CN115678425A - Nano antifouling fiber coating and preparation method thereof - Google Patents
Nano antifouling fiber coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 34
- 239000000835 fiber Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012767 functional filler Substances 0.000 claims abstract description 32
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 150000004812 organic fluorine compounds Chemical class 0.000 claims abstract description 5
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 46
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003973 paint Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
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- 239000000047 product Substances 0.000 claims description 13
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- 230000001105 regulatory effect Effects 0.000 claims description 11
- 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
- 230000001276 controlling effect Effects 0.000 claims description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
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- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 244000063299 Bacillus subtilis Species 0.000 description 2
- 235000014469 Bacillus subtilis Nutrition 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of high polymer coatings, and particularly relates to a nano antifouling fiber coating and a preparation method thereof. The product developed by the invention comprises a low surface energy coating and a functional filler; the functional filler is nano titanium dioxide and carbon nano tubes; wherein, the low surface energy coating is selected from any one of organosilicon waterproof coating or organofluorine waterproof coating; the nano titanium dioxide is adsorbed on the surface of the carbon nano tube, the nano titanium dioxide is monodisperse nano titanium dioxide, the particle size distribution range of the nano titanium dioxide is 5-10nm, and at least part of the nano titanium dioxide is anatase type titanium dioxide. In addition, the surface of the carbon nano tube is doped with a hetero element selected from nitrogen; the mass ratio of the low surface energy coating to the functional filler is 8:1-10:1; the carbon nano tube is in a shrinkage and curling state, and the ratio of the length of the carbon nano tube after being stretched and straightened to the length of the carbon nano tube in the shrinkage state is 1.5:1-1.8:1.
Description
Technical Field
The invention belongs to the technical field of high polymer coatings. More particularly, relates to a nano antifouling fiber coating and a preparation method thereof.
Background
Release antifouling coatings have long been releasing various toxic and harmful substances into the environment, inevitably causing further environmental problems. To a certain extent, it is likely to affect the ecological environment, in particular, the current major antifouling agents such as cuprous oxide.
With the development of the technology, the antifouling paint with single function can not meet the market demand, so that the novel paint organically combined with various effective defense technologies, such as conductive antifouling, low surface energy, bionic structure and the like, can achieve the antifouling aim of high efficiency, no toxicity and energy conservation. But the antifouling technology of the conductive and structural bionic antifouling paint is difficult to break through in a short time, so that the antifouling paint with low surface energy is widely demanded in the market at present.
The low surface energy antifouling paint is based on the physical action of the surface, and the antifouling action is realized as long as the surface keeps the low surface energy state. And does not release toxic substances, and is environment-friendly, safe and nontoxic. Therefore, the researchers concerned and studied the low surface energy antifouling paint, so far, two main categories of organosilicon and organofluorine are mainly included in the reports on the low surface energy antifouling paint at home and abroad.
However, in the practical application process, the inventor finds that the surface energy of the antifouling paint is continuously increased along with the use of the paint, and finally antifouling failure is caused, so how to effectively prolong the service life of the resin type low surface energy paint of organosilicon and organofluorine is one of the core technical problems limiting the wide application of the paint.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings that the surface energy of the existing antifouling paint is continuously increased in the actual use process, and finally the antifouling function is invalid, and provides a nano antifouling fiber paint and a preparation method thereof.
The invention aims to provide a nano antifouling fiber coating.
The invention also aims to provide a preparation method of the nano antifouling fiber coating.
The above purpose of the invention is realized by the following technical scheme:
a nano antifouling fiber coating comprises a low surface energy coating and a functional filler;
the functional filler is nano titanium dioxide and carbon nano tubes;
wherein, the low surface energy coating is selected from any one of organosilicon waterproof coating or organofluorine waterproof coating;
the nano titanium dioxide is adsorbed on the surface of the carbon nano tube, the nano titanium dioxide is monodisperse nano titanium dioxide, the particle size distribution range of the nano titanium dioxide is 5-10nm, and at least part of the nano titanium dioxide is anatase type titanium dioxide.
