CN116063911B - Environment-friendly fast-curing single-component polyurea material and preparation method thereof - Google Patents
Environment-friendly fast-curing single-component polyurea material and preparation method thereof Download PDFInfo
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- CN116063911B CN116063911B CN202211446948.0A CN202211446948A CN116063911B CN 116063911 B CN116063911 B CN 116063911B CN 202211446948 A CN202211446948 A CN 202211446948A CN 116063911 B CN116063911 B CN 116063911B
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- isocyanate
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- component polyurea
- polyurea material
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- 239000000463 material Substances 0.000 title claims abstract description 124
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 239000012948 isocyanate Substances 0.000 claims abstract description 64
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000945 filler Substances 0.000 claims abstract description 36
- 238000004383 yellowing Methods 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000004970 Chain extender Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000002518 antifoaming agent Substances 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 230000004224 protection Effects 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005538 encapsulation Methods 0.000 claims description 6
- 150000001412 amines Chemical group 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 229940018038 sodium carbonate decahydrate Drugs 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 125000000160 oxazolidinyl group Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 238000003860 storage Methods 0.000 abstract description 10
- 239000006096 absorbing agent Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 48
- 239000013078 crystal Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000007726 management method Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- -1 aliphatic isocyanate Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000012974 tin catalyst 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
- C09D175/02—Polyureas
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/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
- C08G18/28—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
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides an environment-friendly fast-curing single-component polyurea material, which comprises, by mass, 80-100 parts of isocyanate semi-prepolymer, 5-40 parts of latent curing agent, 3-18 parts of water-containing filler, 3-15 parts of filler and 5-15 parts of color paste, and further comprises one or more of auxiliary agents such as dispersing agents, defoamers, leveling agents, anti-hydrolysis agents, anti-yellowing agents and ultraviolet absorbers. The environment-friendly rapidly-cured single-component polyurea material provided by the invention has long storage time and rapid curing time, and solves the problem that the existing single-component polyurea material cannot be dried after thick coating and caulking.
Description
Technical Field
The invention belongs to the field of hydraulic and hydroelectric engineering, relates to a hydraulic engineering local repair material, and in particular relates to an environment-friendly rapidly-cured single-component polyurea material and a preparation method thereof.
Background
The polyurea elastomer is prepared by reacting hydroxyl polyether/amino polyether with polyisocyanate to form semi-prepolymer (A component) blocked by isocyanate, and then reacting with resin component (B component) composed of amino-terminated polyether, amino-terminated chain extender and other auxiliary agents to form the elastomer material containing urea bond. At present, polyureas existing in the market in China are distinguished from high to low in durability according to the content of urea bonds, and the polyureas comprise: two-component spray polyurea, two-component spray polyurethane urea, two-component polyaspartic acid ester polyurea, one-component knife coating polyurea and the like. The double-component spray polyurea elastomer coating has excellent performances of aging resistance, long-term water immersion resistance, high-speed water flow impact abrasion resistance, corrosion resistance, freeze thawing resistance, impact resistance, fatigue damage resistance and the like, and is suitable for protecting hydraulic buildings such as dam surfaces, spillways, sand discharge holes, diversion holes, water conveying channels and the like.
However, in the practical application process, special spraying equipment is required for the two-component spraying polyurea, and the two-component spraying polyurea has limitation in the environments of difficult electricity consumption, narrow construction space and local repair treatment. Therefore, in order to solve the problem, the one-component moisture-curing knife coating polyurethane can be used for local repair and reinforcement, the one-component polyurethane absorbs moisture in the air, the blocking of the latent curing agent is relieved, active hydrogen is released, and the active hydrogen reacts with isocyanate to be cured. When the latent curing agent releases a small amount of amino after unblocking, the amino active hydrogen reacts with isocyanate to generate a small amount of urea bond, so that the single-component moisture-cured polyurethane is called a single-component polyurea material in some domestic fields and is used for waterproof, seepage-proof and corrosion-proof of engineering.
