CN116790185A - Method for constructing super-hydrophobic coating on wood surface based on layer-by-layer self-assembly and application - Google Patents
Method for constructing super-hydrophobic coating on wood surface based on layer-by-layer self-assembly and application Download PDFInfo
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- 239000002023 wood Substances 0.000 title claims abstract description 214
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 75
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001338 self-assembly Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000006229 carbon black Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229920002545 silicone oil Polymers 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010276 construction Methods 0.000 claims abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 16
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 230000001680 brushing effect Effects 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 238000005299 abrasion Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002253 acid Substances 0.000 description 12
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000003068 static effect Effects 0.000 description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 7
- 229910010271 silicon carbide Inorganic materials 0.000 description 7
- 244000137852 Petrea volubilis Species 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- -1 perfluoroalkyl triethoxysilane Chemical compound 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- USUXZUDXLLLGLU-UHFFFAOYSA-N 1,3,2,4-dioxadisiletane Chemical group O1[SiH2]O[SiH2]1 USUXZUDXLLLGLU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002073 nanorod Substances 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
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a method for constructing a super-hydrophobic coating on the surface of wood based on layer-by-layer self-assembly and application thereof, comprising the following steps: coating the A component modifying liquid and the B component modifying liquid on the surface of the wood in turn according to preset conditions, and then drying the wood in a preset temperature environment to finish the construction of the super-hydrophobic coating on the surface of the wood; wherein, the A component modifying liquid comprises: a first nonpolar solvent, hydrogen-containing silicone oil, white carbon black and a first catalyst; in addition, the component B modifying liquid comprises: a second nonpolar solvent, white carbon black, a vinyl ring and a second catalyst; the proposal of the invention creatively adopts a chemical driving layer-by-layer self-assembly method to construct the super-hydrophobic organic silicon resin coating on the surface of the wood, the preparation method of the wood with the super-hydrophobic coating is simple, the reaction condition is easy to realize, and the raw materials used for preparation are industrial products with low price; meanwhile, the prepared super-hydrophobic wood has good friction resistance, and has great practical application significance.
Description
Technical Field
The invention relates to the technical field of wood protection, in particular to a method for constructing a super-hydrophobic coating on the surface of wood based on layer-by-layer self-assembly and application thereof.
Background
For a long time, wood is widely applied to constructional engineering and indoor and outdoor decoration because of the advantages of light weight, high strength, easy processing, rich resources, reproducibility and the like. The wood mainly comprises cellulose, hemicellulose, lignin and the like, and the cellulose and the hemicellulose are rich in hydroxyl groups and the like with strong hygroscopicity, so that the wood has strong hygroscopicity, and the wood is often deformed, decayed, discolored and the like due to the existence of moisture in the use process. The superhydrophobic treatment of the wood can endow the surface of the wood with various functions of water resistance, stain resistance, self cleaning, antibiosis and the like, can effectively widen the application range of the wood in production and life, and prolongs the service life of the wood.
In recent years, technology for constructing a superhydrophobic surface on a wood surface based on a lotus leaf effect is continuously applied to the protection of the wood. Research shows that there are two ways to obtain superhydrophobic surfaces:
(1) Constructing a micro-nano hierarchical coarse structure on the surface of a low-surface-energy substance;
(2) Modifying the surface of the rough substance with low surface energy.
The document (appl. Surf. Sci.407 (2017) 479-484) proposes that a super-hydrophobic coating with light stability is constructed on the surface of wood by adopting a hydrothermal method and taking zinc oxide nanorods and stearic acid as modified raw materials; literature (appl. Surf. Sci.258 (2011) 806-810) proposes that a sol-gel method is adopted, perfluoroalkyl triethoxysilane (POTS) is taken as a hydrophobic modifier, and the prepared silica nanoparticles are combined to realize the construction of a super-hydrophobic coating on the surface of wood; the chinese patent publication No. CN103448116B first soaked wood in epoxy resin to cover the surface with a layer of epoxy resin. Then, the silicon dioxide is soaked in silicon dioxide solution grafted with amino groups, so that the silicon dioxide and the epoxy resin react, and the silicon dioxide is adhered to the surface of the epoxy resin to form a micro-nano secondary structure. Finally, carrying out hydrophobic modification on the micro-nano secondary structure on the surface of the wood, thereby preparing the super-hydrophobic wood. However, most of the currently reported methods for preparing the super-hydrophobic wood have complex processes and high cost, and the friction resistance of the super-hydrophobic coating on the surface of the prepared super-hydrophobic wood is poor, so that the effect of lasting super-hydrophobic cannot be achieved. Therefore, a simple, effective and low-cost method for preparing wear-resistant super-hydrophobic wood is needed.
