CN111826075A - Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof - Google Patents
Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof Download PDFInfo
- Publication number
- CN111826075A CN111826075A CN202010635556.3A CN202010635556A CN111826075A CN 111826075 A CN111826075 A CN 111826075A CN 202010635556 A CN202010635556 A CN 202010635556A CN 111826075 A CN111826075 A CN 111826075A
- Authority
- CN
- China
- Prior art keywords
- parts
- modified polyurethane
- fluorine
- silicone oil
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002545 silicone oil Polymers 0.000 claims abstract description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- HBCBCEPGGSBSMF-UHFFFAOYSA-N 4-(4-sulfanylanilino)benzenethiol Chemical compound Sc1ccc(Nc2ccc(S)cc2)cc1 HBCBCEPGGSBSMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 11
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 15
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000003446 memory effect Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229920000136 polysorbate Polymers 0.000 abstract description 4
- 229910018557 Si O Inorganic materials 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 11
- 230000006870 function Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- -1 vinyl hydroxyl Chemical group 0.000 description 1
Images
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
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a self-repairing organic fluorine-silicon modified polyurethane waterproof coating and a preparation method thereof, wherein the self-repairing organic fluorine-silicon modified polyurethane waterproof coating comprises the following raw materials in parts by mass: 60-80 parts of polytetramethylene ether glycol, 15-30 parts of perfluoropolyether glycol, 40-60 parts of isophorone diisocyanate, 20-35 parts of 4,4' -dithio diphenylamine, 20-30 parts of fluorine-containing hydroxyl silicone oil, 30-40 parts of tetrahydrofuran, 0.8-2 parts of dibutyltin dilaurate, 802-3 parts of tween, 15-20 parts of nano calcium carbonate, 5-10 parts of nano calcium hydroxy phosphate and 10-20 parts of deionized water; the preparation method comprises the following steps: s1: preparing a polyurethane prepolymer; s2: dissolving 4,4' -dithiodiphenylamine and fluorine-containing vinyl silicone oil in tetrahydrofuran, adding a polyurethane prepolymer, and stirring and reacting at 60 ℃ for 3-6 hours in a nitrogen atmosphere; s3: preparing the organic fluorine-silicon modified polyurethane waterproof coating. The invention combines disulfide bond, shape memory effect and organic fluorine-silicon modification, and obviously improves the performances of hydrophobicity, oleophobicity, high and low temperature resistance, weather resistance, corrosion resistance and the like by introducing S-S, C-F, Si-O bond into a polyurethane molecular chain.
Description
Technical Field
The invention belongs to the technical field of waterproof materials, and particularly relates to a self-repairing organic fluorine-silicon modified polyurethane waterproof coating and a preparation method thereof.
Background
The self-repairing polyurethane material is a bionic intelligent material with high elasticity and self-repairing capability, and the self-repairing purpose is realized mainly by introducing a reversible valence covalent bond, such as a reversible disulfide bond, a reversible acylhydrazone bond and a Diels-Alder reaction, and under the stimulation of external conditions such as light, heat and the like, cracks generated by polyurethane are repaired through recombination of the covalent bond, so that the expansion of the cracks is avoided.
The organic fluorine-silicon material is a novel material which is organically synthesized by carrying out molecular structure design on organic fluorine and organic silicon materials, has the advantages of organic fluorine and organic silicon, and has excellent chemical properties such as high and low temperature resistance, super-hydrophobic and oleophobic property, photo-thermal resistance, weather resistance and the like.
In the prior art, although a synthesis method of various self-repairing polyurethane materials or a method of modifying polyurethane with organic fluorine silicon is disclosed, relevant documents or patents for further modifying polyurethane containing disulfide bonds by using organic fluorine silicon to enable the polyurethane to have functions of repeatable self-repairing and shape memory effect are not disclosed, for example, a patent with the application number of CN201910799259.X discloses a disulfide bond and hydrogen bond dual self-repairing polyurethane coating for invisible car clothes and a preparation method thereof.
