CN116135935B - High-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection and preparation method thereof - Google Patents
High-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection and preparation method thereof Download PDFInfo
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- CN116135935B CN116135935B CN202310155695.XA CN202310155695A CN116135935B CN 116135935 B CN116135935 B CN 116135935B CN 202310155695 A CN202310155695 A CN 202310155695A CN 116135935 B CN116135935 B CN 116135935B
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- epoxy resin
- aqueous polyurethane
- chain extender
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- ketimine
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 100
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 100
- 239000004970 Chain extender Substances 0.000 claims abstract description 69
- 150000004658 ketimines Chemical class 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003860 storage Methods 0.000 claims abstract description 31
- 150000002576 ketones Chemical class 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000004078 waterproofing Methods 0.000 claims abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 37
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 229920003009 polyurethane dispersion Polymers 0.000 abstract description 22
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 3
- 229920006264 polyurethane film Polymers 0.000 description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 150000002009 diols Chemical class 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 150000003335 secondary amines Chemical group 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 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 description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011527 polyurethane coating Substances 0.000 description 4
- 150000003384 small molecules Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- -1 polyhexamethylene adipate Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920006276 ketonic resin Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/488—Other macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C04B41/4884—Polyurethanes; Polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/63—Macromolecular compounds
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
- C08G18/287—Imine compounds
-
- 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
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/20—Diluents or solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a high storage stability room temperature self-curing aqueous polyurethane for concrete protection and a preparation method thereof, at least comprising the following raw materials: 8.0 to 15.0 parts by mass of diisocyanate; 8.0-15.0 parts by mass of dihydric alcohol; 1.5 to 3.0 parts by mass of a hydrophilic chain extender; 1.5 to 3.0 parts by mass of a chain extender; 1.0 to 2.0 parts by mass of a neutralizing salifying agent; 1.0 to 3.0 parts by mass of an epoxy resin; 0.5-1.5 parts by mass of ketimine post-chain extender; 3.0 to 5.0 parts by mass of a ketone solvent; 70.0-100.0 parts by mass of deionized water. The invention adopts epoxy resin as a comonomer and ketimine containing secondary amine groups as a rear chain extender, and prepares the modified aqueous polyurethane dispersion with high storage stability and room temperature self-curing through a ketimine method. The obtained aqueous polyurethane dispersion can be stably stored for 6-12 months at room temperature, can form a film on the surface of concrete at room temperature, can realize self-curing through the crosslinking reaction between macromolecular chains at room temperature, and can be applied to the fields of building waterproofing, concrete protection and the like.
Description
Technical Field
The invention relates to the field of waterborne polyurethane for concrete protection, in particular to high-storage-stability self-curing waterborne polyurethane for concrete protection at room temperature and a preparation method thereof.
Background
Cement concrete is the most widely used civil and architectural engineering material, but aggressive media such as Cl -、CO2 and SO 4 2- in the use environment can enter the interior of the concrete through pores in the cement concrete and cause corrosion and aging through physical and chemical actions, leading to early failure of the materials and structures of the cement concrete. Paint protection is an important measure for improving the corrosion resistance of concrete. The aqueous polyurethane coating has the characteristics of good flexibility, strong adhesive force, good weather resistance, excellent solvent resistance, environmental friendliness and the like, and has wide application prospect in concrete structure protection. However, the hydrophilic groups in the aqueous polyurethane dispersion lead to slow curing of the coating film, and the cured film has poor water resistance, so that the protective performance of the aqueous polyurethane coating on concrete is affected.