Disclosure of Invention
Therefore, the invention aims to provide a method for constructing a super-hydrophobic coating on the surface of a wood based on layer-by-layer self-assembly, which is convenient to operate and good in durability, and application.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for constructing a super-hydrophobic coating on the surface of a wood based on layer-by-layer self-assembly comprises the following steps:
coating the A component modifying liquid and the B component modifying liquid on the surface of the wood in turn according to preset conditions, and then drying the wood in a preset temperature environment to finish the construction of the super-hydrophobic coating on the surface of the wood;
wherein, the A component modifying liquid comprises: a first nonpolar solvent, hydrogen-containing silicone oil, white carbon black and a first catalyst;
in addition, the component B modifying liquid comprises: the catalyst comprises a second nonpolar solvent, white carbon black, a vinyl ring body and a second catalyst.
As a possible implementation mode, in the component A modified liquid, the mass ratio of the first nonpolar solvent to the hydrogen-containing silicone oil to the white carbon black to the first catalyst is (45-80): 1-8): 0.025-2.5): 0.05-0.5; in the component B modifying liquid, the mass ratio of the second nonpolar solvent to the white carbon black to the vinyl ring and the second catalyst is (45-80), 0.025-2.5, 1-8 and 0.05-0.5.
As one of the preparation methods of the A component modified liquid, it includes: adding a first nonpolar solvent, hydrogen-containing silicone oil, white carbon black and a first catalyst into a container according to the mass ratio of (45-80): (1-8): (0.025-2.5): (0.05-0.5), uniformly mixing, and uniformly dispersing by ultrasonic to obtain the component A modified liquid.
As one of the preparation methods of the component B modifying liquid, it includes: adding a second nonpolar solvent, white carbon black, vinyl ring and a second catalyst into a container according to the mass ratio of (45-80) (0.025-2.5) (1-8) (0.05-0.5), uniformly mixing, and uniformly dispersing by ultrasonic to obtain the component B modified liquid.
As a preferred alternative implementation mode, preferably, the method for sequentially coating the A component modifying liquid and the B component modifying liquid on the surface of the wood in the scheme is soaking, wherein the soaking times are more than one cycle, and the soaking time is more than 2 minutes each time.
As a preferred alternative implementation mode, the method for sequentially coating the A component modifying liquid and the B component modifying liquid on the surface of the wood in the scheme is preferably brushing or spraying, and the coating amount is 800-1500g/m 2 。
As a preferred alternative implementation mode, preferably, the temperature of the drying treatment is between room temperature and 160 ℃, and the super-hydrophobic coating is constructed on the surface of the wood after the first nonpolar solvent and/or the second nonpolar solvent attached to the surface of the wood are dried to a preset state.
As an example, the scheme comprises the steps of uniformly dispersing the A component modifying liquid and the B component modifying liquid by ultrasonic, sequentially coating the A component modifying liquid and the B component modifying liquid on the surface of the wood by adopting a dipping, brushing or spraying method, and finally drying the modified wood at the room temperature to 160 ℃ until the solvent is completely volatilized.
As a preferred alternative embodiment, the first nonpolar solvent and the second nonpolar solvent in this embodiment are preferably n-hexane, cyclohexane, n-heptane or n-pentane.
As a preferred alternative implementation mode, the types of the white carbon black in the A component modified liquid and the B component modified liquid in the scheme are precipitation white carbon black, gas phase white carbon black, hydrophobic modified precipitation white carbon black and hydrophobic modified gas phase white carbon black.