In order to further improve the performances of the disulfide bond polyurethane such as hydrophobicity, oleophobicity, high and low temperature resistance, weather resistance, self-repairing and the like and expand the application range of the disulfide bond polyurethane, the invention utilizes the copolymerization of polytetramethylene ether glycol, perfluoropolyether glycol, isophorone diisocyanate, 4' -dithiodiphenylamine and fluorine-containing hydroxyl silicone oil to prepare the organic fluorine-silicon modified polyurethane waterproof coating with shape memory effect, self-repairing, anti-fouling and waterproof functions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a self-repairing organic fluorine-silicon modified polyurethane waterproof coating and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
the self-repairing organic fluorine-silicon modified polyurethane waterproof coating comprises the following raw materials in parts by mass:
preferably, the preparation method of the fluorine-containing hydroxyl silicone oil comprises the following steps: uniformly mixing trifluoropropylmethyl cyclotrisiloxane, tridecafluorooctyltriethoxysilane and hydroxyl silicone oil, then dropwise adding an ethylenediamine catalyst, introducing nitrogen, stirring and reacting at 100-115 ℃ for 3-8 h, and rotationally evaporating ethylenediamine at 120 ℃ to obtain the fluorine-containing hydroxyl silicone oil.
Preferably, the mass ratio of the trifluoropropylmethyl cyclotrisiloxane to the tridecafluorooctyltriethoxysilane to the hydroxyl silicone oil to the ethylenediamine catalyst is 1: (0.4-0.8): (1.8-3): (0.01-0.05).
The preparation method of the self-repairing organic fluorine-silicon modified polyurethane waterproof coating comprises the following steps:
s1: preparing a polyurethane prepolymer: mixing polytetramethylene ether glycol and perfluoropolyether glycol, dehydrating at 100-115 ℃ for 1-3 h in vacuum, cooling to 70-90 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and reacting for 3-6 h under the condition of heat preservation and stirring in a nitrogen atmosphere to obtain a polyurethane prepolymer;
s2: preparing organic fluorine-silicon modified polyurethane mixed liquid: dissolving 4,4' -dithiodiphenylamine and fluorine-containing vinyl silicone oil in tetrahydrofuran, adding a polyurethane prepolymer, and stirring and reacting at 60 ℃ for 3-6 hours in a nitrogen atmosphere to obtain a modified polyurethane mixed solution;
s3: preparing organic fluorine-silicon modified polyurethane waterproof paint: and (4) adding deionized water, tween 80, nano calcium carbonate and nano calcium hydroxy phosphate into the modified polyurethane mixed solution obtained in the step S2, and stirring and dispersing to obtain the organic fluorine-silicon modified polyurethane waterproof coating.
The invention has the beneficial effects that:
1. the invention combines the disulfide bond, the shape memory effect and the organic fluorine-silicon modification to prepare the modified polyurethane material with self-repairing, anti-fouling, waterproof and weather-proof properties, and uses-NH in 4,4' -dithiodiphenylamine2The addition polymerization reaction between the fluorine-containing hydroxyl silicone oil and-NCO introduces disulfide bonds, the self-repairing function of polyurethane is realized through repeated recombination of covalent bonds between sulfur atoms, the addition polymerization of-OH and-NCO in fluorine-containing hydroxyl silicone oil is utilized, C-F, Si-O bonds are introduced into the molecular chain of polyurethane, the performances of hydrophobicity, oleophobicity, high and low temperature resistance, weather resistance, chemical corrosion resistance and the like are obviously improved, and simultaneously, -NH2The water resistance and the mechanical property of the polyurethane are improved to a certain extent by a urea bond generated by the action of-NCO and an ester bond generated by the action of-OH and-NCO; in addition, the polyurethane with the shape memory effect is prepared by using polytetramethylene ether glycol, perfluoropolyether glycol and isophorone diisocyanate as raw materials, and the shape effect is used as an auxiliary restoring force to further accelerate the self-repairing efficiency of the material.