The water-based polyurethane is modified by utilizing epoxy resin, organic silicon and the like, so that the water resistance, alkali resistance and other performances of a coating film are improved, and the water-based polyurethane is an effective way for realizing the high performance of the water-based polyurethane protective coating for concrete, wherein the epoxy resin modified water-based polyurethane is the most common. However, most of the common epoxy resin modified waterborne polyurethane concrete protective coating is bi-component, the components such as epoxy resin modified waterborne polyurethane dispersoid and curing agent are required to be stored and transported independently, and mixed in proportion before use, so that the construction and use cost is increased, and the product performance is possibly unstable due to the problems of operation, construction and the like; the single-component epoxy resin modified aqueous polyurethane dispersion is applied to concrete protection, has the characteristics of simple transportation and operation, short construction period and the like, but the realization of stable dispersion of the epoxy resin modified aqueous polyurethane prepolymer and the improvement of the storage stability of the dispersion are difficult problems. The thermal crosslinking type epoxy resin modified waterborne polyurethane has a longer storage stability period, but has a higher curing initial temperature, so that the use of the thermal crosslinking type epoxy resin modified waterborne polyurethane is limited. Liu Jiaxin and the like in the room temperature curing single-component building structural adhesive preparation and performance research, 1, 3-cyclohexanediamine and methyl isobutyl ketone are used as raw materials to prepare a ketimine latent curing agent, and the latent curing agent and E-51 epoxy resin form the single-component structural adhesive which has a storage time of 30 days under the condition that the relative humidity is 10%; yang Guo, et al, in the "synthesis of ketone-aldehyde resins and use thereof in latent curing agents", reacted ketone-aldehyde resins with ethylenediamine, hexamethylenediamine and m-phenylenediamine, respectively, to give 3 ketimines, and the storage time of a single-component epoxy resin composed of 3 latent curing agents and an epoxy resin under the condition of air insulation was 63, 33 and 35 days, respectively. The latent type cured epoxy group modified aqueous polyurethane dispersoid can be cured into a film at room temperature, but has the problems of insufficient storage stability and the like of the dispersoid, and influences transportation, storage and use.
Disclosure of Invention
The invention aims to provide high-storage-stability self-curing aqueous polyurethane for concrete protection and a preparation method thereof. The ketimine containing the secondary amine group is used as a rear chain extender of the epoxy resin modified waterborne polyurethane to prepare the waterborne polyurethane dispersoid with high storage stability and room temperature self-curing performance for protecting concrete, so that the high storage stability of the single-component epoxy resin modified waterborne polyurethane dispersoid is realized, the dispersoid can be self-cured at room temperature after film formation, the adhesive force, the water resistance and the corrosion resistance of environmental media to concrete and the like of the film are excellent, and the protection of civil engineering structures such as concrete and the like can be effectively realized.
To achieve the above and other related objects, the present invention provides a high storage stability, room temperature self-curable aqueous polyurethane for concrete protection and a preparation method thereof, which at least comprises the following raw materials:
In some embodiments of the invention, the ketimine post-chain extender comprises a compound having the formula One or more of the compounds of (a) are mixed;
Wherein R 1 and R 2 are alkyl chains.
In some embodiments of the invention, the ketimine post-chain extender comprises at least one secondary amine group.
In some embodiments of the invention, the ketimine post-chain extender is stored and used in the ketone solvent.
In some embodiments of the invention, the epoxy resin is at least one of the following structural formulas One of the compounds of (2);
wherein the average value of the n value range is 1-2.
In some embodiments of the invention, the epoxy resin comprises hydroxyl groups and epoxy groups.
The invention provides a method for preparing high-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection, which is characterized by at least comprising the following steps:
adding polyamine into acetone, adding a dried molecular sieve, and removing water for 8 hours to obtain a ketimine chain extender;
Adding oligomer dihydric alcohol into a reactor, heating to 110-120 ℃ for vacuum dehydration for 1-2 hours, drying and dehydrating a hydrophilic chain extender in a vacuum oven at 80 ℃ for 8 hours, and dehydrating a small molecular chain extender by adopting a molecular sieve;
Adding the dried and dehydrated oligomer dihydric alcohol and diisocyanate into a reactor with a stirring device, polymerizing for 2-3 hours at 85 ℃ to obtain polyurethane prepolymer, cooling to 70-80 ℃, adding the hydrophilic chain extender, the micromolecular chain extender and a catalyst into the polyurethane prepolymer, continuously reacting for 3-4 hours, cooling to 60-70 ℃, adding epoxy resin, reacting for 1-2 hours, and adding ketone solvent in the reaction process to regulate the viscosity to obtain epoxy resin modified waterborne polyurethane prepolymer;
adding a neutralization salifying agent into the epoxy resin modified waterborne polyurethane prepolymer, and carrying out neutralization reaction for 25-35 minutes at the temperature of 40-50 ℃;
Adding deionized water and the ketimine post-chain extender into the epoxy resin modified waterborne polyurethane prepolymer after the neutralization reaction, and carrying out high-speed shearing and emulsification for 25-35 minutes at the temperature of 0-20 ℃ to obtain the waterborne polyurethane dispersion with high storage stability and room temperature self-curing.
In some embodiments of the invention, the epoxy resin mass fraction in the epoxy resin modified waterborne polyurethane is less than 10%.
In some embodiments of the invention, the molar ratio of the number of secondary amine groups of the ketimine post-chain extender to the number of moles of isocyanate end groups of the epoxy resin modified waterborne polyurethane prepolymer is 1.