As a preferred alternative embodiment, preferably, the hydrogen-containing silicone oil in the scheme is polymethyl hydrogen siloxane containing silicon-hydrogen bonds, the hydrogen content of the hydrogen-containing silicone oil is 1.0% -1.6%, and the molecular structural formula of the polymethyl hydrogen siloxane is as follows:
wherein m and n are integers.
As a preferred alternative embodiment, preferably, the vinyl ring is tetramethyl tetravinyl cyclotetrasiloxane, and the molecular structural formula of the tetramethyl tetravinyl cyclotetrasiloxane is:
as a preferred alternative embodiment, the first catalyst and the second catalyst in this embodiment are preferably platinum catalysts that can catalyze a chemical reaction between a silicon hydrogen bond on a polymethylhydrosiloxane chain and a vinyl double bond in a tetramethyl-tetravinyl cyclotetrasiloxane structure, for example, a complex of Pt and divinyl-tetramethyl disiloxane, and the like.
Based on the above, the invention also provides a wood, the surface of which is applied with a super-hydrophobic coating, and the super-hydrophobic coating is applied on the surface of the wood by the method.
The invention has the technical key that a wear-resistant durable super-hydrophobic organic silicon resin coating is constructed on the surface of wood, and the main components of the coating are polymethyl hydrogen siloxane, tetramethyl tetravinyl cyclotetrasiloxane and white carbon black; the white carbon black builds a rough surface, and the polymethylhydrosiloxane can reduce the surface energy of wood on one hand, and can react with hydroxyl groups on the surface of the wood and vinyl groups on the tetramethyl tetravinyl cyclotetrasiloxane in a dehydrogenation and addition way on the other hand, so that an organic silicon resin coating is built on the surface of the wood.
The reaction mechanism of the scheme is that the polymethylhydrosiloxane containing-Si-H bond reacts with-OH groups on the surface of wood and SiCH=CH under the action of a room temperature catalyst 2 The tetramethyl tetravinyl cyclotetrasiloxane is subjected to dehydrogenation and addition reaction to generate an organic silicon resin layer, and the generated organic silicon resin coats the white carbon black on the surface of the wood, so that a rough structure similar to lotus leaves and having low surface energy is formed on the surface of the wood, and the super-hydrophobic and self-cleaning properties of the wood are realized. Because the organic silicon resin has strong bonding effect and is constructed on the surface of the wood in a covalent bond bonding mode, the super-hydrophobic wood obtained by the invention has good friction resistance. The preparation schematic diagram of the super-hydrophobic organic silicon resin coating constructed on the surface of the wood by adopting the chemical driving layer-by-layer self-assembly of the impregnation process is shown in figure 1 (in the injection brushing method and the spraying method, the preparation method of the modifying liquid is consistent, and the modifying liquid is only coated on the surface of the wood by adopting different methods, and the schematic diagram is not drawn one by one).
