CN117089271A - Polyurethane coating with hydrophobicity, icephobic property and self-healing capability, and preparation method and application thereof - Google Patents
Polyurethane coating with hydrophobicity, icephobic property and self-healing capability, and preparation method and application thereof Download PDFInfo
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- CN117089271A CN117089271A CN202311057111.1A CN202311057111A CN117089271A CN 117089271 A CN117089271 A CN 117089271A CN 202311057111 A CN202311057111 A CN 202311057111A CN 117089271 A CN117089271 A CN 117089271A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011527 polyurethane coating Substances 0.000 title abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 84
- 238000000576 coating method Methods 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 7
- KMNKECSEFVPPNJ-UHFFFAOYSA-N 1-(6-isocyanatohexyl)-3-(6-methyl-4-oxo-1h-pyrimidin-2-yl)urea Chemical compound CC1=CC(=O)N=C(NC(=O)NCCCCCCN=C=O)N1 KMNKECSEFVPPNJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 238000007731 hot pressing Methods 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 5
- -1 poly (dimethylsiloxane) Polymers 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 230000003075 superhydrophobic effect Effects 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000005871 repellent Substances 0.000 abstract description 7
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 235000008113 selfheal Nutrition 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000035876 healing Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013005 self healing agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a polyurethane coating with hydrophobicity, ice-repellent property and self-healing capacity, and a preparation method and application thereof, and belongs to the technical field of polyurethane materials. The self-healing polyurethane disclosed by the invention is introduced with bis (3-aminopropyl) end-capped poly (dimethylsiloxane), isophorone diisocyanate, 2- (6-isocyanatohexylaminocarbonylamino) -6-methyl-4-pyrimidinone, hydrophobic nano silicon dioxide and hydrophobic carbon nano tubes, and the obtained material has high-efficiency self-healing, superhydrophobicity and ice-repellent capability and excellent mechanical property. The product can self-heal at normal temperature, does not need to be replaced frequently, has strong deicing and hydrophobic capabilities, can maintain the surface performance of a coating in rainy and snowy days, and can be used for surface protection of infrastructure and transportation. The method has the advantages of simple process, easy operation, low equipment requirement, low cost, suitability for large-scale preparation and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to a polyurethane coating with hydrophobicity, ice-dispelling property and self-healing capacity, and a preparation method and application thereof.
Background
Excessive accumulation of ice and snow and corrosive effects of water can have serious effects on infrastructure and transportation, such as on aircraft, marine structures, wind turbines, power lines, etc., such as accumulation of unwanted ice layers on exposed surfaces can impede the passage of light, thereby causing malfunction of equipment requiring high light transmittance, such as solar panels, windows, and sensors. Conventional deicing, icephobic or hydrophobic treatment methods are classified into active deicing mainly comprising chemical deicing, mechanical deicing, electrothermal deicing and the like and passive deicing mainly comprising a super-hydrophobic coating and a lubricating coating (SLIPS), and the conventional methods are considered to be energy-intensive through active heating or using an antifreezing solution, so that an unresolved environmental problem may be generated. The surface of the coating is easily damaged by the external environment in the long-term use process, so that the ice resistance or the hydrophobicity is lost, and the mechanical durability and the high transparency of the material are also influenced; it is desirable for the material or material coating to have a self-healing function.
The method for realizing self-healing of the material comprises high-temperature oxidation, self-healing agent addition and the like, wherein the high-temperature oxidation requires ultrahigh high temperature (such as 1200 ℃) to form metal oxide to fill the damage in the coating; based on the addition of self-healing agents, mainly with pre-embedded encapsulated reactants, which are released at the crack interface to fill and repair the damage, the self-healing properties of these external healing polymers are effective, but the number of healing cycles in general is limited due to the depletion of the reactants. There is a great need to develop a material or material coating that has excellent hydrophobic icephobicity and is capable of fast self-healing to solve the current technical problems.
