CN114752294A - Wear-resistant high-elasticity polyurethane coating - Google Patents
Wear-resistant high-elasticity polyurethane coating Download PDFInfo
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- CN114752294A CN114752294A CN202210355261.XA CN202210355261A CN114752294A CN 114752294 A CN114752294 A CN 114752294A CN 202210355261 A CN202210355261 A CN 202210355261A CN 114752294 A CN114752294 A CN 114752294A
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- polyurethane coating
- wear
- diisocyanate
- silicone rubber
- modified silicone
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- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 32
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 32
- 239000004945 silicone rubber Substances 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000000839 emulsion Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 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 description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 3
- 239000013523 DOWSIL™ Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- FQEMARONUOAYGT-UHFFFAOYSA-N cyclohexa-1,5-dien-1-ol Chemical group OC1=CCCC=C1 FQEMARONUOAYGT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C09D175/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a wear-resistant high-elasticity polyurethane coating, which comprises modified silicone rubber microspheres, high-molecular-weight polyol, diisocyanate, a catalyst, polyethylene glycol, a hydroxyl-containing hydrophilic monomer, a solvent, organic amine and deionized water; the preparation method comprises the following steps: dehydrating high molecular weight polyol at 60-100 ℃ in vacuum, adding diisocyanate and a catalyst under the protection of nitrogen, and reacting for 3-4 hours at 50-95 ℃ in a heat preservation manner; adding polyethylene glycol, a hydrophilic monomer containing hydroxyl and a solvent, and reacting for 2-4 hours at the temperature of 50-90 ℃ in a heat preservation manner to prepare a polyurethane prepolymer; and cooling the prepolymer to 40-60 ℃, uniformly stirring and dispersing the prepolymer in deionized water containing organic amine to obtain a dispersion, and adding the modified silicone rubber microspheres into the dispersion to perform chain extension reaction to obtain the waterborne polyurethane emulsion. The coating obtained by the invention has the advantages of high elasticity, high wear resistance, high bonding force, no brittleness, no cracking and the like at low temperature.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a wear-resistant high-elasticity polyurethane coating.
Background
The elastic coating keeps higher elasticity, toughness and elongation in a certain temperature range, can effectively cover cracks when being coated on the surface of a base layer, changes correspondingly along with thermal expansion and cold contraction of a heat insulation system, and has good anti-cracking and anti-permeability properties. The resin used by the traditional elastic inner and outer wall paint is acrylic resin which is hot-bonded and cold-brittle, and when the paint is heated at high temperature in summer, the surface is seriously re-bonded, so that dust in the air is easily polluted, and the attractiveness of the coating is influenced; and the coating film is easy to become brittle in winter, thereby affecting the elongation and elasticity of the coating film and even causing cracking.
Mussel-like organisms are of great interest to biochemistry and materials scientists because of their broad spectrum of adhesion exhibited on a variety of surfaces that are wet and complex in construction. Through chemical analysis, the adhesive protein secreted by the mytilus edulis biological silk foot contains a large amount of 3, 4-dihydric phenol structures. The catechol structure can form strong hydrogen bond with hydroxyl on the surface of the substrate, and can form a complex with metal, and can form covalent bonds with a plurality of groups after being oxidized into quinone.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to prepare the polyurethane coating which has high elasticity, high wear resistance and high bonding force, is not brittle at low temperature and does not crack by introducing the modified silicon rubber microspheres as a chain extender.
The technical scheme adopted by the invention for solving the technical problem is as follows: a wear-resistant high-elasticity polyurethane coating comprises modified silicone rubber microspheres, high-molecular-weight polyol, diisocyanate, a catalyst, polyethylene glycol, a hydroxyl-containing hydrophilic monomer, a solvent, organic amine and deionized water; the preparation method of the polyurethane coating comprises the following steps:
s1, carrying out vacuum dehydration on high molecular weight polyol at the temperature of 60-100 ℃, adding diisocyanate and a catalyst under the protection of nitrogen, and carrying out heat preservation reaction at the temperature of 50-95 ℃ for 3-4 hours;
s2, adding polyethylene glycol, a hydrophilic monomer containing hydroxyl and a solvent, and reacting at the temperature of 50-90 ℃ for 2-4 hours in a heat preservation manner to prepare a polyurethane prepolymer containing an isocyanate end group of a hydrophilic group;
s3, cooling the polyurethane prepolymer prepared by the S2 to 40-60 ℃, uniformly stirring and dispersing the polyurethane prepolymer in deionized water containing organic amine to obtain a dispersion, and adding the modified silicone rubber microspheres serving as chain extenders into the dispersion to perform chain extension reaction to obtain the waterborne polyurethane emulsion.
