CN114181605B - Single-component water-based polyurethane waterproof coating and preparation method thereof - Google Patents
Single-component water-based polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN114181605B CN114181605B CN202210048254.5A CN202210048254A CN114181605B CN 114181605 B CN114181605 B CN 114181605B CN 202210048254 A CN202210048254 A CN 202210048254A CN 114181605 B CN114181605 B CN 114181605B
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses a single-component water-based polyurethane waterproof coating and a preparation method thereof. The preparation method of the coating comprises the following raw materials: polyether diol, polyether triol, polytetrahydrofuran ether glycol, fluorine-containing hydroxyl-terminated polysiloxane, diisocyanate, aromatic diamine containing polytetrahydrofuran ether chain segments, a water-based chain extender, a neutralizing agent, a solvent, a catalyst, deionized water, a water-based dispersant, a powder filler, a water-based color paste, a thickening agent, an anti-corrosion bactericide, a defoaming agent and an antifreezing agent. The single-component waterborne polyurethane waterproof coating prepared by the invention has excellent comprehensive performance, the tensile strength of a formed film is 2.4-6.9 MPa, the elongation at break is 534.2-752.1%, and the water resistance can meet the requirements of a solvent type polyurethane waterproof coating.
Description
Technical Field
The invention discloses a single-component water-based polyurethane waterproof coating and a preparation method thereof, belonging to the technical field of waterproof coatings.
Background
The building waterproof paint is an indispensable material in modern building engineering. Wherein, the resin waterproof paint has two common types, one is polyurethane waterproof paint which is solvent type; the other is single-component water-based polyacrylate paint and polymer cement waterproof paint composed of water-based polyacrylate emulsion and cement powder. The polyurethane waterproof coating has the advantages of high strength, good elasticity, strong bonding force, corrosion resistance, strong water resistance and the like, and has a very wide application range, but organic solvents with strong volatility need to be added in the production and construction application processes, so that the body of contact personnel is injured to different degrees, and the ecological environment is polluted. With the enhancement of environmental awareness of people, all countries in the world pay attention to the hazard of Volatile Organic Compounds (VOC) in organic waste gas, and relevant regulations are formulated to limit manufacturers and construction parties of the organic waste gas. Therefore, the water-based waterproof coating is more popular among people, especially in the field of civil buildings.
At the present stage, the execution standards of the water-based propionate waterproof coating products are GB/T23445-2009 polymer cement waterproof coating and JC/T864-2008 polymer emulsion building waterproof coating, and the execution standards of the solvent-based polyurethane waterproof coating are GB/T19250-2013 and TB/T2965-2018 railway bridge concrete bridge deck waterproof layer. Various performance indexes of the water-based polyacrylate waterproof coating are lower than those of the solvent type polyurethane waterproof coating, and the water-based polyacrylate waterproof coating has the defects of low strength, poor extensibility, poor low temperature resistance, poor water resistance and the like in the actual application process, so that the popularization and the application of the water-based polyacrylate waterproof coating are limited.
In the prior art, the research on the water-based acrylate emulsion waterproof coating and the water-based polyurethane waterproof coating reduces the harm caused by organic solvents to a certain extent, and some researchers adopt polyurethane modified water-based polyacrylate emulsion or blend the two, but the mechanical property of the formed film is still inferior to that of pure polyurethane waterproof coating. The pure water polyurethane waterproof coating is prepared by adding a certain amount of hydrophilic monomers in a polymerization chain extension process and adding an emulsifier to realize forced emulsification, but the water resistance of a finished waterproof coating prepared by the two schemes is poor and is far inferior to that of a solvent type polyurethane waterproof coating.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property and poor water resistance of the conventional water-based waterproof coating, and adopts the following technical scheme in order to achieve the technical effect of the invention:
a single-component waterborne polyurethane waterproof coating comprises the following raw materials: 410-530 parts of polyether diol, 50-70 parts of polyether triol, 30-90 parts of polytetrahydrofuran ether glycol, 90-200 parts of fluorine-containing hydroxyl-terminated polysiloxane, 115-250 parts of diisocyanate, 20-150 parts of aromatic diamine containing polytetrahydrofuran ether chain segments, 10-14 parts of water-based chain extender, 5.0-8.0 parts of neutralizer, 65-80 parts of solvent and catalyst, 1.5-2.3 parts of deionized water, 3.0-4.0 parts of water-based dispersant, 900-1000 parts of powder filler, 2.1-3.5 parts of water-based color paste, 5.8-7.2 parts of thickener, 2.9-4.9 parts of antiseptic bactericide, 6.0-9.0 parts of defoaming agent and 100-110 parts of antifreezing agent.
Preferably, the aromatic diamine containing the polytetrahydrofuran ether chain segment is one or a mixture of more than two of Versalink P650, versalink P1000 and Versalink P2000 which are products of Wingsho corporation (originally products of American air chemical industry), and the average molecular weights of the aromatic diamine are 810, 1200 and 2185 respectively;
preferably, the polyether diol is a mixture of two or more of polyether N210, polyether N220 and polyether N204;
preferably, the polyether triol is one of polyether N330 and polyether 330N;
preferably, the polytetrahydrofuran ether glycol (PTMEG) is one or a mixture of more than two of PTMEG-1000, PTMEG-2000 and PTMEG-3000;
preferably, the fluorine-containing hydroxyl-terminated polysiloxane is a product of Shanghai Silan high molecular material Co., ltd, and is selected from one or a mixture of more than two of 550, 1750 and 4200 in average molecular weight;
preferably, the diisocyanate is one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI-80), hexamethylene Diisocyanate (HDI), and liquefied diphenylmethane diisocyanate (MDI-50);
preferably, the solvent is one of acetone, butanone and N, N-dimethylformamide;
preferably, the aqueous chain extender is one of dimethylolpropionic acid and dimethylolbutyric acid;
preferably, the catalyst is one of dibutyltin dilaurate (T-12) and stannous octoate (T-9);
preferably, the neutralizing agent is one of triethylamine or 2-amino-2-methyl-1-propanol (AMP-95).