The inventor finds in the process of practical research that in the process of practical use, although the organosilicon or organic fluororesin coating has low surface energy and ordinary pollutants are difficult to attach to the surface of the coating, microorganisms are easy to attach to the surface of the coating with the help of secretions of the microorganisms along with the prolonging of the use time, an attachment layer directly generated by the attachment of the microorganisms directly changes the surface energy of the antifouling coating along with the increase of the attachment amount of the microorganisms, so that other pollutants are easy to attach, and in addition, the microorganisms continuously grow and influence the structure of the coating to a certain extent, even if the microorganisms are subsequently cleaned and removed, the surface energy of the coating is changed, so that the antifouling performance is reduced;
according to the technical scheme, the functional filler is introduced into the low-surface-energy resin system, specifically, the nano titanium dioxide is adsorbed and fixed on the surface of the carbon nano tube, wherein under the action of the carbon nano tube, the nano titanium dioxide can absorb photons and introduce electrons into a titanium dioxide conduction band, so that the coating system utilizes the photons with the wavelength in a wider range and effectively resists the attachment of microorganisms on the surface of the coating in time;
in addition, the particle size distribution range of the nano titanium dioxide is controlled to enable the particle size distribution area to be concentrated in the range of 5-10nm, so that the nano titanium dioxide with consistent particle size distribution can more easily invade into a cured resin network structure of a high polymer resin system, the functional filler can be effectively fixed by resin, and local antibacterial failure caused by uneven distribution of the functional filler in a paint film due to the fact that a large amount of functional filler is agglomerated is avoided.
Further, the surface of the carbon nano tube is doped with a hetero element, and the hetero element is selected from nitrogen.
According to the technical scheme, the surface of the carbon nano tube is doped with the nitrogen element, so that part of the nitrogen element occupies the position of part of the original element on the surface of the carbon nano tube, the carbon nano tube can assist titanium dioxide to be excited in a visible light region, and the catalytic effect of the titanium dioxide is improved.
Further, in the nano antifouling fiber coating, the mass ratio of the low surface energy coating to the functional filler is 8:1-10:1.
further, the carbon nanotube is in a contracted and curled state, and the ratio of the length of the carbon nanotube after being stretched and straightened to the length of the carbon nanotube in the contracted state is 1.5:1-1.8:1.
the technical scheme further selects the carbon nano tube in the shrinkage and curling state, so that the carbon nano tube can strengthen the reflection or refraction of light at different angles, thereby strengthening the catalytic effect, and is easy to form winding with a molecular chain of resin in the curling state, thereby avoiding the sedimentation or agglomeration in the storage or use process, and ensuring that the functional filler can be stably and uniformly dispersed in a coating system.
A preparation method of a nano antifouling fiber coating comprises the following specific preparation steps:
preparing a functional filler:
dispersing carbon nano tubes in ethanol, adding citric acid and tetrabutyl titanate, carrying out heating reflux reaction, and regulating and controlling the technological parameters of the heating reflux reaction as follows: the reaction temperature is 82-88 ℃, and the reaction time is 45-60min;
after the reflux reaction is finished, filtering and washing, calcining the obtained filter cake at 550-600 ℃ in an inert atmosphere to obtain the functional filler;
preparation of the coating:
and (3) uniformly mixing and dispersing the low-surface-energy coating and the functional filler to obtain the product.
Further, the carbon nano tube is a pretreated carbon nano tube;
the preparation method of the pretreated carbon nanotube comprises the following steps:
dispersing the carbon nano tube in a dopamine solution, stirring for reaction, and filtering to obtain the pretreated carbon nano tube.
The method comprises the steps of pretreating by utilizing dopamine to enable the surfaces of the carbon nanotubes to adsorb a layer of dopamine, wherein in the process of reflux reaction, a titanium dioxide precursor generated by hydrolysis can be effectively adsorbed and fixed under the assistance of the dopamine, and in the process of high-temperature calcination, the stress generated by heating of a part which does not adsorb the titanium dioxide precursor is different from the stress generated by heating of a part which adsorbs the titanium dioxide precursor, so that the fibrous titanium nanotubes are shrunk and curled.