Furthermore, in the polyurethane coating, the using amount of each component is, by mass, 5-20% of high molecular weight polyol, 5-15% of diisocyanate, 2-8% of polyethylene glycol, 1-3% of hydrophilic monomer containing hydroxyl, 0.5-5% of modified silicone rubber microspheres, 0.1-0.5% of catalyst, 2-5% of organic solvent, 0.75-2.5% of organic amine and 50-70% of deionized water.
Further, the molecular weight of the high molecular weight polyol is 1000-5000; the high molecular weight polyol is one or a mixture of more of polyester polyol, polyether polyol and polycarbonate polyol.
Further, the preparation method of the modified silicone rubber microsphere comprises the following steps of adding an organic solvent into 100 parts by mass of surface epoxy functional organic silicon elastomer powder for dispersion, adding 1-10 parts by mass of a polyhydroxy micromolecule functional monomer, heating to 50-100 ℃, reacting for 1-4 hours, filtering, and drying in vacuum to obtain the modified silicone rubber microsphere.
Further, the surface epoxy functional silicone elastomer powder may be DOWSILTMEP-2601、DOWSILTMEP-5500、DOWSILTMOne or a mixture of several of EP-5518; the polyhydroxy micromolecule functional monomer is dopamine; the organic solvent is toluene and ethyl acetate.
Further, the diisocyanate is one or a mixture of hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate; the hydrophilic monomer containing hydroxyl is dimethylolpropionic acid or dimethylolbutyric acid; the catalyst is one of bis dimethylamino ethyl ether, dibutyltin dilaurate and triazine trimerization catalysts; the organic amine is triethylamine and n-propylamine; the solvent is one or more of acetone, methyl ethyl ketone, N-methyl pyrrolidone and N, N-ethyl pyrrolidone.
Further, other additives may be added to the aqueous polyurethane emulsion prepared in step S3 to prepare a polyurethane coating; the other auxiliary agents comprise one or more of pH regulator, defoamer, flatting agent, thickener, filler, film forming agent and preservative.
The beneficial effects of the invention are: compared with the prior art, the wear-resistant high-elasticity polyurethane coating provided by the invention has the following advantages:
1) the modified silicone rubber microspheres are added into the polyurethane coating as a chain extender, and the organic silicon elastomer is combined with the polyurethane, so that the elasticity and the wear resistance of the polyurethane coating are improved;
2) the modified silicone rubber microspheres introduce dopamine into the polyurethane coating in the modification process, so that on one hand, a large amount of amino and hydroxyl groups are contained on the surfaces of the silicone rubber microspheres to play a role of a chain extender, on the other hand, the binding force between a coating and an interface is improved, and the stripping force of the coating is improved;
3) the silicone rubber has excellent low-temperature performance, and can keep good elasticity at a lower temperature, so that the elastic polyurethane coating still has good elasticity at a low temperature, and is not brittle or cracked.
Detailed Description
The invention is further illustrated by the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
1. Preparing modified silicone rubber microspheres:
1kg of DOWSILTMEP-2601 is added into toluene to be dispersed and stirred, 50g of dopamine is added, the mixture is heated to 80 ℃ and stirred to react for 4 hours, and then the mixture is centrifugally filtered and vacuum-dried to obtain white elastic powder, namely the modified silicone rubber microspheres.