2. According to the invention, trifluoropropylmethyl cyclotrisiloxane and tridecafluorooctyltriethoxysilane are used for the first time to modify vinyl hydroxyl silicone oil, the surface tension of the hydroxyl silicone oil is reduced, and simultaneously, the function of a hydroxyl silicone oil coupling agent is endowed, so that nano calcium carbonate and nano calcium hydroxy phosphate are stably dispersed in polyurethane emulsion, and in addition, hydroxyl contained in the nano calcium hydroxy phosphate can react with unreacted-NCO in the polyurethane emulsion and then grafted on a polyurethane molecular chain, and the stability of the coating is further improved.
Drawings
FIG. 1 is a flow chart of a preparation method of the self-repairing organic fluorine-silicon modified polyurethane waterproof coating.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
The preparation method of the self-repairing organic fluorine-silicon modified polyurethane waterproof coating comprises the following steps:
s1: preparing fluorine-containing hydroxyl silicone oil: uniformly mixing trifluoropropylmethyl cyclotrisiloxane, tridecafluorooctyltriethoxysilane and hydroxyl silicone oil, dropwise adding an ethylenediamine catalyst, introducing nitrogen, stirring at 100 ℃ for reaction for 3 hours, and rotationally evaporating ethylenediamine at 120 ℃ to obtain the fluorine-containing hydroxyl silicone oil; the mass ratio of the trifluoropropylmethyl cyclotrisiloxane to the tridecafluorooctyltriethoxysilane to the hydroxyl silicone oil to the ethylenediamine catalyst is 1: 0.4: 1.8: 0.01;
s2: preparing materials: weighing 60 parts of polytetramethylene ether glycol, 15 parts of perfluoropolyether glycol, 40 parts of isophorone diisocyanate, 20 parts of 4,4' -dithio diphenylamine, 20 parts of fluorine-containing hydroxyl silicone oil, 30 parts of tetrahydrofuran, 0.8 part of dibutyltin dilaurate, 802 parts of tween, 15 parts of nano calcium carbonate, 5 parts of nano calcium hydroxy phosphate and 10-20 parts of deionized water according to parts by mass;
s3: preparing a polyurethane prepolymer: mixing polytetramethylene ether glycol and perfluoropolyether glycol, dehydrating at 100 ℃ for 1.5h in vacuum, cooling to 70 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and reacting for 3h under the condition of nitrogen gas and stirring at a constant temperature to obtain a polyurethane prepolymer;
s4: preparing organic fluorine-silicon modified polyurethane mixed liquid: dissolving 4,4' -dithiodiphenylamine and fluorine-containing vinyl silicone oil in tetrahydrofuran, adding a polyurethane prepolymer, and stirring and reacting at 60 ℃ for 3 hours under a nitrogen atmosphere to obtain a modified polyurethane mixed solution;
s5: preparing organic fluorine-silicon modified polyurethane waterproof paint: and (4) adding deionized water, tween 80, nano calcium carbonate and nano calcium hydroxy phosphate into the modified polyurethane mixed solution obtained in the step S4, and stirring and dispersing to obtain the organic fluorine-silicon modified polyurethane waterproof coating.
Example 2
The preparation method of the self-repairing organic fluorine-silicon modified polyurethane waterproof coating comprises the following steps:
s1: preparing fluorine-containing hydroxyl silicone oil: uniformly mixing trifluoropropylmethyl cyclotrisiloxane, tridecafluorooctyltriethoxysilane and hydroxyl silicone oil, dropwise adding an ethylenediamine catalyst, introducing nitrogen, stirring at 110 ℃ for 5 hours to react, and rotationally evaporating ethylenediamine at 120 ℃ to obtain the fluorine-containing hydroxyl silicone oil; the mass ratio of the trifluoropropylmethyl cyclotrisiloxane to the tridecafluorooctyltriethoxysilane to the hydroxyl silicone oil to the ethylenediamine catalyst is 1: 0.6: 2.4: 0.03;
s2: preparing materials: weighing 70 parts of polytetramethylene ether glycol, 25 parts of perfluoropolyether glycol, 50 parts of isophorone diisocyanate, 27 parts of 4,4' -dithio diphenylamine, 25 parts of fluorine-containing hydroxyl silicone oil, 35 parts of tetrahydrofuran, 1.5 parts of dibutyltin dilaurate, 802.5 parts of tween, 18 parts of nano calcium carbonate, 8 parts of nano calcium hydroxy phosphate and 15 parts of deionized water according to parts by mass;
s3: preparing a polyurethane prepolymer: mixing polytetramethylene ether glycol and perfluoropolyether glycol, dehydrating at 110 ℃ for 2h in vacuum, cooling to 80 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and reacting for 5h under the condition of heat preservation and stirring in a nitrogen atmosphere to obtain a polyurethane prepolymer;
s4: preparing organic fluorine-silicon modified polyurethane mixed liquid: dissolving 4,4' -dithiodiphenylamine and fluorine-containing vinyl silicone oil in tetrahydrofuran, adding a polyurethane prepolymer, and stirring and reacting at 60 ℃ for 5 hours under a nitrogen atmosphere to obtain a modified polyurethane mixed solution;
s5: preparing organic fluorine-silicon modified polyurethane waterproof paint: and (4) adding deionized water, tween 80, nano calcium carbonate and nano calcium hydroxy phosphate into the modified polyurethane mixed solution obtained in the step S4, and stirring and dispersing to obtain the organic fluorine-silicon modified polyurethane waterproof coating.
