is centrifuged by a centrifuge at the speed of 7000r/min, and is dried for 12H at the temperature of 180 ℃ and ground by an agate mortar for 30min, so as to obtain 7.7g white fluorocarbon chain modified TiO 2 The mass yield of the nanoparticle powder is 96.8%.
The structure identification is carried out by adopting the method of the embodiment 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the contact angle test hydrophobic angle is 153.2 degrees between 15nm and 20nm, and the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and at a dispersion mass concentration of 0.2%, after standing for 13d, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Example 5
12ml of titanium tetrachloride and 20ml of ice water were taken out by a measuring cylinder. Dropwise adding 12ml (0.046 mol) of titanium tetrachloride into 20ml of ice water at a speed of 5 s/drop in a beaker under the stirring condition of room temperature and a rotating speed of 600r/min, dropwise adding 10.2g (0.048 mol) of heptafluorobutyric acid at a speed of 5 s/drop, stirring for 60min at 600r/min, transferring the reaction solution into a stainless steel reaction kettle, heating to 130 ℃ for reaction for 8h, taking out, respectively washing with hydrofluoroether HFE-458 (1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether) and deionized water for 5 times to remove impurities on the surface, centrifuging at a rotating speed of 7000r/min by a centrifuge after the chloride ion concentration is measured to be 14ppm, drying the obtained solid at 120 ℃ for 20h, grinding for 30min by an agate mortar to obtain 12.3g of white fluorine modified TiO 2 The mass yield of the nanoparticle powder is 96.2%.
The structure identification is carried out by adopting the method of the example 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the contact angle is tested to be 155.4 degrees, and the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and at a dispersion mass concentration of 0.1%, after standing for 15d, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Example 6
5ml of tetrabutyl titanate and 25ml of ice water were taken out by a measuring cylinder. 5ml (0.015 mol) of tetrabutyl titanate is dripped into 25ml of ice water at a speed of 7 s/drop in a beaker under stirring condition at a speed of 400r/min at room temperature, 5.1g (0.045 mol) of trifluoroacetic acid is dripped at a speed of 7 s/drop, after stirring for 60min at 400r/min, the reaction solution is transferred into a stainless steel reaction kettle to be heated to 150 ℃ for reaction for 6h, after being taken out, the mixture is washed with hydrofluoroether HFE-347 (1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether) and deionized water for 4 times respectively to remove impurities on the surface, after the concentration of the chloride ions is measured to be 12ppm by a chloride ion content tester, the obtained solid is dried for 12h at a speed of 4000r/min by a centrifuge, and is ground for 30min by an agate mortar to obtain 7.6g white fluorocarbon chain modified TiO 2 The mass yield of the nanoparticle powder is 95.2%.
The structure identification is carried out by adopting the method of the embodiment 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the contact angle is 152.3 degrees when the contact angle is tested, and the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and at a dispersion mass concentration of 0.5%, after standing for 13d, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Example 7
10ml of titanium tetrachloride and 30ml of ice water were taken out by a measuring cylinder. Dropwise adding 10ml (0.09 mol) of titanium tetrachloride into 30ml of ice water at a speed of 5 s/drop in a beaker under the stirring condition of room temperature and a rotating speed of 700r/min, dropwise adding 10.2g (0.10 mol) of trifluoroethanol at a speed of 5 s/drop, stirring for 60min at the speed of 700r/min, transferring the reaction solution into a stainless steel reaction kettle, heating to 100 ℃ for reaction for 3h, taking out, washing with hydrofluoroether HFE-458 (1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether) and deionized water for 4 times respectively to remove impurities on the surface, centrifuging at a rotating speed of 7000r/min by a centrifuge after the chloride ion concentration is measured to be 10ppm, grinding the obtained solid with an agate mortar for 30min at the temperature of 120 ℃ to obtain 14.1g of white fluorocarbon chain modified TiO 2 The mass yield of the nanoparticle powder is 95.8%.