Disclosure of Invention
The invention aims to solve some defects in the prior art and provide the coating with excellent hydrophobic ice-dispersion performance, short self-healing time under room temperature and atmospheric environment and high self-healing efficiency.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the invention firstly provides a preparation method of a coating with hydrophobicity, ice-repellent property and self-healing capability, which comprises the following steps:
(1) Bis (3-aminopropyl) endblocked poly (dimethylsiloxane) (H 2 N-PDMS-NH 2 ) And isophorone diisocyanate (IPDI) are dissolved in tetrahydrofuran respectively, and the obtained solutions are mixed and stirred for reaction until the reaction is complete.
Wherein the bis (3-aminopropyl) endblocked poly (dimethylsiloxane) (H 2 N-PDMS-NH 2 ) And tetrahydrofuran 15 parts by weight and tetrahydrofuran 50 parts by weight respectively; 1.7 parts by mass of isophorone diisocyanate (IPDI) and 20 parts by mass of tetrahydrofuran; the stirring reaction condition in the oil bath pot is that the reaction is carried out for 46-50 hours at 20-30 ℃, and preferably, the stirring reaction is carried out for 48 hours at 25 ℃; the stirring speed was 300r/min.
Further, the bis (3-aminopropyl) terminated poly (dimethylsiloxane) (H 2 N-PDMS-NH 2 ) Has a molecular weight of 3000 or 1000.
(2) Weighing 2- (6-isocyanatohexylaminocarbonylamino) -6-methyl-4-pyrimidinone (UPy-NCO), adding into the mixed solution in the step (1), stirring for reaction after the temperature is raised, centrifuging until the reaction is complete, and taking supernatant obtained after centrifugation.
Wherein the mass part of the 2- (6-isocyanatohexylaminocarbonylamino) -6-methyl-4-pyrimidinone (UPy-NCO) is 4 parts; the reaction conditions are that stirring reaction is carried out for 11-13 hours at the temperature of 75-85 ℃ in an oil bath pot, and the stirring rotation speed is 300r/min; preferably, the stirring reaction is carried out at 80℃for 12h.
(3) Adding the hydrophobic nano filler powder and the hydrophobic nano silicon dioxide into the supernatant obtained in the step (2), and continuously stirring at room temperature until the reaction is complete; and drying the product and hot-pressing to obtain the coating.
Wherein the weight parts of the hydrophobic nano filler powder and the hydrophobic nano silicon dioxide are respectively 2 parts and 2 parts; the room temperature reaction time is 1h, and the stirring rotating speed is 400r/min; the drying condition is that the oven is at 70 ℃ for 10 hours; the hot pressing temperature is 90-100 ℃; preferably, the hot pressing temperature is 85 ℃.
Further, the preparation method of the hydrophobic nano-filler comprises the following steps:
dissolving a hydrophobic carbon nano tube and hydrophobic nano silicon dioxide in an ethanol solution, stirring for 5-7 hours at room temperature, adjusting the pH value of the solution to be neutral after the reaction is completed, and carrying out suction filtration and drying on the obtained solution to obtain hydrophobic nano filler powder;
wherein the mass ratio of the hydrophobic carbon nano tube to the hydrophobic nano silicon dioxide is 1:1;
the stirring speed was 300r/min.
Preferably, according to embodiments of the present invention, H is utilized having molecular weights of 3000 and 1000, respectively 2 N-PDMS-NH 2 Synthesizing two kinds of paint for raw materials, and mixing the two kinds of paint in a proportion to obtain the paint with hydrophobicity, ice-repellent property and self-healing capability, wherein the mixing proportion is 0-3:4-0; preferably, the mixing ratios are 3:0, 0:3, 3:1, 3:2, 3:3 and 3:4, respectively.
The invention also provides the use of the coating with hydrophobicity, icephobicity and self-healing capability, including the use in the preparation of a material or a coating of a material with hydrophobicity, icephobicity or/and self-healing capability.
Further, the application comprises application in a super-hydrophobic icephobic self-healing coating, a self-healing waterproof adhesive tape or a protective layer of a material which is easy to wet and corrode.