2. Preparing an elastic polyurethane coating:
160g of polycaprolactone 2000 is dehydrated in vacuum at 90 ℃, cooled to room temperature, added with 110g of isophorone diisocyanate and a catalyst under the protection of nitrogen, heated to 90 ℃, and kept for reaction for 3 hours. Cooling to 50 ℃, introducing 17.2g of dimethylolpropionic acid, 31g of polyethylene glycol 400 and a small amount of acetone, and carrying out heat preservation reaction at 85 ℃ for 2.5h to obtain the polyurethane prepolymer. And (2) cooling to 50 ℃, slowly dropwise adding triethylamine for neutralization, adding deionized water, quickly shearing and stirring, and adding 10g of the modified silicone rubber microspheres prepared in the step (1) to obtain the elastic waterborne polyurethane emulsion. Adding a defoaming agent into the elastic aqueous polyurethane emulsion, adjusting the stirring speed to 4000-6000 r/min, keeping stirring for 1h, uniformly mixing the materials, reducing the stirring speed to 300-600 r/min, sequentially adding a film-forming agent, a leveling agent and a thickening agent into a reactor, and stirring for 0.5h to obtain the elastic polyurethane coating.
Example 2
1. Preparing modified silicone rubber microspheres:
1kg of DOWSILTMEP-5500 is added into ethyl acetate for dispersion and stirring, 10g of dopamine is added, the mixture is heated to 80 ℃ and stirred for reaction for 4 hours, and then the mixture is centrifugally filtered and vacuum-dried to obtain white elastic powder, namely the modified silicone rubber microspheres.
2. Preparing an elastic polyurethane coating:
160g of polytetrahydrofuran 3000 is dehydrated in vacuum at 90 ℃, cooled to room temperature, added with 90g of isophorone diisocyanate and catalyst under the protection of nitrogen, heated to 90 ℃, and kept for reaction for 3 hours. Cooling to 50 ℃, introducing 14g of dimethylolpropionic acid, 25g of polyethylene glycol 400 and a small amount of acetone, and carrying out heat preservation reaction at 85 ℃ for 2.5h to obtain the polyurethane prepolymer. And (2) cooling to 50 ℃, slowly dropwise adding triethylamine for neutralization, adding deionized water, quickly shearing and stirring, and adding 20g of the modified silicone rubber microspheres prepared in the step (1) to obtain the elastic waterborne polyurethane emulsion.
Example 3
1. Preparing modified silicone rubber microspheres:
1kg of DOWSILTMEP-2601 is added into toluene to be dispersed and stirred, 50g of dopamine is added, the mixture is heated to 80 ℃ and stirred to react for 4 hours, and then the mixture is centrifugally filtered and dried in vacuum to obtain white elastic powder, namely the modified silicon rubber microspheres.
2. Preparing an elastic polyurethane coating:
82g of polyester polyol and 82g of polytetrahydrofuran are dehydrated in vacuum at 80 ℃, cooled to room temperature, added with 88g of Toluene Diisocyanate (TDI) and a catalyst under the protection of nitrogen, heated to 60-90 ℃, and subjected to heat preservation reaction for 3 hours. And cooling to 50 ℃, introducing 18g of dimethylolpropionic acid, 25g of polyethylene glycol 1000 and a small amount of N, N-methyl pyrrolidone, and carrying out heat preservation reaction for 3h at 90 ℃ to obtain the polyurethane prepolymer. And (2) cooling to 50 ℃, slowly dropwise adding triethylamine for neutralization, adding deionized water, quickly shearing and stirring, and adding 20g of the modified silicone rubber microspheres prepared in the step (1) to obtain the elastic waterborne polyurethane emulsion.
Comparative example 1
160g of polycaprolactone 2000 is dehydrated under vacuum at 90 ℃, cooled to room temperature, added with 110g of isophorone diisocyanate and a catalyst under the protection of nitrogen, heated to 90 ℃, and kept warm for reaction for 3 hours. Cooling to 50 ℃, introducing 17.2g of dimethylolpropionic acid, 31g of polyethylene glycol 400 and a small amount of acetone, and carrying out heat preservation reaction at 90 ℃ for 2.5h to obtain the polyurethane prepolymer. And cooling to 50 ℃, slowly dropwise adding triethylamine for neutralization, adding deionized water, quickly shearing and stirring, and adding 3g of micromolecule chain extender hexamethylene diamine to obtain the elastic waterborne polyurethane emulsion. Adding a defoaming agent into the elastic aqueous polyurethane emulsion, adjusting the stirring speed to 4000-6000 r/min, keeping stirring for 1h, reducing the stirring speed to 300-600 r/min after the materials are uniformly mixed, sequentially adding a film-forming agent, a leveling agent and a thickening agent into a reactor, and stirring for 0.5h to obtain the elastic polyurethane coating.