The traditional single-component polyurea material has the problems of high requirements on construction environment, difficult construction of vertical curved surfaces, incapability of construction in a low-temperature environment (below 25 ℃), easiness in swelling, short storage period, high aging speed and the like in practical application. In particular, the following disadvantages lead to the fact that such materials are not suitable for the rapid repair requirements of hydraulic engineering:
(1) Because the traditional single-component polyurea material contains a solvent and a large amount of filler, the environment-friendly requirement is not met in actual use, and the durability in the actual application process is less than 1 year because of solvent volatilization and excessive filler;
(2) Because the traditional single-component polyurea material is slowly solidified by absorbing moisture in air, under the condition of no catalyst, the general surface drying time is more than 10 hours, under the condition of the coating thickness being less than 1mm, the real drying time is more than 72 hours, and the excessive moisture in the air can react with isocyanate preferentially in a moist low-temperature environment, so that the problems of coating foaming and the like are solved, and the quick repairing requirement in practical application is not met; the addition of the catalyst can accelerate the curing speed of the material, but the catalyst reversely catalyzes the aging reaction of the material after the material is cured, and the existing catalyst comprises mercury catalysts, tin catalysts, bismuth catalysts and the like, so that the heavy metal exceeds the standard after the catalyst is used, and the environmental protection requirement is not met;
(3) The traditional single-component polyurea material needs thin coating construction, wherein the thickness of the thin coating is smaller than 1mm, and the thickness is generally reduced to 0.6-0.8mm for accelerating curing. In the use process, in order to accelerate the curing speed of the first layer and avoid the damage to the first scraping material during the second or third scraping, a non-woven fabric is paved on the surface of the first scraping material, and the non-woven fabric essentially changes the chemical structure of the coating, so that the mechanical property of the coating is rapidly reduced and is inconsistent with the mechanical property required by the standard and design.
Therefore, in order to solve the problems of long curing time, catalyst containing, non-environmental protection and the like, there is a need to develop a novel single-component polyurea material which is green, environment-friendly, fast in curing, long in storage period and low-temperature in construction and is suitable for repairing and reinforcing hydraulic engineering.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an environment-friendly rapidly-cured single-component polyurea material which has long storage time, rapid curing time and low temperature resistance (below 25 ℃) and solves the problem that the conventional single-component polyurea material cannot be rapidly dried after caulking.
Another object of the present invention is to provide a method for preparing the above-described environmentally friendly, fast curing one-component polyurea material.
It is a further object of the present invention to provide the use of the above-described environmentally friendly, fast curing one-component polyurea material.
In order to achieve the aim, the invention provides an environment-friendly fast-curing single-component polyurea material, which comprises, by mass, 80-100 parts of isocyanate semi-prepolymer, 5-40 parts of latent curing agent, 3-18 parts of water-containing filler, 3-15 parts of filler and 5-15 parts of color paste;
wherein the latent curing agent is a commercially available latent curing agent;
the filler is fumed silica, talcum powder or kaolin.
Further, the raw material also comprises an auxiliary agent, wherein the auxiliary agent is one or more of a dispersing agent, a defoaming agent, a leveling agent, an anti-hydrolysis agent, an anti-yellowing agent and an ultraviolet absorber;
wherein the mass of the dispersing agent, the defoaming agent, the leveling agent and the hydrolysis resistance agent is respectively 2-10 per mill of the mass sum of other raw materials except the auxiliary agent;
when the anti-yellowing agent or the ultraviolet absorbent is used alone, the mass of the anti-yellowing agent or the ultraviolet absorbent respectively accounts for 3 to 7 per mill of the sum of the mass of other raw materials except the auxiliary agent; when the anti-yellowing agent and the ultraviolet absorber are used simultaneously, the mass sum of the anti-yellowing agent and the ultraviolet absorber accounts for 3 to 7 per mill of the mass sum of other raw materials except the auxiliary agent.
Further, the isocyanate semi-prepolymer is formed by reacting 36-48 parts of difunctional isocyanate, 36-48 parts of trifunctional isocyanate, 36-48 parts of polyol, 6-30 parts of chain extender and 1-2 parts of silane coupling agent, wherein the NCO mass fraction of the isocyanate semi-prepolymer is 5% -13%;
wherein the difunctional isocyanate is toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate;
the trifunctional isocyanate is an HDI trimer or a TDI trimer;
the polyol is polytetrahydrofuran glycol, polycarbonate glycol, polypropylene glycol, 3-methyl PTMEG or hydroxyl-terminated polybutadiene;
the chain extender is as follows: hindered amine chain extenders or hydroxyl chain extenders;
the silane coupling agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane or gamma-aminopropyl triethoxy silane.
Still further, the aqueous filler is an inorganic material with water of crystallization.
Preferably, the aqueous filler is hydrated alumina or sodium carbonate decahydrate.