By adopting the technical scheme, compared with the traditional technology, the technical scheme has the following beneficial effects:
(1) The proposal of the invention creatively adopts a chemical driving layer-by-layer self-assembly method to construct the super-hydrophobic organic silicon resin coating on the surface of the wood, the preparation method of the wood with the super-hydrophobic coating is simple, the reaction condition is easy to realize, and the raw materials used for preparation are industrial products with low price;
(2) According to the scheme, the adopted raw materials are polymethyl hydrogen siloxane, tetramethyl tetravinyl cyclotetrasiloxane and silicon dioxide nano particles which are industrially produced, A, B double-component modified liquid is prepared through design, then unmodified wood is circularly immersed in A, B double-component modified liquid at normal temperature and normal pressure through a chemical driving layer-by-layer self-assembly method, so that a super-hydrophobic wood sample can be obtained, a super-hydrophobic organic silicon resin coating constructed on the surface of the wood has good water repellency, water drops can roll away from the surface of the wood, in addition, the modified wood has self-cleaning performance, water drops can take away pollutants on the surface of the wood, and meanwhile, the super-hydrophobic wood has good friction resistance, so that the super-hydrophobic wood has greater practical application significance;
(3) According to the scheme, the super-hydrophobic wood prepared by chemical driving layer-by-layer self-assembly modification can effectively inhibit the wood from absorbing moisture from the environment, so that the service life of the wood is prolonged; meanwhile, the super-hydrophobic wood prepared by the method has excellent self-cleaning, friction-resistant and durable performances.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a simplified implementation of the method of the present invention;
FIG. 2 is a schematic illustration of the present invention wherein water droplets are dropped on the surface of wood to which the superhydrophobic coating is applied, and the water droplets roll off the surface of the wood;
FIG. 3 is a schematic illustration of the inventive solution for placing contaminants on the surface of wood with a superhydrophobic coating applied, followed by the dropwise addition of water droplets, which carry away the contaminants on the surface of wood;
FIG. 4 is a schematic illustration of the tape stripping and sandpaper abrasion test performed on a wood surface with a superhydrophobic coating applied according to the inventive protocol;
FIG. 5 is a schematic representation of the contact angle characterization of a drop of water on the surface of the wood (modified wood) of example 1 of the present invention;
FIG. 6 is a schematic representation of the abrasion resistance test performed on the wood surface (modified wood) of example 1 of the present invention;
FIG. 7 is a schematic representation of the contact angle characterization of a drop of water on the surface of the wood (modified wood) of example 2 of the present invention;
FIG. 8 is a schematic representation of the contact angle characterization of a drop of water on the surface of the wood (modified wood) of example 3 of the present invention;
FIG. 9 is a schematic representation of the contact angle characterization of a drop of water on the surface of the wood (modified wood) of example 4 of the present invention;
FIG. 10 is a schematic representation of the contact angle characterization of a drop of water on the surface of the wood (modified wood) of example 5 of the present invention;
FIG. 11 is a schematic representation of the contact angle of a drop of water drop on the wood surface of comparative example 1 of the present invention, wherein the figure is only FIG. 11 (a);
FIG. 12 is a schematic representation of the contact angle of a drop of water drop on the surface of the wood of comparative example 2 of the present invention;
FIG. 13 is a schematic representation of the contact angle of a drop of water drop on the surface of the wood of comparative example 3 of the present invention;
fig. 14 is a schematic representation of the abrasion resistance test of the wood surface of comparative example 3 of the present invention on 1500 mesh silicon carbide sandpaper.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is specifically noted that the following examples are only for illustrating the present invention, but do not limit the scope of the present invention. Likewise, the following examples are only some, but not all, of the examples of the present invention, and all other examples, which a person of ordinary skill in the art would obtain without making any inventive effort, are within the scope of the present invention.
Referring to fig. 1, the method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly comprises the following steps:
(1) Preparing A, B component solution: adding a nonpolar solvent, hydrogen-containing silicone oil, white carbon black and a first catalyst into a container according to the mass ratio of (45-80): (1-8): (0.025-2.5): (0.05-0.5), uniformly mixing, and uniformly dispersing by ultrasonic to obtain a solution A; adding a nonpolar solvent, white carbon black, a vinyl ring body and a second catalyst into a container according to the mass ratio of (45-80) (0.025-2.5) (1-8) (0.05-0.5), uniformly mixing, and uniformly dispersing by ultrasonic to obtain a solution B;
(2) Modification of wood: after the A, B component modified liquid is uniformly dispersed by ultrasonic, A, B component modified liquid is sequentially coated on the surface of the wood by adopting a dipping (or brushing or spraying) method, and finally the modified wood is dried at the room temperature to 160 ℃ until the solvent is completely volatilized.
The hydrogen-containing silicone oil in the step (1) of the scheme refers to polymethyl hydrogen siloxane containing a silicon-hydrogen bond, and the hydrogen content of the hydrogen-containing silicone oil is 1.0% -1.6%; the white carbon black is precipitated white carbon black, fumed white carbon black, hydrophobic modified precipitated white carbon black and hydrophobic modified fumed white carbon black; the vinyl ring is tetramethyl tetravinyl cyclotetrasiloxane sold in the market; the catalyst is a commercially available platinum catalyst which can catalyze the chemical reaction between a silicon-hydrogen bond on a polymethyl hydrosiloxane chain and a vinyl double bond in a tetramethyl tetravinyl cyclodisiloxane structure, such as a complex of Pt and divinyl tetramethyl disiloxane, and the like.