The invention has the following beneficial effects:
(1) The invention has the advantages of low cost of raw materials, simple manufacturing method and short manufacturing period. The invention provides an intrinsic healing material which has self-healing characteristics of inexhaustible materials and is more suitable for materials with long service life.
(2) The self-healing function is introduced into the icephobic material, which is an effective strategy for solving the linkage effect caused by mechanical damage to the material, and is a practical method for improving the durability of the surface hydrophobic icephobic material. According to the invention, the Polydimethylsilane (PDMS) with high flexibility and hydrophobicity is adopted as a chain segment, the prepared elastomer has a lower elastic modulus and a higher water contact angle, the modified UPy-NCO is added for end sealing, the number of hydrogen bonds is increased, the coating has superhydrophobicity and ice-repellent property and rapid self-healing property in the atmosphere and under water, and the added hydrophobic nano silicon dioxide is also helpful for further improving the hydrophobic property of the coating. Meanwhile, the mechanical performance of the material can be recovered by more than 90% in 5h without external extra stimulation conditions; the adhesive has larger adhesive strength to various materials; the prepared polyurethane coating can be repaired and re-adhered by itself after being destroyed, and a new replacement is not needed, so that the service life is prolonged; can be used for self-repairing metal rust-proof layers and the like.
(3) The polyurethane coating prepared by the invention has self-healing performance similar to that of the environment in the atmosphere under water, has stronger adhesiveness, and can be used as a self-repairing waterproof coating to be used in various environment states. The polyurethane coating of the invention has strong advantages in mechanical properties and self-repairing properties.
(4) According to the invention, the hydrophobic carbon nano tube and the hydrophobic nano silicon dioxide particles are mixed, certain structural fluctuation is formed through mutual combination and interlocking of the hydrophobic carbon nano tube and the hydrophobic nano silicon dioxide particles, and the low surface energy of each component is added, so that the stable and durable super-hydrophobic coating is obtained, the anti-icing function is realized, the icing time can be delayed, and the ice layer is easier to remove.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of the hydrophobic icephobic self-healing polyurethane material according to the invention.
FIG. 2 is a flow chart of the preparation of the hydrophobic nanofiller according to the present invention (left panel) and the phenomenon of the hydrophobic nanofiller in water (right panel).
FIG. 3 is a sample graph of the hydrophobic icephobic self-healing polyurethane material prepared according to the present invention, from left to right, H having molecular weights of 3000 and 1000, respectively 2 N-PDMS-NH 2 The coating prepared by synthesizing two products according to the proportion of 3:0, 3:1, 3:2, 3:3, 3:4 and 0:3 for raw materials.
FIG. 4 is a schematic diagram showing the self-healing property test of a sample of the hydrophobic icephobic self-healing polyurethane material prepared according to the present invention, and FIG. A is H with molecular weights of 3000 and 1000, respectively 2 N-PDMS-NH 2 The healing efficiency of the coatings prepared according to different mixing ratios for raw material synthesis of the two products varies with time, and graph B is H with molecular weights of 3000 and 1000 respectively 2 N-PDMS-NH 2 Two products were synthesized for the starting materials according to 3:0 ratio of contact angle at each time point of the prepared coating.
FIG. 5 is a schematic representation of a hydrophobicity test of a coating sample prepared according to the present invention.
Fig. 6 is a schematic diagram showing the icephobic performance test of the sample provided in example 5 of the present invention.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the following detailed description of the preferred embodiments of the present invention is provided, but the following embodiments do not limit the scope of the present invention.
In the examples of the present invention, processes are not described in any more detail by conventional experimental methods, and those skilled in the art can understand and easily implement the processes according to the product specification or the basic knowledge of the art, so that the detailed description will not be given.
Example 1:
(1) Preparation of hydrophobic nanofiller powders
13g of hydrophobic carbon nano tube and 13g of hydrophobic nano silicon dioxide are dissolved in 50g of ethanol solution, the stirring speed is 300r/min at room temperature, the pH value of the solution is required to be adjusted to be neutral after the reaction is completed, the obtained solution is subjected to suction filtration and drying to obtain hydrophobic nano filler powder, part of the hydrophobic nano filler powder is taken to be placed in water, the phenomenon is observed and recorded, and the result shows that the powder can be seen to float on the water surface and good hydrophobicity is shown as shown in figure 2.