The invention also provides a preparation method of the environment-friendly rapidly-cured single-component polyurea material, which comprises the following steps:
1) Preparing isocyanate semi-prepolymer;
2) The prepared isocyanate semi-prepolymer and the rest raw materials in the single-component polyurea material are put into a closed dispersion kettle for dispersion, the dispersion speed is 40-1500 rpm, the temperature is 5-25 ℃, and the dispersion time is 0.5 hour;
the dispersion speed is related to the viscosity of the components, when the material with the viscosity of about 100 mPas is dispersed, the material can be dispersed at a high speed (for example, to 1500 rpm), when the viscosity is above 300 mPas, the material is dispersed at a medium speed (for example, 100-500 rpm), and if the viscosity is above 5000 mPas, the material can only be dispersed at a low speed, and the speed is reduced to 40 rpm, so that the damage of a stirring wheel in a dispersing kettle is prevented. Therefore, the dispersion rotation speed is determined before dispersion according to the viscosity of the raw material used.
3) Vacuum defoaming and nitrogen encapsulation are carried out under the condition of vacuum degree of-0.1, and the preservation is carried out at 5-20 ℃.
The vacuum defoaming step removes air in raw materials in a vacuum mode in the stirring process or in raw materials, and ensures that the whole system is free of air, so that the storage stability can be improved, and on the other hand, the system is free of air in construction, so that the compactness of a coating can be ensured.
More still, the isocyanate semiprepolymer preparation method comprises the following steps:
1) Reaction conditions: nitrogen protection;
2) The polyalcohol and the chain extender are subjected to water removal treatment: adding the polyol into a high-speed dispersion vacuum kettle, heating to 110-130 ℃, dispersing at high speed, vacuumizing, heating for 1-2 hours to remove water in the polyol completely, and obtaining the polyol after water removal; adding the chain extender into a high-speed dispersion vacuum kettle, heating to 110-130 ℃, dispersing at high speed, vacuumizing, heating for 1-2 hours to remove water in the chain extender completely, and obtaining the dehydrated chain extender;
3) Adding difunctional isocyanate and trifunctional isocyanate into a reaction kettle, adding polyol into the reaction kettle, releasing heat from the reaction system, heating the reaction kettle to 85-90 ℃ for reaction for 2.5 hours after the system temperature is stable and does not rise, and obtaining an isocyanate prepolymer;
4) The temperature of the reaction system is reduced to below 20 ℃, a chain extender and a silane coupling agent are added, and after the temperature of the system is stable and does not rise any more, the reaction is carried out for 1 hour at the normal temperature of 20-30 ℃ to obtain the isocyanate semi-prepolymer.
Further, 5) the isocyanate semiprepolymer after completion of the reaction was subjected to nitrogen encapsulation and stored at room temperature of 25 ℃.
The isocyanate semiprepolymer can be directly used after the preparation, and if the isocyanate semiprepolymer needs to be prepared and stored in advance, the isocyanate semiprepolymer needs to be encapsulated by nitrogen.
The invention also provides application of the environment-friendly rapidly-cured single-component polyurea material in an environment which is locally repaired by hydraulic engineering and needs to be operated in a short time.
When the material is used on a construction site, the single-component polyurea material is preheated to 35-60 ℃, and when the central temperature of the material reaches 35 ℃, the material is coated on a construction base surface, and then a scraping plate is used for one-time scraping and coating to form a film or caulking.
The environment-friendly rapidly-cured single-component polyurea material provided by the invention has the advantages that the water-containing filler used in the material can release crystal water on one hand, promote the material to be cured, and can also increase the strength of the material on the other hand; the metal ions in the aqueous filler can improve the bonding strength of the coating material and the basal plane; the cost of materials can be reduced; in addition, as the material has no catalyst such as organic tin, organic bismuth and the like, on one hand, the environmental protection performance of the material is ensured, and on the other hand, the storage property of the material is prolonged to one year (generally, under the condition of the catalyst, the storage property of the existing material in winter is 6 months, and the storage property in summer is 3 months).
The invention has the beneficial effects that:
the invention provides an environment-friendly type fast-curing single-component polyurea material and a preparation method thereof, wherein the material has the advantages of long storage time, fast curing time and environmental low temperature resistance (below 25 ℃), the preparation method is simple, the use is convenient, and the problem that the conventional single-component polyurea material cannot be quickly dried after caulking is solved.
Drawings
FIG. 1 is a photograph of a conventional one-component polyurea material used for more than 1 year.
FIG. 2 is a photograph of delamination of a conventional one-component polyurea material.
FIG. 3 is a photograph showing swelling of a conventional one-component polyurea material when not completely dried.
Fig. 4 is a photograph of example 1 coated with the environmentally friendly, fast curing one-component polyurea material provided herein.
Fig. 5 is a photograph of a 2mm coating of example 2 of the environmentally friendly, fast curing one-component polyurea material provided herein.
Fig. 6 is a photograph of a 2mm coating of example 3 of the environmentally friendly, fast curing one-component polyurea material provided herein.