Example 3
The preparation method of the self-repairing organic fluorine-silicon modified polyurethane waterproof coating comprises the following steps:
s1: preparing fluorine-containing hydroxyl silicone oil: uniformly mixing trifluoropropylmethyl cyclotrisiloxane, tridecafluorooctyltriethoxysilane and hydroxyl silicone oil, dropwise adding an ethylenediamine catalyst, introducing nitrogen, stirring at 115 ℃ for reacting for 8 hours, and rotationally evaporating ethylenediamine at 120 ℃ to obtain the fluorine-containing hydroxyl silicone oil; the mass ratio of the trifluoropropylmethyl cyclotrisiloxane to the tridecafluorooctyltriethoxysilane to the hydroxyl silicone oil to the ethylenediamine catalyst is 1: 0.8: 3: 0.05;
s2: preparing materials: weighing 80 parts of polytetramethylene ether glycol, 30 parts of perfluoropolyether glycol, 60 parts of isophorone diisocyanate, 35 parts of 4,4' -dithio diphenylamine, 30 parts of fluorine-containing hydroxyl silicone oil, 40 parts of tetrahydrofuran, 2 parts of dibutyltin dilaurate, 803 parts of tween, 20 parts of nano calcium carbonate, 10 parts of nano calcium hydroxy phosphate and 20 parts of deionized water according to parts by mass;
s3: preparing a polyurethane prepolymer: mixing polytetramethylene ether glycol and perfluoropolyether glycol, dehydrating at 115 ℃ for 3h in vacuum, cooling to 90 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and reacting for 6h under the condition of heat preservation and stirring in a nitrogen atmosphere to obtain a polyurethane prepolymer;
s4: preparing organic fluorine-silicon modified polyurethane mixed liquid: dissolving 4,4' -dithiodiphenylamine and fluorine-containing vinyl silicone oil in tetrahydrofuran, adding a polyurethane prepolymer, and stirring and reacting at 60 ℃ for 6 hours under a nitrogen atmosphere to obtain a modified polyurethane mixed solution;
s5: preparing organic fluorine-silicon modified polyurethane waterproof paint: and (4) adding deionized water, tween 80, nano calcium carbonate and nano calcium hydroxy phosphate into the modified polyurethane mixed solution obtained in the step S4, and stirring and dispersing to obtain the organic fluorine-silicon modified polyurethane waterproof coating.
Comparative example 1
The same as in example 1, except that: the preparation process does not add fluorine-containing hydroxyl silicone oil and perfluoropolyether diol.
Comparative example 2
The same as in example 1, except that: 4,4' -dithiodiphenylamine is not added in the preparation process.