Further, the carbon nanotubes are selected from single-walled carbon nanotubes, and nitrogen doping is performed on the single-walled carbon nanotubes before the pretreatment, wherein the nitrogen doping comprises:
and (3) performing heat treatment on the single-walled carbon nanotube by adopting boron oxide steam and nitrogen at the temperature of 1350-1400 ℃ to obtain the nitrogen-doped single-walled carbon nanotube.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the invention in any manner. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Doping of single-walled carbon nanotubes:
transferring the single-walled carbon nanotube into a carbonization furnace, introducing mixed steam into the carbonization furnace at the speed of 10mL/min, wherein the mixed steam is formed by mixing boron oxide steam and nitrogen, carrying out high-temperature heat treatment at 1350 ℃ for 3h, cooling to room temperature along with the furnace, and discharging to obtain the nitrogen-doped single-walled carbon nanotube;
pretreating the doped single-walled carbon nanotubes:
introducing the single-walled carbon nanotube doped with nitrogen into a dopamine solution with the mass concentration of 3g/L, wherein the mass ratio of the single-walled carbon nanotube to the dopamine solution is 1:10, stirring and reacting for 20min under the condition that the stirring speed is 300r/min, filtering, and collecting filter cakes to obtain the pretreated single-walled carbon nanotube;
preparing functional filler:
taking 10 parts of pretreated single-walled carbon nanotube, 150 parts of ethanol, 8 parts of citric acid and 10 parts of tetrabutyl titanate in sequence according to parts by weight, mixing the pretreated single-walled carbon nanotube with the ethanol, ultrasonically dispersing for 20min under the condition that the ultrasonic frequency is 60kHz, then adding the citric acid and the tetrabutyl titanate, then transferring the materials into a reaction kettle with a reflux condenser, heating and refluxing for 45min under the condition that the temperature is 82 ℃, filtering, collecting a filter cake, washing the obtained filter cake with deionized water for 3 times, then transferring the washed filter cake into an oven, and drying to constant weight under the condition that the temperature is 100 ℃;
regulating the temperature and time of reflux reaction to regulate the particle size distribution range of the nano titanium dioxide produced by hydrolysis to 6-8nm;
transferring the obtained dry filter cake into a tubular furnace, calcining for 2 hours at 550 ℃ under the condition of nitrogen atmosphere, and regulating and controlling the length ratio of the stretched and straightened length of the carbon nano tube to the length of the contracted state to be 1.5 by regulating and controlling the calcining temperature and the calcining time: 1, cooling to room temperature along with a furnace to obtain a functional filler;
preparing a coating:
the method comprises the steps of selecting RJ-WP03E type organosilicon waterproof emulsion produced by Hangzhou Ruijiang new material technology Limited company as a low-surface-energy coating, and mixing the coating with a functional filler according to a mass ratio of 8:1, stirring and mixing for 2 hours by a stirrer at the rotating speed of 600r/min to obtain a coating product.
Example 2
Doping of single-walled carbon nanotubes:
transferring the single-walled carbon nanotube into a carbonization furnace, introducing mixed steam into the carbonization furnace at the speed of 20mL/min, wherein the mixed steam is formed by mixing boron oxide steam and nitrogen, carrying out high-temperature heat treatment at the temperature of 1380 ℃ for 4 hours, cooling the single-walled carbon nanotube to room temperature along with the furnace, and discharging to obtain the nitrogen-doped single-walled carbon nanotube;
pretreating the doped single-walled carbon nanotube:
introducing the single-walled carbon nanotube doped with nitrogen into a dopamine solution with the mass concentration of 4g/L, wherein the mass ratio of the single-walled carbon nanotube to the dopamine solution is 1:11, stirring and reacting for 30min under the condition that the stirring speed is 400r/min, filtering, and collecting filter cakes to obtain the pretreated single-walled carbon nanotube;
preparing a functional filler:
taking 12 parts of pretreated single-walled carbon nanotube, 180 parts of ethanol, 9 parts of citric acid and 12 parts of tetrabutyl titanate in sequence according to parts by weight, mixing the pretreated single-walled carbon nanotube with the ethanol, ultrasonically dispersing for 25min under the condition that the ultrasonic frequency is 65kHz, then adding the citric acid and the tetrabutyl titanate, then transferring the materials into a reaction kettle with a reflux condenser, heating and refluxing for 50min under the condition that the temperature is 86 ℃, filtering, collecting a filter cake, washing the obtained filter cake with deionized water for 4 times, then transferring the washed filter cake into an oven, and drying to constant weight under the condition that the temperature is 105 ℃;
regulating the temperature and time of the reflux reaction to regulate the particle size distribution range of the nano titanium dioxide produced by hydrolysis to be 6-9nm;
transferring the obtained dry filter cake into a tubular furnace, calcining for 3 hours at 580 ℃ under the condition of nitrogen atmosphere, and regulating and controlling the length ratio of the stretched and straightened length of the carbon nano tube to the length of the contracted state to be 1.6 by regulating and controlling the calcining temperature and the calcining time: 1, cooling to room temperature along with a furnace to obtain a functional filler;
preparing a coating:
the method comprises the steps of selecting RJ-WP03E type organosilicon waterproof emulsion produced by Hangzhou Ruijiang new material technology Limited company as a low-surface-energy coating, and mixing the coating with a functional filler according to a mass ratio of 9:1, stirring and mixing for 3 hours by a stirrer at the rotating speed of 700r/min to obtain a coating product.