Detailed Description
The embodiments of the present invention will be described in detail and fully described below to enable those skilled in the art to more readily understand the advantages and features of the present invention and to make a clear and concise description of the scope of the present invention.
The curing mechanism of the traditional single-component polyurea material is as follows:
the one-component polyurea is formed by mixing an isocyanate polymer prepolymer with a blocked polyamine (such as a latent curing agent) and other adjuvants. When the single-component polyurea material mixture before curing is contacted with air, the blocked polyamine is blocked and released to release the terminal amino-NH 2 or-NH-under the action of moisture, and the terminal amino reacts with-NCO to form urea bond, so that the curing is realized. Within the enclosed space, the one-component polyurea material mixture cannot be deblocked to release the terminal amino groups under conditions of contact with air or moisture and therefore does not react chemically with the semi-prepolymer of-NCO, resulting in the following problems in use:
(1) The thickness of each painting can not exceed 1mm, and the thickness of the painting is required to be 0.6-0.8mm, so that the curing can be ensured.
(2) When the coating thickness exceeds 1mm, the curing time is prolonged, when the coating thickness is thicker, and reaches 2mm or more, there may be a long-term non-curing condition, as shown in fig. 1, in which the conventional single-component polyurea material is not cured in 1 year of coating use in a certain engineering, resulting in deformation of the coating layer; in another process, as shown in fig. 2, the conventional one-component polyurea material has a delamination phenomenon that falls from the coating location.
(3) If the single-component polyurea material is used for the expansion joint caulking, the expansion joint caulking cannot be contacted with air or moisture due to the limitation of a curing space, and the complete curing cannot be realized, so that the expansion joint caulking has the use limitation, such as the condition that the traditional single-component polyurea material is not completely dried and bulges in the expansion joint caulking engineering shown in fig. 3.
If the conventional one-component polyurea material cannot be cured quickly due to moisture in the air, the water is directly mixed into the conventional one-component polyurea material when in use, so that the latent curing agent is ensured to release the end-capping end-amino-NH 2 or-NH-, and thus reacts with the-NCO in the isocyanate prepolymer. However, this reaction is a precise reaction requiring accurate calculation, and the following problems occur when mixing water in situ: (1) poor stirring and partial water content: the redundant water reacts with-NCO to generate bubbles, and the-OH in the water reacts with-NCO instead of polyurea, so that the reaction property of the material is changed; (2) The generated bubbles cause defects of the elastomer, which affect the long-term use performance.
The invention provides an environment-friendly rapid-curing single-component polyurea material, which comprises, by mass, 80-100 parts of isocyanate semi-prepolymer, 5-40 parts of latent curing agent, 3-18 parts of water-containing filler, 3-15 parts of filler and 5-15 parts of color paste. The paint further comprises an auxiliary agent, wherein the auxiliary agent is one or more of a dispersing agent, a defoaming agent, a leveling agent, an anti-hydrolysis agent, an anti-yellowing agent and an ultraviolet absorber.
The amine of the latent curing agent is encapsulated and only in the presence of water vapor is the encapsulated amine released to form a reactive amino group which reacts with the NCO to form an ureido bond, also known as an deblocking reaction.
The water-containing filler added into the single-component polyurea material provided by the invention contains crystal water, and the crystal water in the water-containing filler is changed into free water by heating when the single-component polyurea material is used, so that the single-component polyurea material participates in the deblocking reaction of the latent curing agent, the curing process of the single-component polyurea material is accelerated, and the free water is released into the polyurea material, so that the single-component polyurea material can be still cured when the thickness is fixed; the aqueous filler is uniformly dispersed in the polyurea material, so that the uniformity of curing of the single-component polyurea material is ensured. In addition, the aqueous filler as a filler itself can also increase the strength of the one-component polyurea and at the same time adjust the viscosity of the material system.
The water-containing filler is hydrated alumina or sodium carbonate decahydrate, and the hydrated alumina can be bauxite and other structures which are easy to dissociate crystal water.
Wherein the mass of the dispersing agent, the defoaming agent, the leveling agent and the hydrolysis resistance agent is respectively 2-10 per mill of the mass sum of other raw materials except the auxiliary agent;
when the anti-yellowing agent or the ultraviolet absorbent is used alone, the mass of the anti-yellowing agent or the ultraviolet absorbent respectively accounts for 3 to 7 per mill of the sum of the mass of other raw materials except the auxiliary agent; when the anti-yellowing agent and the ultraviolet absorber are used simultaneously, the mass sum of the anti-yellowing agent and the ultraviolet absorber accounts for 3 to 7 per mill of the mass sum of other raw materials except the auxiliary agent.
Since the respective auxiliaries act independently, the added mass is calculated separately at the time of adding the raw materials.