The invention also provides application of the high-storage-stability room-temperature self-curing aqueous polyurethane for protecting concrete in building waterproofing and engineering protection.
In summary, the invention provides the high-storage-stability self-curable aqueous polyurethane for protecting concrete and the preparation method thereof. Epoxy resin is used as a comonomer, ketimine containing secondary amine groups is used as a rear chain extender, and polyurethane is prepared by the ketimine method, so that the storage stability of the epoxy resin modified polyurethane dispersoid is improved. The dispersion has lower film forming temperature, can realize self-curing through the crosslinking reaction between macromolecular chains at room temperature, and forms a coating, the bonding force between the coating and a concrete substrate is strong, and the water resistance, alkali resistance and corrosion resistance of the coating are improved. The invention uses water as a dispersion medium, is environment-friendly, and reduces the production cost of the epoxy resin modified polyurethane dispersoid.
Drawings
FIG. 1 is a graph showing the swelling experiment of an epoxy-modified aqueous polyurethane film and an aqueous polyurethane film not modified with epoxy resin in tetrahydrofuran solvent in example 3.
Fig. 2 is a stress-strain graph of the epoxy-modified aqueous polyurethane film and the aqueous polyurethane film without the epoxy modification in example 1.
Fig. 3 is a stress-strain graph of the epoxy-modified aqueous polyurethane film and the non-epoxy-modified aqueous polyurethane film of example 3 before and after alkali treatment.
Fig. 4 is a graph comparing the adhesive strength of the epoxy-modified aqueous polyurethane film and the aqueous polyurethane film without the epoxy modification on a concrete substrate in example 3.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the present invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Unless otherwise specified, "%" and "parts" shown in the following examples refer to "% by mass" and "parts by mass", respectively.
The high-storage-stability room-temperature self-curable aqueous polyurethane for concrete protection and the preparation method thereof provided by the invention have the advantages that the obtained high-storage-stability room-temperature self-curable aqueous polyurethane dispersoid for concrete protection has high storage stability, the dispersoid can be self-cured at room temperature to form a coating after film formation, the adhesion force between the dispersoid and a concrete substrate is strong, and the coating has excellent water resistance, alkali resistance and corrosion resistance, so that the aqueous polyurethane can be widely applied to the fields of building waterproofing, engineering protection and the like.
In the embodiment of the invention, the high-storage-stability room-temperature self-curable aqueous polyurethane for protecting concrete comprises raw materials such as diisocyanate, dihydric alcohol, epoxy resin, ketimine rear chain extender and the like. Wherein the content of the diisocyanate is, for example, 8.0 to 15.0 parts by mass, and the diisocyanate is, for example, selected from one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like. In this example, the diisocyanate is, for example, isophorone diisocyanate.
In the embodiment of the present invention, in the aqueous polyurethane, the content of the diol is, for example, 8.0 to 15.0 parts by mass, the diol is, for example, an oligomer diol, and, for example, an oligomer diol having a molecular weight of 1000 to 4000 is selected. The oligomer diol is, for example, one or a mixture of several selected from the group consisting of polyhexamethylene adipate diol, polybutylene adipate diol, polyethylene adipate butanediol diol and polytetrahydrofuran diol, and the specific kind of the oligomer diol is not limited in the present invention. Polyurethane prepolymers are formed by reacting diols and diisocyanates.
In the embodiment of the invention, the content of the ketimine post-chain extender in the aqueous polyurethane is, for example, 0.5 to 1.5 parts by mass. In this embodiment, the ketimine may, for example, comprise a compound of the formulaOne or more of the compounds of (a) wherein R 1 and R 2 are, for example, alkyl chains. And the ketimine post-chain extender, for example, contains at least one secondary amine group, in this embodiment, the ketimine post-chain extender contains, for example, only one secondary amine group. The ketimine rear chain extender is added into the epoxy modified polyurethane, the secondary amine group of the ketimine in the ketimine rear chain extender reacts with the isocyanate group, the primary amino group reacts with the epoxy group, a hydrophobic structure is formed near the hydrophilic group of the polyurethane, and the water resistance of the epoxy resin modified polyurethane coating is improved. Meanwhile, after the dispersion permeates into the pores of the concrete, epoxy groups and amine groups react and solidify to form an anchoring structure, so that the adhesive force between the coating and the concrete base material is improved. The ketimine post-chain extender is produced by polycondensation reaction of a polyamine, such as one or more of diethylenetriamine, dipropylenetriamine or triethylenetetramine, and a ketone, such as one or more of acetone, methyl isopropyl ketone or methyl isobutyl ketone. In this example, the polyamine is selected to be diethylenetriamine, for example, and the ketone is selected to be acetone, for example.