Example 3
Doping of single-walled carbon nanotubes:
transferring the single-walled carbon nanotube into a carbonization furnace, introducing mixed steam into the carbonization furnace at the speed of 30mL/min, wherein the mixed steam is formed by mixing boron oxide steam and nitrogen, carrying out high-temperature heat treatment at the temperature of 1400 ℃ for 5 hours, cooling the single-walled carbon nanotube to room temperature along with the furnace, and discharging to obtain the nitrogen-doped single-walled carbon nanotube;
pretreating the doped single-walled carbon nanotube:
introducing the single-walled carbon nanotube doped with nitrogen into a dopamine solution with the mass concentration of 5g/L, wherein the mass ratio of the single-walled carbon nanotube to the dopamine solution is 1:12, stirring and reacting for 40min under the condition that the stirring speed is 500r/min, filtering, and collecting filter cakes to obtain the pretreated single-walled carbon nanotube;
preparing functional filler:
taking 15 parts of pretreated single-walled carbon nanotube, 200 parts of ethanol, 10 parts of citric acid and 15 parts of tetrabutyl titanate in sequence according to parts by weight, mixing the pretreated single-walled carbon nanotube with the ethanol, ultrasonically dispersing for 30min under the condition that the ultrasonic frequency is 70kHz, then adding the citric acid and the tetrabutyl titanate, then transferring the materials into a reaction kettle with a reflux condenser, heating and refluxing for reaction for 60min under the condition that the temperature is 88 ℃, filtering, collecting a filter cake, washing the obtained filter cake with deionized water for 5 times, then transferring the washed filter cake into an oven, and drying to constant weight under the condition that the temperature is 110 ℃;
regulating the temperature and time of reflux reaction to regulate the particle size distribution range of the nano titanium dioxide produced by hydrolysis to be 5-10nm;
transferring the obtained dry filter cake into a tubular furnace, calcining for 2-4h at 600 ℃ under the condition of nitrogen atmosphere, and regulating the length ratio of the stretched and straightened length of the carbon nano tube to the contracted length of the carbon nano tube to be 1.5 by regulating and controlling the calcining temperature and the calcining time: 1-1.8:1, cooling to room temperature along with a furnace to obtain a functional filler;
preparing a coating:
the method selects RJ-WP03E type organosilicon waterproof emulsion produced by Hangzhou Ruijiang new material technology Limited company as a low surface energy coating, and the coating and a functional filler are mixed according to the mass ratio of 10:1, stirring and mixing for 4 hours by a stirrer at the rotating speed of 800r/min to obtain a coating product.
Example 4
This example differs from example 1 in that:
the single-walled carbon nanotube is not doped with nitrogen element, and the rest conditions are kept unchanged.
Example 5
This example differs from example 1 in that:
and replacing the dopamine solution with deionized water with equal mass, and keeping the rest conditions unchanged.
Comparative example 1
Doping of single-walled carbon nanotubes:
transferring the single-walled carbon nanotube into a carbonization furnace, introducing mixed steam into the carbonization furnace at the speed of 10mL/min, wherein the mixed steam is formed by mixing boron oxide steam and nitrogen, carrying out high-temperature heat treatment at 1350 ℃ for 3h, cooling to room temperature along with the furnace, and discharging to obtain the nitrogen-doped single-walled carbon nanotube;
pretreating the doped single-walled carbon nanotubes:
introducing the nitrogen-doped single-walled carbon nanotube into a dopamine solution with the mass concentration of 3g/L, wherein the mass ratio of the single-walled carbon nanotube to the dopamine solution is 1:10, stirring and reacting for 20min under the condition that the stirring speed is 300r/min, filtering, and collecting filter cakes to obtain the pretreated single-walled carbon nanotube;
preparing functional filler:
sequentially taking 10 parts by weight of pretreated single-walled carbon nanotube and 5 parts by weight of anatase type nano titanium dioxide, and stirring and mixing for 10min at the rotating speed of 200r/min by using a stirrer to obtain a functional filler;
preparing a coating:
the method comprises the steps of selecting RJ-WP03E type organosilicon waterproof emulsion produced by Hangzhou Ruijiang new material technology Limited company as a low-surface-energy coating, and mixing the coating with a functional filler according to a mass ratio of 8:1, stirring and mixing for 2 hours by a stirrer at the rotating speed of 600r/min to obtain a coating product.