The auxiliary agent is selectively added according to different application occasions: in the open air, ultraviolet absorbers and/or anti-yellowing agents are required; under water, an anti-hydrolysis agent is needed; when the system is relatively viscous, a dispersant must be added to provide a more uniform dispersion. When bubbles exist in the system and a defoaming agent exists, the defoaming agent is easy to defoam during defoam. When the viscosity of the system is high and flatness is required, a leveling agent is required.
The single-component polyurea material of the invention belongs to polyurethane systems, and the defoamer used in the polyurethane systems is selected, and is usually BYK535 or BYK530.
The silane coupling agent is selected according to the primer material matched with the single-component polyurea material, and gamma- (2, 3-glycidoxy) propyl trimethoxy silane belongs to the silane coupling agent containing epoxy groups, so that the adhesive property between the single-component polyurea material and the epoxy primer can be improved when the silane coupling agent is used on the epoxy primer, and common commercial products include Michaelsen A187, KH-560 and the like; the gamma-aminopropyl triethoxy silane belongs to an amino-containing silane coupling agent, can improve the adhesive property of a single-component polyurea material and a polyurethane primer when used on the polyurethane primer, and is commonly used in the commercial products such as Michaelsen A1100, KH-550 and the like.
The color paste is used for coordinating and conforming the single-component polyurea material with an application scene, and if the single-component polyurea material is applied to a common engineering, gray color paste which is close to the color of concrete is selected, blue color paste and the like are selected when the single-component polyurea material is applied to the periphery of the bottom of a swimming pool, and the color paste is a commercial product.
The raw material models used in the following examples are all conventional product models in the field except for the limitation, but not only the model products can be used, but also the products with the same effects can be replaced.
Example 1
Preparing a single-component polyurea material, wherein the single-component polyurea material comprises the following components in parts by mass: 85 parts of isocyanate semi-prepolymer, 7 parts of latent curing agent (oxazolidine latent curing agent TP-830), 6 parts of hydrated alumina filler, 5 parts of filler fumed silica and 5 parts of color paste (Stemburg color paste).
The hydrated alumina in this example is bauxite.
The auxiliary agent simultaneously uses dispersant BYK-163, defoamer BYK535, leveling agent BYK370 and anti-hydrolysis agent JR7000, wherein the dispersant is 0.5 part, the defoamer is 0.5 part, the leveling agent is 0.5 part and the anti-hydrolysis agent is 0.5 part.
The isocyanate semi-prepolymer in the raw materials is produced by the reaction of the following materials: 45 parts of toluene diisocyanate, 43 parts of HDI trimer, 45 parts of polytetrahydrofuran diol, 21.5 parts of hydroxyl chain extender (1, 4-butanediol, also called BDO) and 187.1 parts of silane coupling agent A, wherein the mass fraction of NCO of the prepared isocyanate semi-prepolymer is 8.5%.
The single-component polyurea material prepared in this example is used in a long-term water-immersion environment, and in order to prevent the coating from hydrolyzing, a hydrolysis-resistant agent is added to improve the durability of long-term water immersion. In addition, since the NCO of the designed formula is relatively low and the viscosity of the system is relatively high, a dispersing agent and a defoaming agent are required to be added, so that the uniformity of dispersion is improved, and bubbles generated in the system during dispersion are eliminated. In addition, the single-component polyurea material prepared in the embodiment is used on a bottom plate in a water delivery culvert, and in order to reduce the over-flow roughness, the surface is required to be smooth and free of marks, so that a leveling agent is also required to be added.
The preparation process of the single-component polyurea material of this example is as follows:
1. preparing isocyanate semi-prepolymer:
1) Nitrogen protection;
2) Respectively adding polytetrahydrofuran dihydric alcohol and a hydroxyl chain extender into different reaction kettles, heating to 110 ℃ and carrying out water removal treatment for 1 hour;
3) Sequentially adding toluene diisocyanate and TDI trimer into another reaction kettle, then adding dehydrated polytetrahydrofuran diol, releasing heat from the reaction system, and heating to 90 ℃ after the system temperature is stable and does not rise any more, so as to ensure the system to react for 2.5 hours;
4) The temperature of the reaction system is reduced to below 20 ℃, a hydroxyl chain extender and a silane coupling agent are added, and after the system temperature is stable, the reaction is carried out for 1 hour at the normal temperature of 25 ℃.
When the isocyanate semiprepolymer is not used, the isocyanate semiprepolymer after the reaction can be subjected to nitrogen encapsulation management and stored at room temperature (25 ℃) for subsequent use.