The dipping process in the step (2) of the scheme is that wood blocks are sequentially dipped into A, B component modifying liquid, and the dipping time of self-assembly of chemical driving layers for one time is more than 2 min; when the modified liquid is applied by brushing or spraying, the modified liquid is coated on the surface of the wood by a brushing process, and the coating amount of the modified liquid is 800-1500g/m 2 。
The wood with the super-hydrophobic coating applied by the scheme of the invention has stronger hydrophobicity, wherein fig. 2 is a schematic diagram of the scheme of the invention, in which water drops are dripped on the surface of the wood with the super-hydrophobic coating applied, and the water drops roll away from the surface of the wood.
In addition, fig. 3 is a schematic diagram of placing pollutants on the surface of the wood with the super-hydrophobic coating, then dripping water drops to take away the pollutants on the surface of the wood, and it can be known that the modified wood has self-cleaning performance, and the water drops can take away the pollutants on the surface of the wood.
The superhydrophobic organic silicon resin coating on the surface of the modified wood has excellent wear resistance and can be subjected to tape stripping and abrasive paper wear tests, wherein fig. 4 is a schematic diagram of the proposal of the invention for carrying out tape stripping and abrasive paper wear tests on the surface of the wood with the superhydrophobic coating.
The scheme of the invention is further illustrated by comparison with a plurality of examples and comparative examples as follows:
example 1
With reference to the schematic operation flow diagram shown in fig. 1, the method for constructing the superhydrophobic coating on the surface of the wood based on layer-by-layer self-assembly in this embodiment includes:
(1) 55g of n-hexane, 4g of polymethylhydrosiloxane, 1g of hydrophobic white carbon black and 0.1g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content is 2000 ppm) are added into a container, and after ultrasonic dispersion is uniform, the A component modified liquid is obtained. 55g of n-hexane, 0.5g of hydrophobic white carbon black, 2g of tetramethyl tetravinyl cyclotetrasiloxane and 0.1g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyl disiloxane (Pt content is 2000 ppm) are added into another container, and the B component modified liquid is obtained after ultrasonic dispersion is uniform.
(2) Surface hydrophobic modification of wood: the wood block is immersed into the A component modifying liquid for 3 min, and then is immersed into the B component modifying liquid for 3 min after being immersed and taken out. And (5) immersing A, B the modified liquid for 2 times through chemical driving layer-by-layer self-assembly circulation to obtain a modified wood sample.
(3) Drying the modified wood block: and (3) placing the wood blocks soaked in the step (2) in a 60 ℃ oven for drying for 100 min.
(4) The modified wood in this example was subjected to contact angle and sand paper abrasion tests.
Performance testing
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test result shows that the modified wood achieves super-hydrophobic property, and the contact angle of water drops on the diameter section of the wood is 163.1 degrees (shown in figure 5).
The modified wood in this example was placed on 1500 mesh silicon carbide sandpaper for abrasion resistance testing and a 10g weight was placed on the modified wood surface (as shown in fig. 6). The test result shows that the maximum abrasion resistance length of the modified wood is 200cm, and when the abrasion length exceeds 200cm, the modified wood loses the superhydrophobic performance.
Example 2
The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly comprises the following steps:
(1) 65g cyclohexane, 4g polymethylhydrosiloxane, 1g hydrophilic white carbon black and 0.15g complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content is 2000 ppm) are added into a container, and after ultrasonic dispersion is uniform, the A component modified liquid is obtained. 65g cyclohexane, 0.5g hydrophilic white carbon black, 2g tetramethyl tetravinyl cyclotetrasiloxane and 0.15g complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyl disiloxane (Pt content is 2000 ppm) are added into another container, and after ultrasonic dispersion is uniform, the component B modified liquid is obtained.