(2) Preparation of coatings with hydrophobicity, icephobicity and self-healing ability
15g of H with a molecular weight of 3000 are weighed out 2 N-PDMS-NH 2 And 50g of tetrahydrofuran were added to a three-necked flask and mixed, 1.7g of IPDI and 20g of tetrahydrofuran were weighed and mixed at the same time, and the resulting solution was mixed and stirred in an oil bath at 25℃for 48 hours until the reaction was completed. 4g UPy-NCO is weighed and added into the three-necked flask, the temperature of an oil bath pot is raised to 80 ℃ for stirring reaction, the stirring rotation speed is 400r/min, and the reaction is carried out for 12 hours until the reaction is complete. Taking out the solution for centrifugal treatment, adding 2g of hydrophobic carbon nanotube powder and 2g of hydrophobic nano silicon dioxide into supernatant obtained after centrifugation, stirring at room temperature for 1h for reaction, stirring at the speed of 400r/min, and bottling and placing the solution after the reaction is completed.
15g of H with a molecular weight of 1000 are weighed out 2 N-PDMS-NH 2 And 50g of tetrahydrofuran were added to a three-necked flask and mixed, and 0.9g of IPDI and 20g of tetrahydrofuran were weighed and mixed at the same time, and the resulting solution was mixed and stirred in an oil bath at 25℃for 48 hours until the reaction was completed. 4g UPy-NCO is weighed and added into the three-necked flask, the temperature of an oil bath pot is raised to 80 ℃ for stirring reaction, the stirring rotation speed is 400r/min, and the reaction is carried out for 12 hours until the reaction is complete. Taking out the solution for centrifugal treatment, adding 2g of hydrophobic carbon nanotube powder and 2g of hydrophobic nano silicon dioxide into supernatant obtained after centrifugation, stirring at room temperature for 1h for reaction, stirring at the speed of 400r/min, and bottling and placing the solution after the reaction is completed.
The above-mentioned raw material H 2 N-PDMS-NH 2 The products with molecular weights of 3000 and 1000 are respectively prepared, the products are stirred for 10min in an ultrasonic instrument according to the mass ratio of 0:3 for uniform mixing, the mixed solution is taken out for reverse molding, the mixed solution is put into a 70 ℃ oven for drying, and then the sample is taken out for hot pressing treatment, wherein the preparation method comprises the following steps ofThe hot pressing temperature is 95 ℃, and the coating can be obtained.
(3) The coatings were tested for self-healing, hydrophobic and icephobic properties, respectively:
in the self-healing performance test, after a sample is irradiated for 30min under ultraviolet light with the wavelength of 365-400 nm, the sample is placed in a 60 ℃ oven for 2h, and the contact angles before and after the sample are respectively measured, so that the healing rate of the sample is 98%, and the sample can be proved to have excellent self-healing performance; in the hydrophobic property test, the contact angle of the sample is measured to be 109.8 degrees, which indicates that the sample has better hydrophobic property.
Example 2:
(1) Preparation of hydrophobic nanofiller powders
13g of hydrophobic carbon nano tube and 13g of hydrophobic nano silicon dioxide are dissolved in 50g of ethanol solution, the stirring speed is 300r/min at room temperature, the pH value of the solution is required to be adjusted to be neutral after the reaction is completed, the obtained solution is subjected to suction filtration and drying to obtain hydrophobic nano filler powder, and part of the hydrophobic nano filler powder is taken to be placed in water, so that the powder can be seen to float on the water surface, and good hydrophobicity is shown.