2. Preparing a single-component polyurea material:
1) Adding the prepared isocyanate semi-prepolymer, a latent curing agent, a dispersing agent, a defoaming agent, a leveling agent, an anti-hydrolysis agent, a water-containing filler, fumed silica and color paste into a closed dispersing kettle, and dispersing for 3 hours at a low temperature of 10 ℃ at a rotating speed of 40 rpm;
since the bound water in the 40 ℃ aqueous filler absorbs heat and becomes free water, resulting in solidification of the product, the raw materials need to be kept at a lower temperature of 5-25 ℃ when mixed, so as to prevent the raw materials from being solidified before use and not being used any more.
2) Vacuumizing and defoaming; and (5) packaging with nitrogen and storing at a low temperature (10 ℃).
The method is used in the field:
the one-component polyurea is heated (50 ℃) to release the crystal water in the aqueous filler from the crystalline state, and the crystal water exists in the system as normal water to promote the solidification of the material, so that the one-component polyurea needs to be used as soon as possible.
FIG. 4 is a photograph showing caulking using the one-component polyurea described above. In fig. 4, the caulking is 2cm wide and 2cm deep, the single-component polyurea filled in the caulking is not exposed to air and cannot contact with water vapor in the air, and the material curing is promoted due to the release of crystal water in the single-component polyurea, so that the whole curing and drying are realized after about 1 hour of test.
Example 2
Preparing a single-component polyurea material, wherein the single-component polyurea material comprises the following components in parts by mass: 110 parts of isocyanate semiprepolymer, 25 parts of latent curing agent, 15 parts of hydrated alumina serving as a water-containing filler, 7 parts of fumed silica serving as a filler, 7 parts of color paste and an auxiliary agent.
The hydrated alumina is mainly bauxite.
The auxiliary agents simultaneously use a defoaming agent BYK535, a leveling agent BYK370, a polyurethane anti-yellowing agent PUB-380 and an ultraviolet absorber UV531, wherein the defoaming agent is 0.5 part, the leveling agent is 0.5 part, the anti-yellowing agent is 0.5 part and the ultraviolet absorber is 0.5 part.
The isocyanate semi-prepolymer in the raw materials is produced by the reaction of the following materials: 48 parts of isophorone diisocyanate, 48 parts of HDI trimer, 36 parts of polytetrahydrofuran dihydric alcohol, 15 parts of hydroxyl chain extender (1, 4-butanediol, also called BDO) and 1100 parts of silane coupling agent A, wherein the mass fraction of NCO of the prepared isocyanate semi-prepolymer is 10.2%.
The single-component polyurea material prepared in the embodiment is used in an exposed sun exposure environment, and in order to prevent the coating from aging under ultraviolet rays, an anti-yellowing agent and an ultraviolet absorber are added to improve the ultraviolet resistance durability under long-term exposure. In addition, the single-component polyurea material prepared in the embodiment has higher NCO and better system viscosity, so that the single-component polyurea material can be dispersed uniformly without adding a dispersing agent. In addition, in order to prevent the problems such as yellowing of the exposed materials, the aliphatic isocyanate is used, so that the durability of the exposed materials for a long time can be improved, and the yellowing resistance of other materials can be reduced by the anti-yellowing agent and the ultraviolet absorber. In addition, the material is designed for external concrete, and a leveling agent is added for improving the aesthetic property of the coating.
The preparation process of the single-component polyurea material of this example is as follows:
1. preparing isocyanate semi-prepolymer:
1) Nitrogen protection;
2) Respectively adding polytetrahydrofuran dihydric alcohol and a hydroxyl chain extender into different reaction kettles, heating to 110 ℃ and carrying out water removal treatment for 1 hour;
3) Sequentially adding isophorone diisocyanate and HDI trimer into another reaction kettle, then adding dehydrated polytetrahydrofuran diol, releasing heat from the reaction system, and heating to 90 ℃ after the system temperature is stable and does not rise any more, so as to ensure the system to react for 2.5 hours;
4) And (3) reducing the temperature of the reaction system to below 20 ℃, adding a hydroxyl chain extender and a silane coupling agent, and keeping the normal temperature at 25 ℃ for reaction for 1 hour after the system temperature is stable, so as to obtain the isocyanate semi-prepolymer.
When the reaction is not finished, the isocyanate semiprepolymer is subjected to nitrogen encapsulation management and stored at room temperature (25 ℃).
2. Preparing a single-component polyurea material:
1) Adding the prepared isocyanate semi-prepolymer, a latent curing agent TP-830, a defoaming agent, a leveling agent, an anti-yellowing agent, an ultraviolet absorber, an aqueous filler, fumed silica and color paste into a closed dispersion kettle, and dispersing for 3 hours at a low temperature of 10 ℃ at a rotational speed of 800 rpm;
2) Vacuumizing and defoaming; and (5) packaging with nitrogen and storing at a low temperature (10 ℃).