Table 1 results of performance tests of the polyurethane coatings obtained in examples 1 to 3 and comparative example 1.
In conclusion, the polyurethane coating prepared by using the modified silicone rubber elastomer has high strength and elongation at break, particularly the elongation at break at low temperature is obviously improved, and the high-elasticity coating can be prepared. Meanwhile, the modified silicone rubber elastomer has a polyfunctional group, so that the cohesive force of the polymer is improved, and the peel strength of the coating is improved.
The above embodiments are only for illustrating the invention and are not to be construed as limiting the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention, therefore, all equivalent technical solutions also belong to the scope of the invention, and the scope of the invention is defined by the claims.
Claims (7)
1. A wear-resistant high-elasticity polyurethane coating is characterized in that: the polyurethane coating comprises modified silicone rubber microspheres, high molecular weight polyol, diisocyanate, a catalyst, polyethylene glycol, a hydroxyl-containing hydrophilic monomer, a solvent, organic amine and deionized water; the preparation of the polyurethane coating comprises the following steps:
S1, carrying out vacuum dehydration on high molecular weight polyol at the temperature of 60-100 ℃, adding diisocyanate and a catalyst under the protection of nitrogen, and carrying out heat preservation reaction at the temperature of 50-95 ℃ for 3-4 hours;
s2, adding polyethylene glycol, a hydrophilic monomer containing hydroxyl and a solvent, and reacting for 2-4 hours at the temperature of 50-90 ℃ to prepare a polyurethane prepolymer containing an isocyanate end group of a hydrophilic group;
s3, cooling the polyurethane prepolymer prepared from the S2 to 40-60 ℃, uniformly stirring and dispersing the polyurethane prepolymer in deionized water containing organic amine to obtain a dispersion, and adding the modified silicone rubber microspheres serving as chain extenders into the dispersion to carry out chain extension reaction to obtain the waterborne polyurethane emulsion.
2. The wear-resistant highly elastic polyurethane coating material according to claim 1, wherein: the polyurethane coating comprises, by mass, 5-20% of high molecular weight polyol, 5-15% of diisocyanate, 2-8% of polyethylene glycol, 1-3% of hydrophilic monomer containing hydroxyl, 0.5-5% of modified silicone rubber microspheres, 0.1-0.5% of catalyst, 2-5% of organic solvent, 0.75-2.5% of organic amine and 50-70% of deionized water.
3. The wear-resistant highly elastic polyurethane coating material according to claim 1, wherein: the molecular weight of the high molecular weight polyol is 1000-5000; the high molecular weight polyol is one or a mixture of more of polyester polyol, polyether polyol and polycarbonate polyol.
4. The wear-resistant highly elastic polyurethane coating material according to claim 1, wherein: the preparation method of the modified silicone rubber microsphere comprises the following steps of adding an organic solvent into 100 parts by mass of surface epoxy functional organic silicon elastomer powder for dispersion, adding 1-10 parts by mass of a polyhydroxy micromolecule functional monomer, heating to 50-100 ℃, reacting for 1-4 hours, filtering, and drying in vacuum to obtain the modified silicone rubber microsphere.
5. The wear-resistant highly elastic polyurethane coating material according to claim 4, wherein: the surface epoxy functional organosilicon elastomer powder can be one or more of DOWSIL-EP-2601, DOWSIL-EP-5500, DOWSIL-5518; the polyhydroxy micromolecule functional monomer is dopamine; the organic solvent is toluene and ethyl acetate.
6. The wear-resistant highly elastic polyurethane coating material according to claim 1, wherein: the diisocyanate is one or a mixture of hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate; the hydrophilic monomer containing hydroxyl is dimethylolpropionic acid or dimethylolbutyric acid; the catalyst is one of bis dimethylamino ethyl ether, dibutyltin dilaurate and triazine trimerization catalysts; the organic amine is triethylamine and n-propylamine; the solvent is one or more of acetone, methyl ethyl ketone, N-methyl pyrrolidone and N, N-ethyl pyrrolidone.
7. The wear-resistant highly elastic polyurethane coating material according to claim 1, wherein: the waterborne polyurethane emulsion prepared in the step S3 can be added with other additives to prepare a polyurethane coating; the other auxiliary agents comprise one or more of pH regulator, defoamer, flatting agent, thickener, filler, film forming agent and preservative.
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