Uniformly coating the polyurethane waterproof coatings prepared in the examples 1-3 and the comparative examples 1-2 on the surface of a glass substrate, drying and curing, and measuring the water contact angle theta of the surface of a coating film by using a JC2000C type dynamic contact angle measuring instrument; rubbing the surface of the coating film by using a 15N scraping assembly to ensure that the surface of the coating film is completely scraped, taking the area of the coating film as an initial scratch damage area S1, performing heat treatment at 100 ℃ for 2 hours, measuring the treated scratch damage area S2, and calculating self-repairing efficiency according to a formula of 100% × (S1-S2)/S1; and further measured according to GBT19250-2013 polyurethane waterproof paint, the test results are shown in the following table:
as can be seen from the above table, the modified polyurethane material capable of self-repairing, anti-fouling, waterproof and weather-resistant is prepared by combining disulfide bond, shape memory effect and organic fluorine-silicon modification, and the-NH in 4,4' -dithiodiphenylamine is utilized2The addition polymerization reaction between the fluorine-containing hydroxyl silicone oil and-NCO introduces disulfide bonds, the self-repairing function of polyurethane is realized through repeated recombination of covalent bonds between sulfur atoms, the addition polymerization of-OH and-NCO in fluorine-containing hydroxyl silicone oil is utilized, C-F, Si-O bonds are introduced into the molecular chain of polyurethane, the performances of hydrophobicity, oleophobicity, high and low temperature resistance, weather resistance, chemical corrosion resistance and the like are obviously improved, and simultaneously, -NH2The water resistance and the mechanical property of the polyurethane are improved to a certain extent by a urea bond generated by the action of-NCO and an ester bond generated by the action of-OH and-NCO.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (4)
1. The self-repairing organic fluorine-silicon modified polyurethane waterproof coating is characterized by comprising the following raw materials in parts by mass:
2. the self-repairing organic fluorosilicone modified polyurethane waterproof coating of claim 1, which is characterized in that the preparation method of the fluorine-containing hydroxyl silicone oil comprises the following steps: uniformly mixing trifluoropropylmethyl cyclotrisiloxane, tridecafluorooctyltriethoxysilane and hydroxyl silicone oil, then dropwise adding an ethylenediamine catalyst, introducing nitrogen, stirring and reacting at 100-115 ℃ for 3-8 h, and rotationally evaporating ethylenediamine at 120 ℃ to obtain the fluorine-containing hydroxyl silicone oil.
3. The self-repairing organic fluorosilicone modified polyurethane waterproof coating of claim 2, wherein the mass ratio of trifluoropropylmethyl cyclotrisiloxane to tridecafluorooctyltriethoxysilane to hydroxyl silicone oil to ethylenediamine catalyst is 1: (0.4-0.8): (1.8-3): (0.01-0.05).
4. The preparation method of the self-repairing organic fluorine-silicon modified polyurethane waterproof coating as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
s1: preparing a polyurethane prepolymer: mixing polytetramethylene ether glycol and perfluoropolyether glycol, dehydrating at 100-115 ℃ for 1-3 h in vacuum, cooling to 70-90 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and reacting for 3-6 h under the condition of heat preservation and stirring in a nitrogen atmosphere to obtain a polyurethane prepolymer;
s2: preparing organic fluorine-silicon modified polyurethane mixed liquid: dissolving 4,4' -dithiodiphenylamine and fluorine-containing vinyl silicone oil in tetrahydrofuran, adding a polyurethane prepolymer, and stirring and reacting at 60 ℃ for 3-6 hours in a nitrogen atmosphere to obtain a modified polyurethane mixed solution;
s3: preparing organic fluorine-silicon modified polyurethane waterproof paint: and (4) adding deionized water, tween 80, nano calcium carbonate and nano calcium hydroxy phosphate into the modified polyurethane mixed solution obtained in the step S2, and stirring and dispersing to obtain the organic fluorine-silicon modified polyurethane waterproof coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010635556.3A CN111826075B (en) | 2020-07-03 | 2020-07-03 | Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010635556.3A CN111826075B (en) | 2020-07-03 | 2020-07-03 | Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111826075A true CN111826075A (en) | 2020-10-27 |