(2) Surface hydrophobic modification of wood: the wood block is immersed into the A component modifying liquid for 5 min, and then is immersed into the B component modifying liquid for 5 min after being immersed and taken out. And (5) immersing A, B the modified liquid for 4 times through chemical driving layer-by-layer self-assembly circulation to obtain a modified wood sample.
(3) Drying the modified wood block: and (3) placing the wood blocks soaked in the step (2) in a 60 ℃ oven for drying for 100 min.
(4) The modified wood in this example was subjected to contact angle and sand paper abrasion tests.
Performance testing
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test result shows that the modified wood achieves super-hydrophobic property, and the contact angle of water drops on the diameter section of the wood is 160.3 degrees (shown in figure 7).
The modified wood in this example was placed on 1500 mesh silicon carbide sandpaper for abrasion resistance testing and a 10g weight was placed on the modified wood surface (as shown in fig. 6). The test result shows that the maximum abrasion resistance length of the modified wood is 320cm, and when the abrasion length exceeds 320cm, the modified wood loses the superhydrophobic performance.
Example 3
The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly comprises the following steps:
(1) 60g of n-heptane, 4g of polymethylhydrosiloxane, 1g of hydrophilic white carbon black and 0.2g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content is 2000 ppm) are added into a container, and after ultrasonic dispersion is uniform, the A component modified liquid is obtained. 60g of n-heptane, 0.5g of hydrophilic white carbon black, 2g of tetramethyl tetravinyl cyclotetrasiloxane and 0.2g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyl disiloxane (Pt content is 2000 ppm) are added into another container, and after ultrasonic dispersion is uniform, the component B modified liquid is obtained.
(2) Surface hydrophobic modification of wood: the wood block is immersed into the A component modifying liquid for 10 min, and then is immersed into the B component modifying liquid for 10 min after being immersed and taken out. And (5) dipping A, B the modified liquid for 6 times through chemical driving layer-by-layer self-assembly circulation to obtain a modified wood sample.
(3) Drying the modified wood block: and (3) placing the wood blocks soaked in the step (2) in a 60 ℃ oven for drying for 100 min.
(4) The modified wood in this example was subjected to contact angle and sand paper abrasion tests.
Performance testing
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test result shows that the modified wood achieves super-hydrophobic property, and the contact angle of water drops on the diameter section of the wood is 158.6 degrees (shown in figure 8).
The modified wood in this example was placed on 1500 mesh silicon carbide sandpaper for abrasion resistance testing and a 10g weight was placed on the modified wood surface (as shown in fig. 6). The test result shows that the maximum abrasion resistance length of the modified wood is 420cm, and when the abrasion length exceeds 420cm, the modified wood loses the superhydrophobic performance.
Example 4
The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly comprises the following steps:
(1) 55g of n-pentane, 4g of polymethylhydrosiloxane, 1g of hydrophobic white carbon black and 0.2g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content is 2000 ppm) are added into a container, and after ultrasonic dispersion is uniform, the A component modified liquid is obtained. 55g of n-pentane, 0.5g of hydrophobic white carbon black, 4g of tetramethyl tetravinyl cyclotetrasiloxane and 0.2g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyl disiloxane (Pt content is 2000 ppm) are added into another container, and the B component modified liquid is obtained after ultrasonic dispersion is uniform.
(2) Surface hydrophobic modification of wood: the wood block is immersed in the A component modifying liquid for 15 min, and then is immersed in the B component modifying liquid for 15 min after being immersed and taken out. And (5) immersing A, B the modified liquid for 4 times through chemical driving layer-by-layer self-assembly circulation to obtain a modified wood sample.
(3) Drying the modified wood block: and (3) placing the wood blocks soaked in the step (2) in a 60 ℃ oven for drying for 100 min.
(4) The modified wood in this example was subjected to contact angle and sand paper abrasion tests.
Performance testing
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test result shows that the modified wood achieves super-hydrophobic property, and the contact angle of water drops on the diameter section of the wood is 154.3 degrees (shown in figure 9).