The method is used in the field:
heating the monocomponent polyurea to 60 ℃, and carrying out crystallization removal treatment on crystal water in the water-containing filler by heating, wherein the crystal water exists in a system as normal water. The heated one-component polyurea was then used over a period of 2 hours.
A photo of the one-component polyurea prepared was coated 2mm thick and cured after 1 hour as shown in fig. 5. The single-component polyurea material prepared according to the experiment can be stored for more than 1 year at 10 ℃ before being used.
Example 3
Preparing a single-component polyurea material, wherein the single-component polyurea material comprises the following components in parts by mass: 100 parts of isocyanate semi-prepolymer, 28 parts of latent curing agent, 8 parts of sodium carbonate decahydrate containing water filler, 5 parts of filler fumed silica and 5 parts of color paste.
The isocyanate semi-prepolymer in the raw materials is produced by the reaction of the following materials: 46 parts of 4,4' -dicyclohexylmethane diisocyanate, 43 parts of HDI trimer, 38 parts of polycarbonate diol, 30 parts of hindered amine chain extender (NH 1420), 187 parts of silane coupling agent A and 9.8% of NCO mass fraction of the prepared isocyanate semi-prepolymer.
The single-component polyurea material prepared by the embodiment is used in northern cold region environments with larger deformation. The single-component polyurea material prepared by the embodiment has higher NCO and better system viscosity, so that the single-component polyurea material can be dispersed uniformly without adding a dispersing agent. In order to adapt to the large deformation structure in the northern cold region, the deformation performance of the material can be improved by using the polycarbonate diol.
The preparation process of the single-component polyurea material of this example is as follows:
1. preparing isocyanate semi-prepolymer:
1) Nitrogen protection;
2) Respectively adding polycarbonate dihydric alcohol and a hindered ammonia chain extender into different reaction kettles, heating to 110 ℃ and carrying out water removal treatment for 1 hour;
3) Sequentially adding 4,4' -dicyclohexylmethane diisocyanate and an HDI trimer into another reaction kettle, then adding dehydrated polytetrahydrofuran diol, releasing heat from a reaction system, and heating to 90 ℃ after the temperature of the system is stable and does not rise any more, so as to ensure the system to react for 2.5 hours;
4) The temperature of the reaction system is reduced to below 20 ℃, a steric hindrance ammonia chain extender and a silane coupling agent are added, and after the system temperature is stable, the reaction is carried out for 1 hour at the normal temperature of 25 ℃, so as to obtain the isocyanate semi-prepolymer.
When the reaction is not finished, the isocyanate semiprepolymer is subjected to nitrogen encapsulation management and stored at room temperature (25 ℃).
2. Preparing a single-component polyurea material:
1) Adding the prepared isocyanate semi-prepolymer, a latent curing agent TP-830, an aqueous filler, fumed silica and color paste into a closed dispersing kettle, and dispersing for 3 hours at a low temperature of 10 ℃ at a rotating speed of 200 rpm;
2) Vacuumizing and defoaming; and (5) packaging with nitrogen and storing at a low temperature (10 ℃).
The method is used in the field:
heating the single-component polyurea to 40 ℃, and carrying out crystallization removal treatment on crystal water in the water-containing filler by heating, wherein the crystal water exists in a system as normal water.
As shown in FIG. 6, a photo of a single-component polyurea coating with a thickness of 2mm is shown, wherein the middle carrier is a ceramic tile, the left and right carriers are concrete blocks, the single-component polyurea and the commercial single-component polyurea of the embodiment are respectively coated on the ceramic tile and the concrete blocks, the left and lower parts are the commercial single-component polyurea materials with waterproof and anti-corrosion properties, the right and upper parts are the single-component polyurea prepared in the embodiment, and the curing environment is Beijing outdoor in winter (about-10 ℃ outdoor). The one-component polyurea material prepared in this example was cured in 1 hour, whereas the commercially available one-component polyurea was surface dried in 6 hours, and foamed internally due to the low environment Wen Weiwan through full cure.
Further according to experiments, the prepared single-component polyurea material can be stored for more than 1 year at 10 ℃ before being used.