The structure identification is carried out by adopting the method of the embodiment 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the contact angle is 152.3 degrees when the contact angle is tested, and the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and at a dispersion mass concentration of 0.4%, after 12d of standing, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Example 8
10ml of titanium tetrachloride and 40ml of ice water were taken out by a measuring cylinder. Adding 10ml (0.09 mol) of titanium tetrachloride into 30ml of ice water at a speed of 6 s/drop in a beaker under stirring at a speed of 600r/min at room temperature, dropwise adding 18.1g (0.12 mol) of pentafluoropropanol at a speed of 6 s/drop in a beaker, stirring at a speed of 600r/min for 60min, transferring the reaction solution into a stainless steel reaction kettle, heating to 110 ℃ for reaction for 4h, taking out, washing with hydrofluoroether HFE-347 and deionized water for 5 times respectively to remove impurities on the surface, measuring the chloride ion concentration to be 12ppm by a chloride ion content tester, centrifuging at a speed of 7000r/min, drying the obtained solid at 130 ℃ for 20h, grinding for 30min by an agate mortar to obtain 18.2g white fluorocarbon chain modified TiO 2 The mass yield of the nanoparticle powder is 95.1%.
The structure identification is carried out by adopting the method of the example 1, the fluorocarbon chain is successfully grafted on the titanium dioxide, the particle size is smaller, the average particle size is 10-15nm, and the contact angle test hydrophobic angle is 152.2 degrees, which shows that the fluorocarbon chain has a super-hydrophobic structure. The dispersibility was examined by the method of example 1, and at a dispersion mass concentration of 0.2%, after standing for 13d, the fluorocarbon chain-modified titanium dioxide was excellent in dispersibility in the fluorinated liquid, while the unmodified titanium dioxide was largely precipitated in the fluorinated liquid. The results show that the dispersibility of the fluorocarbon chain modified titanium dioxide in the fluoridation liquid is obviously better than that of the unmodified titanium dioxide.
Claims (10)
1. Super-hydrophobic fluorocarbon chain modified TiO 2 Nanoparticles characterized in that the fluorocarbon chain modified TiO 2 The nanoparticle is prepared as follows: slowly dripping a titanium source compound into ice water at room temperature under stirring, adding a fluorine source compound, stirring and uniformly mixing at room temperature, stirring and reacting for 1-8h at 80-150 ℃, respectively washing the reaction liquid with hydrofluoroether and deionized water until the chloride ion content in the washing liquid is less than 20ppm, centrifuging, precipitating and drying to obtain fluorocarbon chain modified TiO 2 A nanoparticle; the titanium source compound is one of titanium tetrachloride or tetrabutyl titanate; the fluorine source compound is fluorocarbonic acid, acyl fluoride compound or fluorocarbon alcohol.
2. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 The nanoparticle is characterized in that the fluorine source compound is one of 2, 2-difluoropropionic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, hexafluoropropylene oxide dimer, heptafluorobutyric acid, trifluoroethanol or pentafluoropropanol.
3. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 Nanoparticle characterized in that the ratio of the amounts of titanium source compound to fluorine source compound species is 1:1-4; the volume ratio of the titanium source compound to the ice water is 1:1-5.
4. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 The nanoparticle is characterized in that the adding speed of the titanium source compound and the fluorine source compound is 2-7 s/drop.
5. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 The nano particles are characterized in that the stirring speed is 400-700 r/min.
6. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 Nanoparticle characterized in that the hydrofluoroether is one of HFE-347, HFE-6512, HFE-449 or HFE-458.
7. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 Nanoparticle, characterized in that the reaction is carried out at 90-130 ℃ for 3-6h.
8. The superhydrophobic fluorocarbon chain modified TiO of claim 1 2 Nanoparticle, characterized in that the drying is at 60-180 ℃ for 10-24h.
9. A fluorocarbon chain modified TiO as defined in claim 1 2 Use of nanoparticles for the preparation of a fluorine-containing coolant additive.
10. Use according to claim 9, characterized in that it is a fluorocarbon chain modified TiO 2 The nano particles are added into the fluorine-containing cooling liquid in the mass concentration of 0.1-0.5%.
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