The products obtained in examples 1 to 5 and comparative example 1 were subjected to performance tests, and the specific test methods and test results were as follows:
taking a Q235B steel plate with the thickness of 3mm, the length of 10cm and the width of 8cm as a base material, after oil removal, respectively coating the coating products obtained in the examples or the comparative examples on two sides, controlling the density of the coated surface to be 180 g/square meter, and after coating is finished, fully drying to respectively obtain the steel plates coated with the coatings of different examples or comparative examples;
placing the steel plate coated with the coating into a beef extract peptone culture medium, inoculating bacillus subtilis into each culture medium according to the inoculation amount of 0.3%, and after the inoculation is finished, placing the culture medium in a constant-temperature constant-humidity environment at the temperature of 35 DEG CCulturing for 10 days under the conditions of relative humidity of 75% and indoor illumination intensity of 200Lx, taking out the steel plate from the culture medium, and using tap water at a flow rate of 3m 3 The flow rate is/h, the steel plate is flushed through a pipeline with the pipe diameter of 10 square centimeters, after flushing is finished, the colony attachment areas S1 on the surfaces of different steel plates are counted, and specific test results are shown in table 1;
fully brushing and cleaning the steel plates corresponding to the products of each example or comparative example by using a brush to remove residual bacteria, putting the steel plates into a beef extract peptone culture medium again, inoculating bacillus subtilis into each culture medium according to the inoculation amount of 0.3%, after the inoculation is finished, putting the culture medium into a constant-temperature constant-humidity environment, continuously culturing for 10 days again under the conditions that the temperature is 35 ℃, the relative humidity is 75% and the indoor illumination intensity is 200Lx, taking out the steel plates in the culture medium, and using tap water to make the flow rate be 3m 3 The flow rate is/h, the steel plate is flushed through a pipeline with the pipe diameter of 10 square centimeters, after flushing is finished, the colony attachment areas S2 on the surfaces of different steel plates are counted, and specific test results are shown in table 1;
table 1: product performance test results
As shown in the test results in Table 1, the product obtained by the invention can effectively resist the attachment of microorganisms, and after being cleaned, the surface property of the product is stable, and the product can still maintain a considerable resistance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The nano antifouling fiber coating is characterized by comprising a low surface energy coating and a functional filler;
the functional filler is nano titanium dioxide and carbon nano tubes;
wherein, the low surface energy coating is selected from any one of organosilicon waterproof coating or organofluorine waterproof coating;
the nano titanium dioxide is adsorbed on the surface of the carbon nano tube, the nano titanium dioxide is monodisperse nano titanium dioxide, the particle size distribution range of the nano titanium dioxide is 5-10nm, and at least part of the nano titanium dioxide is anatase type titanium dioxide.
2. The nano antifouling fiber paint as claimed in claim 1, wherein the surface of the carbon nanotubes is doped with a hetero element selected from nitrogen.
3. The nano antifouling fiber paint as claimed in claim 1, wherein the mass ratio of the low surface energy paint to the functional filler in the nano antifouling fiber paint is 8:1-10:1.
4. the nano antifouling fiber paint as claimed in claim 1, wherein the carbon nanotubes are in a contracted and curled state, and the ratio of the length of the carbon nanotubes after stretching and straightening to the length of the carbon nanotubes in the contracted state is 1.5:1-1.8:1.
5. a method for preparing the nano antifouling fiber coating as claimed in any one of claims 1 to 4, wherein the specific preparation steps comprise:
preparing functional filler:
dispersing carbon nano tubes in ethanol, adding citric acid and tetrabutyl titanate, carrying out heating reflux reaction, and regulating and controlling the technological parameters of the heating reflux reaction as follows: the reaction temperature is 82-88 ℃, and the reaction time is 45-60min;
after the reflux reaction is finished, filtering and washing, calcining the obtained filter cake at 550-600 ℃ in an inert atmosphere to obtain the functional filler;
preparation of the coating:
and (3) uniformly mixing and dispersing the low-surface-energy coating and the functional filler to obtain the product.
6. The method for preparing nano antifouling fiber paint as claimed in claim 5, wherein the carbon nanotubes are pretreated carbon nanotubes;
the preparation method of the pretreated carbon nanotube comprises the following steps:
dispersing the carbon nano tube in a dopamine solution, stirring for reaction, and filtering to obtain the pretreated carbon nano tube.
7. The method of claim 6, wherein the carbon nanotubes are selected from single-walled carbon nanotubes, and the single-walled carbon nanotubes are doped with nitrogen before the pretreatment, wherein the doping with nitrogen comprises:
and (3) performing heat treatment on the single-walled carbon nanotube by adopting boron oxide steam and nitrogen at the temperature of 1350-1400 ℃ to obtain the nitrogen-doped single-walled carbon nanotube.
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