(2) Preparation of coatings with hydrophobicity, icephobicity and self-healing ability
15g of H with a molecular weight of 3000 are weighed out 2 N-PDMS-NH 2 And 50g of tetrahydrofuran were added to a three-necked flask and mixed, 1.7g of IPDI and 20g of tetrahydrofuran were weighed and mixed at the same time, and the resulting solution was mixed and stirred in an oil bath at 20℃for 50 hours until the reaction was completed. 4g UPy-NCO is weighed and added into the three-necked flask, the temperature of an oil bath pot is raised to 75 ℃ for stirring reaction, the stirring rotation speed is 400r/min, and the reaction is carried out for 13h until the reaction is complete. Taking out the solution for centrifugal treatment, adding 2g of hydrophobic carbon nanotube powder and 2g of hydrophobic nano silicon dioxide into supernatant obtained after centrifugation, stirring at room temperature for 1h for reaction, stirring at the speed of 400r/min, and bottling and placing the solution after the reaction is completed.
15g of H with a molecular weight of 1000 are weighed out 2 N-PDMS-NH 2 Mixing with 50g tetrahydrofuran in a three-necked flask, simultaneously weighing 0.9g IPDI and 20g tetrahydrofuran, mixing, stirring the obtained solution in an oil bath at 20deg.C for 50hUntil the reaction was complete. 4g UPy-NCO is weighed and added into the three-necked flask, the temperature of an oil bath pot is raised to 75 ℃ for stirring reaction, the stirring rotation speed is 400r/min, and the reaction is carried out for 13h until the reaction is complete. Taking out the solution for centrifugal treatment, adding 2g of hydrophobic carbon nanotube powder and 2g of hydrophobic nano silicon dioxide into supernatant obtained after centrifugation, stirring at room temperature for 1h for reaction, stirring at the speed of 400r/min, and bottling and placing the solution after the reaction is completed.
The above-mentioned raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 0:3, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 90 ℃, thus obtaining the coating.
Example 3:
(1) Preparation of hydrophobic nanofiller powders
13g of hydrophobic carbon nano tube and 13g of hydrophobic nano silicon dioxide are dissolved in 50g of ethanol solution, and are stirred at room temperature for 6 hours at the stirring speed of 300r/min, the pH value of the solution is required to be adjusted to be neutral after the reaction is completed, the obtained solution is subjected to suction filtration and drying to obtain hydrophobic nano filler powder, and part of the hydrophobic nano filler powder is taken to be placed in water, so that the powder can be seen to float on the water surface, and good hydrophobicity is shown.
(2) Preparation of coatings with hydrophobicity, icephobicity and self-healing ability
15g of H with a molecular weight of 3000 are weighed out 2 N-PDMS-NH 2 And 50g of tetrahydrofuran were added to a three-necked flask and mixed, 1.7g of IPDI and 20g of tetrahydrofuran were weighed and mixed at the same time, and the resulting solution was mixed and stirred in an oil bath at 30℃for 46 hours until the reaction was completed. 4g UPy-NCO is weighed and added into the three-necked flask, the temperature of an oil bath pot is raised to 85 ℃ for stirring reaction, the stirring rotation speed is 400r/min, and the reaction is carried out for 11h until the reaction is complete. Taking out the solution for centrifugal treatment, adding 2g of hydrophobic carbon nanotube powder and 2g of hydrophobic nano silicon dioxide into supernatant obtained after centrifugation, stirring at room temperature for 1h for reaction, stirring at the speed of 400r/min, and bottling and placing the solution after the reaction is completed.
15g of H with a molecular weight of 1000 are weighed out 2 N-PDMS-NH 2 And 50g of tetrahydrofuran were added to a three-necked flask and mixed, and 0.9g of IPDI and 20g of tetrahydrofuran were weighed and mixed at the same time, and the resulting solution was mixed and stirred in an oil bath at 30℃for 46 hours until the reaction was completed. 4g UPy-NCO is weighed and added into the three-necked flask, the temperature of an oil bath pot is raised to 85 ℃ for stirring reaction, the stirring rotation speed is 400r/min, and the reaction is carried out for 11h until the reaction is complete. Taking out the solution for centrifugal treatment, adding 2g of hydrophobic carbon nanotube powder and 2g of hydrophobic nano silicon dioxide into supernatant obtained after centrifugation, stirring at room temperature for 1h for reaction, stirring at the speed of 400r/min, and bottling and placing the solution after the reaction is completed.