In the embodiment of the invention, the content of the epoxy resin in the aqueous polyurethane is, for example, 1.0 to 3.0 parts by mass. In this embodiment, the epoxy resin comprises a structural formula of
One or more of the compounds of (a) are mixed, i.e. the epoxy resin for example contains at least one hydroxyl group and at least one epoxy group, wherein n has an average value in the range of, for example, 1-2. The epoxy resin is, for example, one or a mixture of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a polyphenol type glycidyl ether epoxy resin, or the like, and in this embodiment, the epoxy resin is, for example, a bisphenol F type epoxy resin. The epoxy resin is added in the preparation process of the waterborne polyurethane, so that the modification of the waterborne polyurethane is realized, the hydrophobic epoxy groups in the obtained epoxy resin modified polyurethane dispersoid are coated in the epoxy resin modified waterborne polyurethane emulsion particles, and the hydrophilic amine groups are arranged on the outer surfaces of the emulsion particles, so that the dispersoid has good storage stability, the alkali resistance of a coating formed by the dispersoid is improved, and the polymer in the coating is formed into a network structure by the crosslinking and curing of the epoxy resin, so that the performances of corrosion resistance and the like of the coating are improved.
In the embodiment of the invention, the content of the hydrophilic chain extender in the aqueous polyurethane dispersion is, for example, 1.5 to 3.0 parts by mass, and the hydrophilic chain extender is, for example, one or a mixture of several of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid and the like, and is, for example, 2-dimethylolpropionic acid. The content of the neutralizing salifying agent is, for example, 1.0-2.0 parts by mass, and the neutralizing salifying agent is, for example, triethylamine, or one or a mixture of sodium hydroxide, ammonia water and the like, and is, for example, triethylamine. The content of the chain extender is, for example, 0.5 to 3.0 parts by mass, and the chain extender is, for example, one or a mixture of a plurality of small molecule chain extenders such as 1, 4-butanediol, ethylene glycol, diethylene glycol or hexanediol, and the like, and is, for example, 1, 4-butanediol. The content of the ketone solvent is, for example, 3.0 to 5.0 parts by mass, and the ketone solvent is, for example, one or a mixture of several selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. In the aqueous polyurethane dispersion, the content of deionized water is, for example, 70.0 to 100.0 parts by mass, and water is used as a dispersion medium, so that the aqueous polyurethane dispersion is environment-friendly, and the production cost of the epoxy resin modified polyurethane dispersion is reduced.
The invention provides a preparation method of high-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection, which comprises the following steps of S10-S50.
Step S10, adding polyamine into acetone, adding a dried molecular sieve, for example, dehydrating for 8 hours, and obtaining a ketimine rear chain extender;
Step S20, adding the oligomer dihydric alcohol into a reactor with a stirring device, heating to 110-120 ℃ for vacuum dehydration, wherein the dehydration time is 1-2 hours, drying and dehydrating the hydrophilic chain extender in a vacuum oven at 80 ℃ for 8 hours, and dehydrating the small molecular chain extender by using a molecular sieve;
Step S30, adding diisocyanate and the oligomer dihydric alcohol in the step S20 into a reactor with a stirring device, carrying out polymerization reaction at a temperature of, for example, 85 ℃ for 2-3 hours to obtain a polyurethane prepolymer, cooling to, for example, 70-80 ℃, adding a catalyst into the polyurethane prepolymer, continuing to react with the hydrophilic chain extender and the small molecule chain extender in the step S20 for 3-4 hours, cooling to, for example, 60-70 ℃, adding an epoxy resin, reacting for 1-2 hours, and adding a ketone solvent in the reaction process to regulate the viscosity to obtain the epoxy resin modified aqueous polyurethane prepolymer;
Step S40, adding a neutralization salifying agent into the epoxy resin modified waterborne polyurethane prepolymer, and carrying out neutralization reaction at the temperature of, for example, 40-50 ℃ for 25-35 minutes;
And S50, adding deionized water and the ketimine post-chain extender in the step S10 into the epoxy resin modified waterborne polyurethane prepolymer after the neutralization reaction, and shearing and emulsifying at a high speed, for example, at a temperature of between 0 and 20 ℃ for 25 to 35 minutes to obtain the high-storage-stability waterborne polyurethane dispersion capable of being modified by the room-temperature self-cured epoxy resin for protecting concrete.