The modified wood in this example was placed on 1500 mesh silicon carbide sandpaper for abrasion resistance testing and a 10g weight was placed on the modified wood surface (as shown in fig. 6). The test result shows that the maximum abrasion resistance length of the modified wood is 280cm, and when the abrasion length exceeds 280cm, the modified wood loses the superhydrophobic performance.
Example 5
The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly comprises the following steps:
(1) 50g of cyclohexane, 6g of polymethylhydrosiloxane, 1g of hydrophobic white carbon black and 0.25g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content is 2000 ppm) are added into a container, and after ultrasonic dispersion is uniform, the A component modified liquid is obtained. 50g of cyclohexane, 0.5g of hydrophobic white carbon black, 2g of tetramethyl tetravinyl cyclotetrasiloxane and 0.25g of complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyl disiloxane (Pt content is 2000 ppm) are added into another container, and the B component modified liquid is obtained after ultrasonic dispersion is uniform.
(2) Surface hydrophobic modification of wood: the wood block is immersed into the A component modifying liquid for 6 min, the wood block is immersed into the B component modifying liquid for 6 min after being immersed and taken out. And (5) immersing A, B modified liquid for 3 times through chemical driving layer-by-layer self-assembly circulation to obtain a modified wood sample.
(3) Drying the modified wood block: and (3) placing the wood blocks soaked in the step (2) in a 60 ℃ oven for drying for 100 min.
(4) The modified wood in this example was subjected to contact angle and sand paper abrasion tests.
Performance testing
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test result shows that the modified wood achieves super-hydrophobic property, and the contact angle of water drops on the diameter section of the wood is 155.6 degrees (shown in figure 10).
The modified wood in this example was placed on 1500 mesh silicon carbide sandpaper for abrasion resistance testing and a 10g weight was placed on the modified wood surface (as shown in fig. 6). The test result shows that the maximum abrasion resistance length of the modified wood is 260cm, and when the abrasion length exceeds 260cm, the modified wood loses the superhydrophobic performance.
Comparative example 1
The wood block is not modified in the comparative example, and is only dried at 100 ℃ for 100 min.
Contact angle tests were performed on the unmodified wood in this comparative example.
Performance testing
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The unmodified wood of this comparative example was placed on a test platform and tested for its static contact angle with water and test drop volume of 0.5 microliter. The test results showed that the unmodified wood had excellent hydrophilicity, and the contact angle of the water drop on the diameter section of the wood was 36.3 ° (as shown in fig. 11 (a)).
Comparative example 2
In this comparative example, 0.25g of polymethylhydrosiloxane and 49.75g of n-hexane were mixed, and stirred with a glass rod at room temperature for 1 min, then 0.15g of a complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content: 2000 ppm) was added thereto, and stirring was continued for 1 min to obtain a hydrophobically modified liquid. Then, the unmodified wood is immersed in the modifying liquid for 1 min, and after the immersing, the wood is left to be dried in the room temperature environment.
Performance testing
The contact angle test was performed on the modified wood in this comparative example.
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this comparative example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test results show that the hydrophobicity of the modified wood is improved, and the contact angle of water drops on the diameter section of the wood is 139.6 degrees (shown in figure 12).
Comparative example 3
In this comparative example, 1g of hydrophilic white carbon black was dispersed in 80g of tetrahydrofuran solution, and then magnetically stirred at room temperature for 5 min. Subsequently, to the solution prepared above, 2g of polymethylhydrosiloxane and 0.15g of a complex of chloroplatinic acid and 1, 3-divinyl-1, 3-tetramethyldisiloxane (Pt content: 2000 ppm) were added, and after continuing magnetic stirring for 30 min, a hydrophobically modified liquid was obtained. The unmodified wood was then immersed in the hydrophobic modification solution for 5 min, after which the wood was dried in an oven at 80 ℃ for 30 min.
Performance testing
Contact angle and sand paper abrasion tests were performed on the modified wood in this comparative example.