The above-mentioned raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 0:3, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 100 ℃, thus obtaining the coating.
Example 4:
step (1) and step (2) are the same as in example 1, except that:
raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 3:0, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 95 ℃ to obtain the coating.
The coatings were tested for self-healing, hydrophobic and icephobic properties, respectively:
in the self-healing performance test, after a sample is irradiated for 30min under ultraviolet light with the wavelength of 365-400 nm, the sample is placed in a 60 ℃ oven for 2h, and the contact angles before and after the sample are respectively measured, so that the healing rate of the sample is 98%, and the sample can be proved to have excellent self-healing performance; in the hydrophobic property test, the contact angle of the sample is 110.0 degrees, which indicates that the sample has better hydrophobic property.
Example 5:
step (1) and step (2) are the same as in example 1, except that:
raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 3:1, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 95 ℃, thus obtaining the coating.
The coatings were tested for self-healing, hydrophobic and icephobic properties, respectively:
in the self-healing performance test, after a sample is irradiated for 30min under ultraviolet light with the wavelength of 365-400 nm, the sample is placed in a 60 ℃ oven for 2h, and the contact angles before and after the sample are respectively measured, so that the healing rate of the sample is 94%, and the sample can be proved to have excellent self-healing performance; in the hydrophobic property test, the contact angle of the sample is 113.8 degrees, which shows that the sample has better hydrophobic property. Since the ice-repellent performance was also best with the maximum contact angle of the sample at the ratio of 3:1, the samples currently selected for the comparative example of 3:1 were tested for ice adhesion strength by vertical shear experiments, and as can be seen from FIG. 6, the coating had a lower ice adhesion strength of 38.3.+ -. 0.5kPa, well below the defined anti-icing threshold (< 100 kPa), and well below the similar thickness of commercial silica gel (Sylgard 184:169.6.+ -. 3.3 kPa), indicating excellent ice-repellent performance.
Example 6:
step (1) and step (2) are the same as in example 1, except that:
raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 3:2, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 95 ℃, thus obtaining the coating.
The coatings were tested for self-healing, hydrophobic and icephobic properties, respectively:
in the self-healing performance test, after a sample is irradiated for 30min under ultraviolet light with the wavelength of 365-400 nm, the sample is placed in a 60 ℃ oven for 2h, and the contact angles before and after the sample are respectively measured, so that the healing rate of the sample is 99%, and the sample can be proved to have excellent self-healing performance; in the hydrophobic property test, the contact angle of the sample is 108.2 degrees, which indicates that the sample has better hydrophobic property.
Example 7:
step (1) and step (2) are the same as in example 1, except that:
raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 3:3, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 95 ℃ to obtain the coating.
The coatings were tested for self-healing, hydrophobic and icephobic properties, respectively:
in the self-healing performance test, after a sample is irradiated for 30min under ultraviolet light with the wavelength of 365-400 nm, the sample is placed in a 60 ℃ oven for 2h, and the contact angles before and after the sample are respectively measured, so that the healing rate of the sample is 84%, and the sample can be proved to have excellent self-healing performance; in the hydrophobic property test, the contact angle of the sample was measured to be 89.3 °, and it can be seen that the contact angle was greatly reduced, indicating the reduction of the hydrophobic property.
Example 8:
step (1) and step (2) are the same as in example 1, except that:
raw material H 2 N-PDMS-NH 2 And (3) uniformly mixing the products prepared by the molecular weights of 3000 and 1000 respectively in an ultrasonic instrument for 10min according to the mass ratio of 3:4, taking out the mixed solution, pouring the mixed solution, putting the mixed solution into a 70 ℃ oven for drying, taking out the sample, and carrying out hot pressing treatment, wherein the hot pressing temperature is 95 ℃, thus obtaining the coating.
The coatings were tested for self-healing, hydrophobic and icephobic properties, respectively:
in the self-healing performance test, after a sample is irradiated for 30min under ultraviolet light with the wavelength of 365-400 nm, the sample is placed in a 60 ℃ oven for 2h, and the contact angles before and after the sample are respectively measured, so that the healing rate of the sample is 97%, and the sample can be proved to have excellent self-healing performance; in the hydrophobic property test, the contact angle of the sample was 80.5 °, and it can be seen that the contact angle was greatly reduced, indicating the reduction of the hydrophobic property.