In an embodiment of the present invention, in step S10, a polycondensation reaction of a polyamine, for example, with a ketone, is carried out to produce a ketimine, which is used, for example, as a post-chain extender, and the ketimine post-chain extender is stored and used, for example, in a ketone solvent. In step S20, the molecular weight of the oligomeric diol is, for example, 1000 or 2000.
In the embodiment of the present invention, in steps S20 to S30, the oligomer diol, the hydrophilic chain extender, the small molecule chain extender, the diisocyanate, and the obtained polyurethane prepolymer are dried before the reaction.
In the embodiment of the present invention, in step S50, the ketimine post-chain extender prepared in step S10 is added, wherein the ratio of the number of moles of secondary amine groups of the added ketimine post-chain extender to the number of moles of isocyanate end groups in the epoxy resin modified aqueous polyurethane prepolymer after the neutralization reaction is, for example, 1. The obtained aqueous polyurethane dispersion with high storage stability for concrete protection, which can be modified by room temperature self-curing epoxy resin, and the mass fraction of epoxy resin in the epoxy resin modified aqueous polyurethane is less than 10 percent.
In the embodiment of the invention, a preparation method of the aqueous polyurethane film with high storage stability and room temperature self-curable epoxy resin for concrete protection is also provided, and the preparation method comprises the steps of pouring the prepared epoxy resin modified aqueous polyurethane dispersion into a mold, for example, a tetrafluoro mold. Drying for e.g. three days at room temperature and transferring to an oven for e.g. one day, the oven temperature being e.g. set at 60 c, a crosslinked epoxy resin modified waterborne polyurethane film is obtained.
In the examples of the present invention, the water absorption of the aqueous polyurethane films for concrete protection of examples 1 to 3 and comparative examples 1 to 3, which were high in storage stability, were self-curable at room temperature, were tested. The samples of the aqueous polyurethane films of example 3 and comparative example 3 were tested for swelling in tetrahydrofuran solvent. The stress-strain curves of the aqueous polyurethane film samples of example 1 and comparative example 1, and the stress-strain curves of the aqueous polyurethane film samples of example 3 and comparative example 3 before and after alkali treatment were tested. Meanwhile, the aqueous polyurethane film samples of example 3 and comparative example 3 were tested for adhesive strength on concrete substrates.
The invention will be described in more detail below by introducing specific examples.
Example 1
The aqueous polyurethane dispersoid modified by the room temperature self-curing epoxy resin and having high storage stability for protecting concrete is prepared.
Step S10, adding 0.3 part by mass of diethylenetriamine into acetone, adding the acetone into a dried molecular sieve, and removing water for 8 hours to obtain a ketimine post-chain extender;
Step S20, heating 14.6 parts by mass of oligomer dihydric alcohol with the molecular weight of 1000 to 110 ℃ in a reactor, carrying out vacuum drying and dewatering for 2 hours under mechanical stirring, drying and dewatering 1.1 parts by mass of hydrophilic chain extender 2, 2-dimethylolpropionic acid in a vacuum oven at 80 ℃ for 8 hours, and dewatering 1.4 parts by mass of small molecular chain extender 1, 4-butanediol by using a molecular sieve;
Step S30, adding the oligomer dihydric alcohol in the step S20 and 9.7 parts by mass of isophorone diisocyanate after water removal into a reactor with a stirring device, polymerizing for 3 hours at 85 ℃ to obtain a polyurethane prepolymer, cooling to 80 ℃, adding a catalyst dibutyl tin dilaurate and a hydrophilic chain extender in the step S20 into the polyurethane prepolymer, reacting for 3 hours, continuously adding the micromolecule chain extender in the step S20 into the system, reacting for 1 hour, then adding 2.7 parts by mass of bisphenol F type epoxy resin, reacting for 2 hours, and adding a ketone solvent in the reaction process to regulate the viscosity to obtain the epoxy resin modified waterborne polyurethane prepolymer;
step S40, cooling the epoxy resin modified waterborne polyurethane prepolymer in the step S30 to 40 ℃, and then adding a neutralization salifying agent triethylamine for neutralization reaction for 30 minutes;
And S50, cooling the epoxy resin modified waterborne polyurethane prepolymer in the step S40 to room temperature, adding 70.0 parts by mass of deionized water under the stirring of 1500rpm, stirring for 5min, adding 0.3 parts by mass of ketimine post-chain extender in the step S10, and carrying out high-speed shearing and emulsification for 30min at 0-20 ℃ to obtain the waterborne polyurethane dispersion with high storage stability for protecting concrete and capable of being modified by the room temperature self-curing epoxy resin.
The aqueous polyurethane film modified by the room-temperature self-curing epoxy resin and having high storage stability for protecting concrete is prepared.
And (3) pouring the aqueous polyurethane dispersion which is prepared in the steps (S10-S50) and is modified by the epoxy resin and can be self-cured at room temperature into a tetrafluoro mold, drying for three days at room temperature, and transferring into a 60 ℃ oven for drying for one day to obtain the crosslinked aqueous polyurethane film modified by the epoxy resin, namely the aqueous polyurethane film which is prepared by the step (S10-S50) and is high in storage stability and can be self-cured at room temperature and is named WPUE-A.
Example 2
The aqueous polyurethane dispersoid modified by the room temperature self-curing epoxy resin and having high storage stability for protecting concrete is prepared.
Step S10, adding 0.3 part by mass of diethylenetriamine into acetone, adding the acetone into a dried molecular sieve, and removing water for 8 hours to obtain a ketimine post-chain extender;
step S20, heating 12.5 parts by mass of oligomer dihydric alcohol with the molecular weight of 1000 to 110 ℃ in a reactor, carrying out vacuum drying and dewatering for 2 hours under mechanical stirring, drying and dewatering 1.1 parts by mass of hydrophilic chain extender 2, 2-dimethylolpropionic acid in a vacuum oven at 80 ℃ for 8 hours, and dewatering 2.2 parts by mass of small molecular chain extender 1, 4-butanediol by using a molecular sieve;
Step S30, adding the oligomer dihydric alcohol in the step S20 and 11.2 parts by mass of isophorone diisocyanate after water removal into a reactor with a stirring device, polymerizing for 3 hours at 85 ℃ to obtain a polyurethane prepolymer, cooling to 80 ℃, adding a catalyst dibutyl tin dilaurate and a hydrophilic chain extender in the step S20 into the polyurethane prepolymer, reacting for 3 hours, continuously adding the micromolecule chain extender in the step S20 into the system, reacting for 1 hour, then adding 2.7 parts by mass of bisphenol F type epoxy resin, reacting for 2 hours, and adding a ketone solvent in the reaction process to regulate the viscosity to obtain the epoxy resin modified waterborne polyurethane prepolymer;
step S40, cooling the epoxy resin modified waterborne polyurethane prepolymer in the step S30 to 40 ℃, and then adding a neutralization salifying agent triethylamine for neutralization reaction for 30 minutes;
And S50, cooling the epoxy resin modified waterborne polyurethane prepolymer in the step S40 to room temperature, adding 70.0 parts by mass of deionized water under the stirring of 1500rpm, stirring for 5min, adding 0.3 parts by mass of ketimine post-chain extender in the step S10, and carrying out high-speed shearing and emulsification for 30min at 0-20 ℃ to obtain the high-storage-stability room-temperature self-curable epoxy resin modified waterborne polyurethane dispersion for protecting concrete.
The preparation method is used for preparing the aqueous polyurethane film modified by the epoxy resin and capable of self-curing at room temperature, and the aqueous polyurethane film is high in storage stability and capable of self-curing at room temperature for protecting concrete.
And (3) pouring the high-storage-stability room-temperature self-curable epoxy resin modified aqueous polyurethane dispersion for concrete protection prepared in the steps S10-S50 into a tetrafluoro mold, drying for three days at room temperature, and transferring into a 60 ℃ oven for drying for one day to obtain a crosslinked epoxy resin modified aqueous polyurethane film, namely the high-storage-stability room-temperature self-curable epoxy resin modified aqueous polyurethane film for concrete protection, which is named WPUE-B.
Example 3
The epoxy modified aqueous polyurethane dispersion with high storage stability and room temperature self-curing performance for protecting concrete is prepared.
Step S10, adding 0.3 part by mass of diethylenetriamine into acetone, adding the acetone into a dried molecular sieve, and removing water for 8 hours to obtain a ketimine post-chain extender;
Step S20, heating 15.5 parts by mass of oligomer dihydric alcohol with the molecular weight of 2000 to 110 ℃ in a reactor, carrying out vacuum drying and dewatering for 2 hours under mechanical stirring, drying and dewatering 1.1 parts by mass of hydrophilic chain extender 2, 2-dimethylolpropionic acid in a vacuum oven with the temperature of 80 ℃ for 8 hours, and dewatering 1.7 parts by mass of small molecular chain extender 1, 4-butanediol by using a molecular sieve;
Step S30, adding the oligomer dihydric alcohol in the step S20 and 9.7 parts of dried isophorone diisocyanate into a reactor with a stirring device, polymerizing for 3 hours at 85 ℃ to obtain a polyurethane prepolymer, cooling to 80 ℃, adding a catalyst dibutyl tin dilaurate and a hydrophilic chain extender in the step S20 into the polyurethane prepolymer, reacting for 3 hours, continuously adding the small molecule chain extender in the step S20 into the system, reacting for 1 hour, then adding 2.7 parts by mass of bisphenol F type epoxy resin, reacting for 2 hours, and adding a ketone solvent in the reaction process to adjust the viscosity to obtain the epoxy resin modified waterborne polyurethane prepolymer;
step S40, cooling the epoxy resin modified waterborne polyurethane prepolymer in the step S30 to 40 ℃, and then adding a neutralization salifying agent triethylamine for neutralization reaction for 30 minutes;
And S50, cooling the epoxy resin modified waterborne polyurethane prepolymer in the step S40 to room temperature, adding 70.0 parts by mass of deionized water under the stirring of 1500rpm, stirring for 5min, adding 0.3 parts by mass of ketimine post-chain extender in the step S10, and carrying out high-speed shearing and emulsification for 30min at 0-20 ℃ to obtain the epoxy resin modified waterborne polyurethane dispersion with high storage stability and room temperature self-curing for concrete protection.
The aqueous polyurethane film modified by the epoxy resin which has high storage stability and can be self-cured at room temperature is prepared for protecting concrete.
And (3) pouring the high-storage-stability room-temperature self-curable aqueous polyurethane dispersion for concrete protection prepared in the steps S10-S50 into a tetrafluoro mold, drying for three days at room temperature, and transferring into a 60 ℃ oven for drying for one day to obtain the crosslinked epoxy resin modified aqueous polyurethane film, namely the high-storage-stability room-temperature self-curable aqueous polyurethane film for concrete protection, which is named WPUE-C.
Comparative examples 1-3 were the non-epoxidized aqueous polyurethane films prepared according to the experimental procedure of examples 1-3, designated WPU-A, WPU-B and WPU-C, respectively, i.e., comparative example 1 was the non-epoxidized aqueous polyurethane film prepared according to the experimental procedure and experimental conditions of example 1, designated WPU-a, comparative example 2 corresponds to example 2, and comparative example 3 corresponds to example 3.
Water absorption test data of the aqueous polyurethane films prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
As can be seen from Table 1, the aqueous polyurethane films modified with the epoxy resin, which have high storage stability and can be self-cured at room temperature, for protecting concrete prepared in examples 1 to 3 all have lower water absorption than the aqueous polyurethane film not modified with the epoxy resin, which indicates that the introduction of the epoxy resin causes the system to crosslink and reduces the water absorption of the film. And the water absorption rate of the epoxy modified waterborne polyurethane film with high storage stability and room temperature self-curing for concrete protection prepared in the examples 1-3 is less than 5%, thereby meeting the use requirement of the building waterproof coating.
TABLE 1 Water absorption test data for aqueous polyurethane films prepared in examples 1-3 and comparative examples 1-3
Fig. 1 shows the swelling experiments of WPU-C and WPUE-C in tetrahydrofuran solvent for the aqueous polyurethane film sample in example 3, and the experiments show that WPU-C is dissolved in tetrahydrofuran, and WPUE-C generates a crosslinked structure due to the introduction of epoxy resin, so that only the WPU-C swells and is not dissolved, thus indicating that the solvent resistance of the epoxy resin modified aqueous polyurethane film can be improved.
Fig. 2 is a stress-strain curve of the aqueous polyurethane film samples of example 1 and comparative example 1, and fig. 3 is a stress-strain curve of the aqueous polyurethane film samples of example 3 and comparative example 3 before and after alkali treatment. Fig. 2 and 3 show that the mechanical properties, alkali resistance and corrosion resistance of the epoxy resin modified aqueous polyurethane film are improved compared with the unmodified aqueous polyurethane film. Fig. 4 shows the adhesive strength of the aqueous polyurethane film sample of example 3 and comparative example 3 on the concrete substrate, and the adhesive strength of the epoxy resin modified aqueous polyurethane film of example 3 on the concrete substrate is significantly stronger than that of the unmodified aqueous polyurethane film of comparative example 3.
In summary, the invention provides the high-storage-stability room-temperature self-curable aqueous polyurethane for concrete protection and the preparation method thereof, wherein epoxy resin is adopted as a comonomer, ketimine containing secondary amine groups is adopted as a rear chain extender, and the epoxy resin modified aqueous polyurethane dispersion is prepared by a ketimine method, so that the prepared high-storage-stability room-temperature self-curable epoxy resin modified aqueous polyurethane dispersion for concrete protection has high storage stability and room-temperature self-curing performance, the water resistance, the corrosion resistance and the alkali resistance of the aqueous polyurethane film prepared by the high-storage-stability room-temperature self-curable aqueous polyurethane dispersion for concrete protection are improved, and the adhesive force between the aqueous polyurethane coating and a concrete substrate is enhanced.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The high-storage-stability room-temperature self-curing aqueous polyurethane for protecting concrete is characterized by at least comprising the following raw materials:
wherein the ketimine post-chain extender comprises at least one secondary amine group;
the epoxy resin comprises hydroxyl groups and epoxy groups;
The ketimine post-chain extender comprises a structural formula of One or more of the compounds of (a) and (b), R 1 and R 2 are alkyl chains.
2. The high storage-stable, room-temperature self-curable aqueous polyurethane for concrete protection according to claim 1, wherein the ketimine post-chain extender is stored and used in the ketone solvent.
3. The high storage-stable room-temperature self-curable aqueous polyurethane for concrete protection according to claim 1, wherein the epoxy resin comprises at least a structural formula as shown in One of the compounds of (2);
wherein the average value of the n value range is 1-2.
4. A process for preparing a high storage-stable, room-temperature self-curable aqueous polyurethane for concrete protection according to any one of claims 1 to 3, characterized by comprising at least the following steps:
adding polyamine into acetone, adding a dried molecular sieve, and removing water for 8 hours to obtain a ketimine chain extender;
Adding dihydric alcohol into a reactor, heating to 110-120 ℃ for vacuum dehydration for 1-2 hours, drying and dehydrating the hydrophilic chain extender in a vacuum oven at 80 ℃ for 8 hours, and dehydrating the small molecular chain extender by adopting a molecular sieve;
Adding the dihydric alcohol and the diisocyanate after drying and dewatering into a reactor with a stirring device, polymerizing for 2-3 hours at 85 ℃ to obtain polyurethane prepolymer, cooling to 70-80 ℃, adding the hydrophilic chain extender, the micromolecular chain extender and the catalyst into the polyurethane prepolymer, continuously reacting for 3-4 hours, cooling to 60-70 ℃, adding epoxy resin, reacting for 1-2 hours, and adding ketone solvent in the reaction process to regulate viscosity to obtain epoxy resin modified waterborne polyurethane prepolymer;
adding a neutralization salifying agent into the epoxy resin modified waterborne polyurethane prepolymer, and carrying out neutralization reaction for 25-35 minutes at the temperature of 40-50 ℃;
Adding deionized water and the ketimine post-chain extender into the epoxy resin modified waterborne polyurethane prepolymer after the neutralization reaction, and shearing and emulsifying at a high speed for 25-35 minutes at a temperature of 0-20 ℃ to obtain the waterborne polyurethane with high storage stability for protecting concrete and room temperature self-curing.
5. The method for preparing a high storage-stability room-temperature self-curable aqueous polyurethane for concrete protection according to claim 4, wherein the mass fraction of the epoxy resin in the epoxy resin modified aqueous polyurethane prepolymer is less than 10%.
6. The method for preparing a high storage-stable, room-temperature self-curable aqueous polyurethane for concrete protection according to claim 4, wherein the ratio of the number of moles of secondary amine groups of the ketimine rear chain extender to the number of moles of isocyanate end groups of the epoxy resin-modified aqueous polyurethane prepolymer is 1.
7. Use of a high storage-stable, room-temperature self-curable aqueous polyurethane for concrete protection according to any one of claims 1 to 3 for waterproofing and engineering protection of buildings.
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| CN115058176A (en) * | 2022-05-31 | 2022-09-16 | 广东粤港澳大湾区黄埔材料研究院 | Epoxy modified self-extinction waterborne polyurethane emulsion and preparation method thereof |
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| CN115058176A (en) * | 2022-05-31 | 2022-09-16 | 广东粤港澳大湾区黄埔材料研究院 | Epoxy modified self-extinction waterborne polyurethane emulsion and preparation method thereof |
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