| CN111826075B CN111826075B (en) | 2021-09-21 |
Family
ID=72900090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010635556.3A Active CN111826075B (en) | 2020-07-03 | 2020-07-03 | Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111826075B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680082A (en) * | 2020-12-25 | 2021-04-20 | 广东炫丽新材料科技有限公司 | Preparation method of TPE (thermoplastic elastomer) anti-oil stain agent and anti-oil stain agent |
| CN112920632A (en) * | 2021-03-22 | 2021-06-08 | 上海先权光纤科技有限公司 | Heat-resistant photocuring optical fiber coating and preparation method thereof |
| CN114133525A (en) * | 2021-12-16 | 2022-03-04 | 胡先海 | Preparation method and application of self-repairing high-temperature-resistant polyurethane elastomer |
| CN114181605A (en) * | 2022-01-17 | 2022-03-15 | 雨中情防水技术集团股份有限公司 | Single-component water-based polyurethane waterproof coating and preparation method thereof |
| CN114957592A (en) * | 2022-04-21 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Polyurethane elastomer capable of self-healing blood environment and preparation method and application thereof |
| CN115094642A (en) * | 2022-02-22 | 2022-09-23 | 合肥柔性科天机器人材料有限公司 | Replaceable flexible robot skin preparation method |
| CN115368819A (en) * | 2022-07-08 | 2022-11-22 | 深圳市派恩新材料技术有限公司 | Fluorine-containing coating and preparation method and use method thereof |
| CN116656203A (en) * | 2023-08-02 | 2023-08-29 | 江西永通科技股份有限公司 | Coating composition with mildew-proof and antibacterial properties and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555192A (en) * | 2013-11-21 | 2014-02-05 | 武汉大学 | Organic silicon-modified water-based UV (ultraviolet) coating and preparation method thereof |
| CN103613993A (en) * | 2013-11-21 | 2014-03-05 | 武汉大学 | Hydroxyl silicone oil modified waterborne UV (Ultraviolet) printing ink and preparation method thereof |
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
| JP5732748B2 (en) * | 2010-05-31 | 2015-06-10 | 株式会社ニコン | Optical element paint, film, optical element and optical device |
| CN110982413A (en) * | 2019-12-16 | 2020-04-10 | 重庆致径路面材料有限公司 | Road paint and preparation method and using method thereof |
-
2020
- 2020-07-03 CN CN202010635556.3A patent/CN111826075B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5732748B2 (en) * | 2010-05-31 | 2015-06-10 | 株式会社ニコン | Optical element paint, film, optical element and optical device |
| CN103555192A (en) * | 2013-11-21 | 2014-02-05 | 武汉大学 | Organic silicon-modified water-based UV (ultraviolet) coating and preparation method thereof |
| CN103613993A (en) * | 2013-11-21 | 2014-03-05 | 武汉大学 | Hydroxyl silicone oil modified waterborne UV (Ultraviolet) printing ink and preparation method thereof |
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
| CN110982413A (en) * | 2019-12-16 | 2020-04-10 | 重庆致径路面材料有限公司 | Road paint and preparation method and using method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680082A (en) * | 2020-12-25 | 2021-04-20 | 广东炫丽新材料科技有限公司 | Preparation method of TPE (thermoplastic elastomer) anti-oil stain agent and anti-oil stain agent |
| CN112920632A (en) * | 2021-03-22 | 2021-06-08 | 上海先权光纤科技有限公司 | Heat-resistant photocuring optical fiber coating and preparation method thereof |
| CN112920632B (en) * | 2021-03-22 | 2022-11-15 | 上海先权光纤科技有限公司 | Heat-resistant photocuring optical fiber coating and preparation method thereof |
| CN114133525A (en) * | 2021-12-16 | 2022-03-04 | 胡先海 | Preparation method and application of self-repairing high-temperature-resistant polyurethane elastomer |
| CN114181605A (en) * | 2022-01-17 | 2022-03-15 | 雨中情防水技术集团股份有限公司 | Single-component water-based polyurethane waterproof coating and preparation method thereof |
| CN115094642A (en) * | 2022-02-22 | 2022-09-23 | 合肥柔性科天机器人材料有限公司 | Replaceable flexible robot skin preparation method |
| CN115094642B (en) * | 2022-02-22 | 2024-04-02 | 合肥柔性科天机器人材料有限公司 | Replaceable flexible robot skin preparation method |