It should be understood that although the present disclosure has been described in terms of various embodiments, not every embodiment is provided with a separate technical solution, and this description is for clarity only, and those skilled in the art should consider the disclosure as a whole, and the technical solutions in the various embodiments may be combined appropriately to form other embodiments that will be understood by those skilled in the art.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a coating having hydrophobicity, icephobicity and self-healing capability, said method comprising:
(1) Respectively dissolving bis (3-aminopropyl) end-capped poly (dimethyl siloxane) and isophorone diisocyanate in tetrahydrofuran, mixing the obtained solutions, and stirring for reaction until the reaction is complete;
(2) Weighing 2- (6-isocyanatohexylaminocarbonylamino) -6-methyl-4-pyrimidinone, adding into the mixed solution obtained in the step (1), stirring and reacting after the temperature is raised until the reaction is completed, centrifuging, and taking supernatant obtained after centrifuging;
(3) Adding the hydrophobic nano filler powder and the hydrophobic nano silicon dioxide into the supernatant obtained in the step (2), and continuing to stir at room temperature for reaction until the reaction is complete; and drying the product and hot-pressing to obtain the coating.
2. The method according to claim 1, wherein the bis (3-aminopropyl) terminated poly (dimethylsiloxane) and tetrahydrofuran in step (1) are 15 parts by mass and 50 parts by mass, respectively, and the isophorone diisocyanate and tetrahydrofuran are 1.7 parts by mass and 20 parts by mass, respectively, and the stirring reaction condition is 20 to 30 ℃ for 46 to 50 hours.
3. The method of claim 1, wherein the bis (3-aminopropyl) -terminated poly (dimethylsiloxane) in step (1) has a molecular weight of 3000 or 1000.
4. The method according to claim 1, wherein the mass fraction of 2- (6-isocyanatohexylaminocarbonylamino) -6-methyl-4-pyrimidinone in step (2) is 4 parts; the reaction condition is that stirring reaction is carried out for 11-13 h at 75-85 ℃.
5. The method according to claim 1, wherein in the step (3), the hydrophobic nano filler powder and the hydrophobic nano silica are 2 parts by mass, the room temperature reaction time is 1h, the drying condition is 70 ℃ oven for 10h, and the hot pressing temperature is 90-100 ℃.
6. The method according to claim 1, wherein the preparation method of the hydrophobic nanofiller in step (3) comprises the steps of:
dissolving the hydrophobic carbon nano tube and the hydrophobic nano silicon dioxide in ethanol solution, stirring at room temperature for reaction for 5-7 h, adjusting the pH value of the solution to be neutral after the reaction is completed, and carrying out suction filtration and drying on the obtained solution to obtain the hydrophobic nano filler powder.
7. The method of claim 6, wherein the mass ratio of hydrophobic carbon nanotubes to hydrophobic nanosilica is 1:1; the stirring speed was 300r/min.
8. The method according to any one of claims 1 to 7, wherein the coating with hydrophobicity, icephobicity and self-healing capacity prepared by the method is obtained by synthesizing two coatings by taking H2N-PDMS-NH2 with molecular weights of 3000 and 1000 respectively as raw materials and then mixing the two coatings in a ratio of 0-3:4-0; preferably, the mixing ratios are 3:0, 0:3, 3:1, 3:2, 3:3 and 3:4, respectively.
9. A coating having hydrophobicity, icephobicity and self-healing ability prepared according to any one of claims 1 to 8.
10. Use of a coating prepared according to the method of any one of claims 1-8 or a coating according to claim 9 for preparing a material or material coating having hydrophobic, icephobic or/and self-healing capabilities; preferably, the application comprises application in a super-hydrophobic icephobic self-healing coating, a self-healing waterproof adhesive tape or a protective layer of a material which is easy to wet and corrode.
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