Test instrument: domestic contact angle measuring instrument (HARKE-SPCA-1)
The modified wood of this comparative example was placed on a test platform and tested for its static contact angle with water, and the test drop volume was 0.5 microliter. The test result shows that the modified wood achieves super-hydrophobic property, and the contact angle of water drops on the diameter section of the wood is 158 degrees (shown in figure 13).
The modified wood of this comparative example was placed on 1500 mesh silicon carbide sandpaper for abrasion resistance testing, and a 10g weight was placed on the surface of the modified wood (as shown in fig. 14). The test result shows that the maximum abrasion resistance length of the modified wood is 120cm, and when the abrasion length exceeds 120cm, the modified wood loses the superhydrophobic performance.
The foregoing description is only a partial embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent devices or equivalent processes using the descriptions and the drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A method for constructing a super-hydrophobic coating on the surface of a wood based on layer-by-layer self-assembly is characterized by comprising the following steps:
coating the A component modifying liquid and the B component modifying liquid on the surface of the wood in turn according to preset conditions, and then drying the wood in a preset temperature environment to finish the construction of the super-hydrophobic coating on the surface of the wood;
wherein, the A component modifying liquid comprises: a first nonpolar solvent, hydrogen-containing silicone oil, white carbon black and a first catalyst;
in addition, the component B modifying liquid comprises: the catalyst comprises a second nonpolar solvent, white carbon black, a vinyl ring body and a second catalyst.
2. The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly according to claim 1, wherein in the component A modifying solution, the mass ratio of the first nonpolar solvent to the hydrogen-containing silicone oil to the white carbon black to the first catalyst is (45-80): (1-8): (0.025-2.5): (0.05-0.5);
in the component B modifying liquid, the mass ratio of the second nonpolar solvent to the white carbon black to the vinyl ring and the second catalyst is (45-80), 0.025-2.5, 1-8 and 0.05-0.5.
3. The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly according to claim 1 or 2, wherein the method for sequentially coating the A component modifying liquid and the B component modifying liquid on the surface of the wood is soaking, the soaking times are more than one cycle, and the soaking time is more than 2 minutes each time.
4. The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly according to claim 1 or 2, wherein the method for sequentially coating the A component modifying liquid and the B component modifying liquid on the surface of the wood is brushing or spraying, and the coating amount is 800-1500g/m 2 。
5. The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly according to claim 1 or 2, wherein the temperature of the drying treatment is between room temperature and 160 ℃, and the super-hydrophobic coating on the surface of the wood is constructed after the first nonpolar solvent and/or the second nonpolar solvent attached to the surface of the wood are dried to volatilize to a preset state.
6. The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly according to claim 1 or 2, wherein the first nonpolar solvent and the second nonpolar solvent are n-hexane, cyclohexane, n-heptane or n-pentane;
the types of the white carbon black in the component A modified liquid and the component B modified liquid are precipitated white carbon black, gas phase white carbon black, hydrophobic modified precipitated white carbon black and hydrophobic modified gas phase white carbon black.
7. The method for constructing the super-hydrophobic coating on the surface of the wood based on layer-by-layer self-assembly according to claim 1 or 2, wherein the hydrogen-containing silicone oil is polymethylhydrosiloxane containing silicon-hydrogen bonds, the hydrogen content of the hydrogen-containing silicone oil is 1.0% -1.6%, and the polymethylhydrosiloxane has a molecular structural formula as follows:
wherein m and n are integers.
8. The method for constructing a superhydrophobic coating on a wood surface based on layer-by-layer self-assembly according to claim 7, wherein the vinyl ring is tetramethyl tetravinyl cyclotetrasiloxane, and the molecular structural formula of the tetramethyl tetravinyl cyclotetrasiloxane is:
9. the method for constructing a superhydrophobic coating on a wood surface based on layer-by-layer self-assembly according to claim 8, wherein the first catalyst and the second catalyst are platinum catalysts capable of catalyzing chemical reaction between a silicon hydrogen bond on a polymethylhydrosiloxane chain and a vinyl double bond in a tetramethyl tetravinyl cyclotetrasiloxane structure.
10. A wood, characterized in that: a superhydrophobic coating applied to the surface of wood by the method of any one of claims 1-9.
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