| CN114957592A (en) * | 2022-04-21 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Polyurethane elastomer capable of self-healing blood environment and preparation method and application thereof |
| CN115368819A (en) * | 2022-07-08 | 2022-11-22 | 深圳市派恩新材料技术有限公司 | Fluorine-containing coating and preparation method and use method thereof |
| CN116656203A (en) * | 2023-08-02 | 2023-08-29 | 江西永通科技股份有限公司 | Coating composition with mildew-proof and antibacterial properties and preparation method thereof |
| CN116656203B (en) * | 2023-08-02 | 2023-10-27 | 江西永通科技股份有限公司 | Coating composition with mildew-proof and antibacterial properties and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111826075B (en) | 2021-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111826075B (en) | Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof | |
| CN105255348A (en) | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof | |
| CN104448183A (en) | Plant oil-based polyurethane composite material and preparation method thereof | |
| CN110499094B (en) | Graphene-modified waterborne polyurethane anticorrosive paint and preparation method thereof | |
| Zeng et al. | Facile fabrication of durable superhydrophobic and oleophobic surface on cellulose substrate via thiol-ene click modification | |
| CN107418420A (en) | A kind of hydrophobic polyurethane hybrid coating and preparation method thereof | |
| CN111849298B (en) | Organic fluorine-silicon/fluorine-containing acrylate modified polyurethane waterproof coating and preparation method thereof | |
| CN111434740A (en) | Ultraviolet-cured fluorine-containing polyurethane acrylate coating | |
| CN111171276B (en) | Modified graphene water-based polyurea resin and preparation method and application thereof | |
| Jiao et al. | Preparation and characterization of UV-curable urethane acrylate oligomers modified with cycloaliphatic epoxide resin | |
| CN110862765B (en) | Coating for surface of silicon rubber substrate and preparation method thereof | |
| CN114276519B (en) | Self-extinction waterborne polyurethane and preparation method thereof | |
| CN109796576B (en) | Glass fiber film forming agent and preparation method thereof | |
| CN109054476B (en) | Waterproof coating for zipper and preparation method thereof | |
| CN103396558A (en) | Vinyl-terminated fluorosilicone graft polymer, and preparation method and applications thereof | |
| CN110734533A (en) | terminal/side fluoroalkyl co-modified polyurethane nano hybrid emulsion and preparation method thereof | |
| CN114196304A (en) | Solvent-free fluorine-modified polyaspartic acid ester multifunctional heat-insulating coating | |
| Cai et al. | Preparation and surface properties of silicon-containing waterborne polyurethane functionalized with fluorine-containing acrylate and micro-nano silica | |
| CN111548731A (en) | Room-temperature self-repairing polycarbonate surface coating and preparation method thereof | |
| CN108753134B (en) | Water-based metallic paint and preparation method thereof | |
| CN114854304A (en) | Super-hydrophobic coating with environmental protection and antifouling performance | |
| CN112625578B (en) | Preparation method of micro-nano silicon dioxide/fluorinated polyurethane wear-resistant super-hydrophobic coating | |
| CN113354790A (en) | Fluorine-containing and phosphorus-containing waterborne polyurethane material and preparation method thereof | |
| CN112661933A (en) | Preparation method of reactive waterborne polyurethane | |
| CN110551288A (en) | Room-temperature self-repairing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 231533 Mahe Road, Weidang village, Tongda Town, Lujiang County, Hefei City, Anhui Province Patentee after: Anhui langkaiqi Technology Co.,Ltd. Address before: 231533 Mahe Road, Weidang village, Tongda Town, Lujiang County, Hefei City, Anhui Province Patentee before: ANHUI LENCAQI WATERPROOF TECHNOLOGY CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Self repairing organic fluorine silicon modified polyurethane waterproof coating and its preparation method Effective date of registration: 20231228 Granted publication date: 20210921 Pledgee: Lujiang County small and medium-sized enterprises financing Company limited by guarantee Pledgor: Anhui langkaiqi Technology Co.,Ltd. Registration number: Y2023980074957 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |