CN116875174A - Silane modified polyurethane waterproof coating and preparation method thereof - Google Patents
Silane modified polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN116875174A CN116875174A CN202310992581.0A CN202310992581A CN116875174A CN 116875174 A CN116875174 A CN 116875174A CN 202310992581 A CN202310992581 A CN 202310992581A CN 116875174 A CN116875174 A CN 116875174A
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- Prior art keywords
- silane
- parts
- modified polyurethane
- polyurethane waterproof
- polyether polyol
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- 239000004432 silane-modified polyurethane Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 claims abstract description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- 239000003973 paint Substances 0.000 claims description 29
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 22
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000004658 ketimines Chemical class 0.000 claims description 14
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 11
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 3
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 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 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
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 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 2
- 238000004321 preservation Methods 0.000 claims description 2
- RXQXPMOQOKMLRT-UHFFFAOYSA-N n'-[[methoxy-methyl-(2-methylpropyl)silyl]oxymethyl]ethane-1,2-diamine Chemical compound CC(C)C[Si](C)(OC)OCNCCN RXQXPMOQOKMLRT-UHFFFAOYSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- JEBKVIMEQBQNPT-UHFFFAOYSA-N 1-(5-bromo-2-methoxyphenyl)sulfonylpiperidine Chemical compound COC1=CC=C(Br)C=C1S(=O)(=O)N1CCCCC1 JEBKVIMEQBQNPT-UHFFFAOYSA-N 0.000 description 9
- SVSGVNLFCVYWRB-UHFFFAOYSA-N 1-[methoxy-methyl-(2-methylpropyl)silyl]oxypropane-1,1-diamine Chemical compound CCC(N)(N)O[Si](C)(OC)CC(C)C SVSGVNLFCVYWRB-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000013530 defoamer Substances 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 4
- 238000004078 waterproofing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- YPXOWDVLPADBEP-UHFFFAOYSA-N NNCCC[Si](OC(C)CC)(OCC)OCC Chemical compound NNCCC[Si](OC(C)CC)(OCC)OCC YPXOWDVLPADBEP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of waterproof coatings, and provides a silane modified polyurethane waterproof coating and a preparation method thereof. The silane modified polyurethane waterproof coating comprises the following raw materials in parts by mass: 3-8 parts of polyisocyanate, 15-35 parts of polyether polyol, 10-20 parts of plasticizer, 40-60 parts of filler, 0.05-0.1 part of catalyst, 0.15-0.25 part of silane coupling agent, 0.5-1 part of auxiliary agent, 5-10 parts of solvent and 1-2 parts of curing agent; the silane coupling agent includes silane having two amino structures and epoxysilane. By the technical scheme, the problem that the tensile strength, the bonding strength and the waterproof performance of the silane modified polyurethane waterproof coating in the prior art are required to be further improved is solved.
Description
Technical Field
The invention relates to the technical field of waterproof coatings, in particular to a silane modified polyurethane waterproof coating and a preparation method thereof.
Background
The polyurethane waterproof paint is one kind of waterproof polymer material with polyurethane resin as main film forming matter and consists of polyurethane prepolymer with isocyanate group (-NCO) and hydroxyl group (-OH) or amino group (-NH) 2 ) A reactive coating waterproof material formed by mixing the curing agent and other auxiliary agents.
The polyurethane waterproof coating is mainly used for connecting expansion joint materials and concrete in bridge engineering, so the polyurethane waterproof coating has good mechanical properties, good bonding strength with concrete and good waterproof performance, but the mechanical properties, bonding strength and waterproof performance of the polyurethane waterproof coating in the current market are not ideal.
In recent years, many researches on silane modified polyurethane waterproof paint are carried out, and on the basis of ensuring high elasticity, excellent low-temperature flexibility and wear resistance, the tensile strength, bonding strength and waterproof performance of the waterproof paint are improved. Among the various silanes, the silane having a diamino structure can react with the prepolymer, grafted on the main polymer chain, and the siloxane is grafted on the side chain and exposed outside, so that the polyurethane waterproof coating is endowed with an optimal waterproof effect, but the silane having a diamino structure reacts with isocyanate groups in the prepolymer very fast, so that the viscosity of the system increases faster, and the capability of improving the tensile strength, the adhesive strength and the waterproof performance of the silane modified polyurethane waterproof coating is limited.
Disclosure of Invention
The invention provides a silane modified polyurethane waterproof coating and a preparation method thereof, which solve the problem that the tensile strength, the bonding strength and the waterproof performance of the silane modified polyurethane waterproof coating in the related art are required to be further improved.
The technical scheme of the invention is as follows:
a silane modified polyurethane waterproof coating comprises the following raw materials in parts by mass: 3-8 parts of polyisocyanate, 15-35 parts of polyether polyol, 10-20 parts of plasticizer, 40-60 parts of filler, 0.05-0.1 part of catalyst, 0.15-0.25 part of silane coupling agent, 0.5-1 part of auxiliary agent, 5-10 parts of solvent and 1-2 parts of curing agent;
the silane coupling agent includes silane having two amino structures and epoxysilane.
As a further technical scheme, the silane with two amino structures comprises amino ethyl amino isobutyl methyl dimethoxy silane; the epoxysilane includes beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane and/or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane.
As a further technical scheme, the mass of the silane with two amino structures is equal to or higher than that of the epoxy silane.
As a further technical scheme, the mass of the silane with two amino structures is more than 1.5 times of that of the epoxy silane.
As a further technical scheme, the mass ratio of the silane with two amino structures to the epoxy silane is 0.13:0.07-0.15:0.05.
As a further technical scheme, the polyisocyanate comprises one or more of TDI, MDI, HMDI, IPDI;
the polyether polyol comprises one or more of polyether polyol 210, polyether polyol 220 and polyether polyol 330N.
As a further technical scheme, the plasticizer comprises one or more of dioctyl phthalate, dibutyl phthalate and dibutyl sebacate;
the filler comprises one or more of kaolin, talcum powder and carbon black;
the catalyst comprises dibutyl tin dilaurate and/or stannous octoate;
the auxiliary agent comprises one or more of an antifoaming agent, a dispersing agent and an antioxidant.
As a further technical scheme, the solvent comprises one or more of dimethylbenzene and methylbenzene;
the curing agent comprises one or more of ketimine curing agent DA-315, ketimine curing agent DA-134 and oxazolidine latent curing agent XY-401.
The invention also provides a preparation method of the silane modified polyurethane waterproof paint, which comprises the following steps: uniformly mixing polyether polyol, plasticizer, filler and auxiliary agent, vacuum dehydrating, adding polyisocyanate and solvent for a first reaction, adding 1/2 mass of catalyst for a second reaction, adding curing agent and silane coupling agent for heat preservation, adding the rest catalyst for a third reaction, and obtaining the silane modified polyurethane waterproof coating.
As a further technical scheme, the temperature of the vacuum dehydration is 110-120 ℃, and the vacuum degree is less than or equal to minus 0.09MPa.
The working principle and the beneficial effects of the invention are as follows:
the silane with two amino structures and the epoxy silane are matched for use, so that the reactivity of the silane coupling agent with two amino structures is improved, the reaction speed of the silane coupling agent and isocyanate groups in the prepolymer is optimized, and the viscosity of the system is adjusted, thereby improving the tensile strength, the bonding strength and the waterproof performance of the polyurethane waterproof coating, and solving the problem that the capability of improving the tensile strength, the bonding strength and the waterproof performance of the polyurethane waterproof coating by the silane modified polyurethane waterproof coating in the prior art is limited.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a graph showing the water contact angle of the silane-modified polyurethane waterproof paint obtained in example 1 of the present invention;
fig. 2 is a water contact angle test chart of the silane-modified polyurethane waterproof paint obtained in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are heated at the temperature for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.05 part of (amino ethylamino) -3-isobutyl dimethyl methoxysilane and 0.15 part of 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, are cooled to 65 ℃ and are further added with 0.04 part of dibutyltin dilaurate for 20 minutes, so as to obtain the silane modified polyurethane waterproof paint.
Example 2
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are heated at the temperature for 0.5 hour by adding 1.5 parts of ketimine curing agent DA-315 and 0.05 part of N-aminoethyl-3-aminopropyl triethoxysilane and 0.15 part of 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, are cooled to 65 ℃, are further added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and the silane modified polyurethane waterproof paint is obtained.
Example 3
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.05 part of amino ethyl amino isobutyl methyl dimethoxy silane, are heated for 0.5 hour, are cooled to 65 ℃, are added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and are obtained.
Example 4
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.1 part of amino ethyl amino isobutyl methyl dimethoxy silane, are heated for 0.5 hour, are cooled to 65 ℃, are added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and are obtained.
Example 5
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.12 part of amino ethyl amino isobutyl methyl dimethoxy silane, are heated for 0.08 part of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, are cooled to 65 ℃, are added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and the silane modified polyurethane waterproof paint is obtained.
Example 6
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.13 part of amino ethyl amino isobutyl methyl dimethoxy silane, are heated for 0.07 part of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, are cooled to 65 ℃, are added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and the silane modified polyurethane waterproof paint is obtained.
Example 7
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.15 part of amino ethyl amino isobutyl methyl dimethoxy silane, are heated for 0.5 hour, are cooled to 65 ℃, are added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and are obtained.
Example 8
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃, are added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃, are added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are added with 1.5 parts of ketimine curing agent DA-315 and 0.18 part of amino ethyl amino isobutyl methyl dimethoxy silane, are heated for 0.02 part of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, are cooled to 65 ℃, are added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and the silane modified polyurethane waterproof paint is obtained.
Example 9
15 parts of polyether polyol 220, 10 parts of dibutyl sebacate, 40 parts of kaolin and 0.5 part of antioxidant 1010 are uniformly mixed at 115 ℃, are dehydrated in vacuum at-0.1 MPa for 2 hours, are cooled to 85 ℃, are added with 3 parts of HMDI and 5 parts of dimethylbenzene for 3 hours, are cooled to 75 ℃, are added with 0.025 part of stannous octoate for 0.5 hours, are heated at the temperature for 0.5 hour by adding 1 part of oxazolidine latent curing agent XY-401 and 0.05 part of (amino ethyl amino) -3-isobutyl dimethyl methoxy silane and 0.1 part of beta- (3, 4-epoxycyclohexyl) ethyl triethoxy silane, are cooled to 65 ℃, are further added with 0.025 part of stannous octoate for continuous reaction for 20 minutes, and the silane modified polyurethane waterproof paint is obtained.
Example 10
Mixing 35 parts of polyether polyol 330N, 20 parts of dibutyl phthalate, 60 parts of carbon black and 1 part of laurinol polyoxyethylene ether uniformly at 120 ℃, dewatering for 2 hours under vacuum at-0.1 MPa, cooling to 85 ℃, adding 8 parts of MDI and 10 parts of toluene for reaction for 3 hours, cooling to 75 ℃, adding 0.05 part of dibutyltin dilaurate for reaction for 0.5 hour, adding 2 parts of ketimine curing agent DA-134 and 0.1 part of (amino-ethylamino) -3-isobutyl dimethyl methoxy silane at the temperature, preserving heat for 0.15 part of beta- (3, 4-epoxycyclohexyl) ethyl triethoxy silane, cooling to 65 ℃, adding 0.05 part of dibutyltin dilaurate, and continuing to react for 20 minutes to obtain the silane modified polyurethane waterproof paint.
Comparative example 1
25 parts of polyether polyol 210, 15 parts of dioctyl phthalate, 50 parts of talcum powder and 0.8 part of Airase-5600 defoamer are uniformly mixed at 110 ℃, are dehydrated in vacuum at-0.09 MPa for 2 hours, are cooled to 85 ℃ and added with 5 parts of TDI and 8 parts of toluene for 3 hours, are cooled to 75 ℃ and added with 0.04 part of dibutyltin dilaurate for 0.5 hour, are heated to 1.5 parts of ketimine curing agent DA-315 and 0.2 part of (amino ethylamino) -3-isobutyl dimethyl methoxy silane at the temperature for 0.5 hour, are cooled to 65 ℃ and are further added with 0.04 part of dibutyltin dilaurate for continuous reaction for 20 minutes, and the silane modified polyurethane waterproof paint is obtained.
The silane modified polyurethane waterproof coatings obtained in examples 1-10 and comparative example 1 were tested for tensile strength and the like by referring to the method of GB/T16777-2008 building waterproof coating test method, and the tensile speed was 500mm/min; the adhesive strength before and after soaking was tested by referring to the method A in GB/T16777-2008 "test method for building waterproof paint", and the adhesive strength retention was calculated according to the following formula to evaluate waterproof performance:
adhesive strength retention (%) =adhesive strength after 7 days immersion ≡adhesive strength before immersion × 100
The results are recorded in table 1.
TABLE 1 tensile Strength, bond Strength and Water resistance of silane modified polyurethane Water-proofing coating
As can be seen from Table 1, the tensile strength of the silane modified polyurethane waterproof coating provided by the invention is more than 2.94MPa, the bonding strength before soaking is more than 2.15MPa, the bonding strength after soaking for 7 days is more than 1.85MPa, the bonding strength retention rate is more than 86.05%, and the silane modified polyurethane waterproof coating has good tensile strength, bonding strength and waterproof performance.
Example 1 in comparison with comparative example 1, the addition of (aminoethylamino) -3-isobutyldimethylmethoxysilane and 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane to example 1 and the addition of (aminoethylamino) -3-isobutyldimethylmethoxysilane to example 1 gave a silane-modified polyurethane waterproofing paint having a higher tensile strength, adhesive strength before immersion and adhesive strength retention than comparative example 1, indicating that the use of (aminoethylamino) -3-isobutyldimethylmethoxysilane and 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane gave a silane-modified polyurethane waterproofing paint having a better tensile strength, adhesive strength and waterproofing performance than the use of (aminoethylamino) -3-isobutyldimethylmethoxysilane alone.
In example 1, as compared with examples 2 to 3, (amino ethyl amino) -3-isobutyl dimethyl methoxy silane and 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane are added in example 1, N-amino ethyl-3-amino propyl triethoxy silane and 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane are added in example 2, amino ethyl amino isobutyl methyl dimethoxy silane and 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane are added in example 3, and the tensile strength, the bond strength before soaking and the bond strength retention rate of the silane modified polyurethane waterproof paint obtained in example 3 are higher than those of examples 1 to 2, which means that the amino ethyl amino isobutyl methyl dimethoxy silane and 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane are used together, so that the provided silane modified polyurethane waterproof paint has the best tensile strength, bond strength and waterproof performance.
The silane-modified polyurethane waterproof paint obtained in example 1 and comparative example 1 was coated on a glass substrate to form a coating layer of the same thickness, and a water contact angle test was performed, the test results are shown in fig. 1 to 2, and the results are recorded in table 2.
TABLE 2 Water contact Angle test results
As can be seen from Table 2, the silane having two amino structures and the epoxysilane of the present invention are used in combination with better hydrophobic effect than the silane-modified polyurethane waterproof paint obtained by using a single silane having two amino structures.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The silane modified polyurethane waterproof coating is characterized by comprising the following raw materials in parts by mass: 3-8 parts of polyisocyanate, 15-35 parts of polyether polyol, 10-20 parts of plasticizer, 40-60 parts of filler, 0.05-0.1 part of catalyst, 0.15-0.25 part of silane coupling agent, 0.5-1 part of auxiliary agent, 5-10 parts of solvent and 1-2 parts of curing agent;
the silane coupling agent includes silane having two amino structures and epoxysilane.
2. A silane-modified polyurethane waterproof paint according to claim 1, wherein the silane having two amino structures comprises aminoethylamino isobutyl methyl dimethoxy silane; the epoxysilane includes beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane and/or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane.
3. A silane-modified polyurethane waterproof paint according to claim 2, wherein the mass of the silane having two amino structures is equal to or higher than the mass of the epoxysilane.
4. A silane-modified polyurethane waterproof paint according to claim 3, wherein the mass of the silane having two amino groups is 1.5 times or more higher than that of the epoxysilane.
5. The silane-modified polyurethane waterproof paint according to claim 4, wherein the mass ratio of silane with two amino structures to epoxy silane is 0.13:0.07-0.15:0.05.
6. A silane-modified polyurethane waterproof paint according to claim 1, wherein the polyisocyanate comprises one or more of TDI, MDI, HMDI, IPDI;
the polyether polyol comprises one or more of polyether polyol 210, polyether polyol 220 and polyether polyol 330N.
7. The silane modified polyurethane waterproof paint according to claim 1, wherein the plasticizer comprises one or more of dioctyl phthalate, dibutyl phthalate and dibutyl sebacate;
the filler comprises one or more of kaolin, talcum powder and carbon black;
the catalyst comprises dibutyl tin dilaurate and/or stannous octoate;
the auxiliary agent comprises one or more of an antifoaming agent, a dispersing agent and an antioxidant.
8. The silane-modified polyurethane waterproof paint according to claim 1, wherein the solvent comprises one or more of xylene and toluene;
the curing agent comprises one or more of ketimine curing agent DA-315, ketimine curing agent DA-134 and oxazolidine latent curing agent XY-401.
9. The preparation method of the silane modified polyurethane waterproof paint according to any one of claims 1 to 8, which is characterized by comprising the following steps: uniformly mixing polyether polyol, plasticizer, filler and auxiliary agent, vacuum dehydrating, adding polyisocyanate and solvent for a first reaction, adding 1/2 mass of catalyst for a second reaction, adding curing agent and silane coupling agent for heat preservation, adding the rest catalyst for a third reaction, and obtaining the silane modified polyurethane waterproof coating.
10. The preparation method of the silane modified polyurethane waterproof coating according to claim 9, wherein the vacuum dehydration temperature is 110-120 ℃ and the vacuum degree is less than or equal to-0.09 MPa.
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