From the above embodiment, the environment-friendly type fast-curing single-component polyurea material provided by the invention has long storage time, fast curing time and environmental low temperature resistance, and solves the problem that the caulking of the existing single-component polyurea material cannot be dried fast.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. The environment-friendly type fast-curing single-component polyurea material is characterized by comprising, by mass, 80-100 parts of isocyanate semi-prepolymer, 5-40 parts of latent curing agent, 3-18 parts of water-containing filler, 3-15 parts of filler and 5-15 parts of color paste;
the isocyanate semi-prepolymer is formed by reacting 36-48 parts of difunctional isocyanate, 36-48 parts of trifunctional isocyanate, 36-48 parts of polyol, 6-30 parts of chain extender and 1-2 parts of silane coupling agent, wherein the NCO mass fraction of the isocyanate semi-prepolymer is 5% -13%;
wherein the difunctional isocyanate is toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate;
the trifunctional isocyanate is an HDI trimer or a TDI trimer;
the polyol is polytetrahydrofuran glycol, polycarbonate glycol, polypropylene glycol or hydroxyl-terminated polybutadiene;
the chain extender is as follows: hindered amine chain extenders or hydroxyl chain extenders;
the silane coupling agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane or gamma-aminopropyl triethoxy silane;
the latent curing agent is a commercially available latent curing agent; the commercial latent curing agent is an oxazolidine latent curing agent TP-830;
the filler is fumed silica, talcum powder or kaolin;
the water-containing filler is hydrated alumina or sodium carbonate decahydrate.
2. The environmentally friendly rapidly curing one-component polyurea material according to claim 1, wherein the raw material further comprises an auxiliary agent which is one or more of a dispersant, a defoamer, a leveling agent, an anti-hydrolysis agent, an anti-yellowing agent, and an ultraviolet absorber;
wherein the mass of the dispersing agent, the defoaming agent, the leveling agent and the hydrolysis resistance agent is respectively 2-10 per mill of the mass sum of other raw materials except the auxiliary agent;
when the anti-yellowing agent or the ultraviolet absorber is used independently, the mass of the anti-yellowing agent or the ultraviolet absorber respectively accounts for 3 to 7 per mill of the sum of the mass of other raw materials except the auxiliary agent; when the anti-yellowing agent and the ultraviolet absorber are used simultaneously, the mass sum of the anti-yellowing agent and the ultraviolet absorber accounts for 3 to 7 per mill of the mass sum of other raw materials except the auxiliary agent.
3. A method for preparing the environment-friendly rapidly curing single-component polyurea material as claimed in claim 1 or 2, comprising the steps of:
1) Preparing isocyanate semi-prepolymer;
2) The prepared isocyanate semi-prepolymer and the rest raw materials in the single-component polyurea material are put into a closed dispersion kettle for dispersion, the dispersion speed is 40-1500 rpm, the temperature is 5-25 ℃, and the dispersion time is 0.5 hour;
3) Vacuum defoamation and nitrogen encapsulation are carried out under the condition of vacuum degree of-0.1, and the preservation is carried out at 5-20 ℃.
4. The method for preparing an environment-friendly and rapidly curing one-component polyurea material as claimed in claim 3, wherein the method for preparing the isocyanate semiprepolymer comprises the following steps:
1) Reaction conditions: nitrogen protection;
2) The polyalcohol and the chain extender are subjected to water removal treatment: adding the polyol into a high-speed dispersion vacuum kettle, heating to 110-130 ℃, dispersing at high speed, vacuumizing, heating for 1-2 hours to remove water in the polyol completely, and obtaining the polyol after water removal; adding the chain extender into a high-speed dispersion vacuum kettle, heating to 110-130 ℃, dispersing at high speed, vacuumizing, heating for 1-2 hours to remove water in the chain extender completely, and obtaining the dehydrated chain extender;
3) Sequentially adding difunctional isocyanate and trifunctional isocyanate into a reaction kettle, adding polyol into the reaction kettle, releasing heat from a reaction system, heating the reaction kettle to 85-90 ℃ for reaction for 2.5 hours after the system temperature is stable and does not rise, and obtaining an isocyanate prepolymer;
4) And (3) reducing the temperature of the reaction system to below 20 ℃, adding a chain extender and a silane coupling agent, and keeping the normal temperature at 20-30 ℃ for reaction for 1 hour after the temperature of the system is stable and does not rise, so as to obtain the isocyanate semi-prepolymer.
5. The method for preparing an environmentally friendly, fast curing one-component polyurea material as claimed in claim 4, wherein the method for preparing an isocyanate semiprepolymer further comprises, after step 4):
5) And (3) packaging the isocyanate semiprepolymer after the reaction is completed by nitrogen, and preserving at room temperature of 25 ℃.
6. Use of the environmentally friendly, fast curing one-component polyurea material according to claim 1 or 2 in environments where hydraulic engineering is locally repaired and needs to be operated in a short time.
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