Preferably, the dispersant is a dispersant suitable for use in an aqueous system;
preferably, the powder filler is one or a mixture of 800-mesh heavy calcium carbonate and 600-mesh heavy calcium carbonate; the thickener is an aqueous polyurethane associative thickener, preferably one of German Bick chemical products OPTIFLO L100 and OPTIFLO L150;
preferably, the antifreeze is one of ethylene glycol and diethylene glycol.
Preferably, the preparation method of the single-component water-based polyurethane waterproof coating comprises the following steps:
(1) Adding aromatic diamine containing polytetrahydrofuran ether chain segments into a reactor, heating to 60-80 ℃, melting, continuously stirring, heating to 110-120 ℃, dehydrating in vacuum for 2 hours under the condition that the vacuum degree is-0.08 MPa-0.09 MPa, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether diol, polyether triol, polytetrahydrofuran ether glycol (PTMEG) and fluorine-containing hydroxyl-terminated polysiloxane into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 MPa to-0.09 MPa;
(3) When the temperature is reduced to 55-65 ℃, slowly adding diisocyanate, wherein the temperature of the materials in the feeding process does not exceed 85 ℃, and then carrying out heat preservation reaction at 80-90 ℃ for 3-4 hours;
(4) Adding the aromatic diamine containing polytetrahydrofuran ether chain segments metered in the step (1), and reacting for 1-2 hours at the temperature of 80-90 ℃;
(5) Adding a solvent, a water-based chain extender and a catalyst, carrying out heat preservation reaction for 2 hours at the temperature of 80-90 ℃, and cooling to below 55 ℃;
(6) Adding a neutralizing agent and deionized water, dispersing at a high speed for 1 hour under 1000-2000r/min, heating to 50-60 ℃, and removing the solvent in vacuum for 2 hours under the condition that the vacuum degree is-0.08 MPa to-0.09 MPa to obtain the waterborne polyurethane emulsion;
(7) And (3) sequentially adding the aqueous dispersant, the powder filler, the aqueous color paste, the thickener, the antiseptic bactericide, the defoamer and the antifreeze into the aqueous polyurethane emulsion in the step (6), and dispersing and stirring for 1.0-3.0 hours to obtain the single-component aqueous polyurethane waterproof coating.
The invention provides a single-component water-based polyurethane waterproof coating and a preparation method thereof, the prepared single-component water-based polyurethane waterproof coating has excellent mechanical property and water resistance comparable to that of a solvent type polyurethane waterproof coating, is superior to the existing water-based waterproof coating, and more particularly has the following advantages:
(1) According to the invention, fluorine-containing hydroxyl-terminated polysiloxane is used for polymerization, a hydrophobic chain segment polysiloxane chain segment can be introduced into a polymer main chain, strong hydrophobic group fluoroalkyl is introduced into a side chain, and the polymer main chain and the side chain have strong hydrophobic functions, so that the prepared single-component waterborne polyurethane waterproof coating has excellent water resistance.
(2) According to the invention, aromatic diamine containing polytetrahydrofuran ether chain segments is used as a chain extender, besides the molecular weight of the polymer is increased, crystallizable polytetrahydrofuran ether chain segments and rigid benzene rings can be introduced into the polymer chain after the aromatic diamine is involved in a chain extension reaction, and polytetrahydrofuran ether glycol is involved in copolymerization in a prepolymerization stage, so that a prepolymer already has certain crystallinity, and thus, three functional groups are introduced into the main chain of the polymer through two-step polymerization reaction, the crystallinity and rigidity of the side chain of the polymer can be remarkably enhanced, and excellent mechanical properties are endowed to the polyurethane waterproof coating.
(3) The amino group of the aromatic diamine containing the polytetrahydrofuran ether chain segment is connected to the benzene ring and is an oligomer, the reactivity of the aromatic diamine containing the polytetrahydrofuran ether chain segment to isocyanate groups is lower than that of aliphatic primary amino groups (such as micromolecular diamine, polyether amine and the like), the reaction speed is moderate, and the control is easy. The invention adopts a multi-step polymerization-chain extension process, the reactants at the initial stage are polyether, polytetrahydrofuran ether glycol, fluorine-containing hydroxyl-terminated polysiloxane and isocyanate, and a prepolymer terminated by isocyanate groups is generated after heat preservation and curing, and the content of the isocyanate groups in the system is greatly reduced; and the aromatic diamine containing polytetrahydrofuran ether chain segments is added at the later stage and performs chain extension reaction with isocyanate groups at the end groups of the prepolymer, so that the reaction rate is moderate, and the stable production process can be ensured.
Detailed Description
The present invention is described in detail by the following examples, which should be construed as limiting the scope of the invention and that the invention is not limited thereto.
Example 1, a one-component waterborne polyurethane waterproof coating comprises the following components:
150 parts by weight of polyether N210
200 parts by weight of polyether N220
60 parts by weight of polyether N204
50 parts by weight of polyether N330
40 parts by weight of PTMEG-1000
50 parts by weight of PTMEG-2000
100 parts by weight of fluorine-containing hydroxyl terminated polysiloxane (average molecular weight 550)
250 parts by weight of MDI-50
100 parts by weight of Versalink P2000
65 parts by weight of acetone
10 parts by weight of dimethylolpropionic acid
1.5 parts by weight of stannous octoate
5.7 parts by weight of triethylamine
1100 parts by weight of deionized water
3.5 parts by weight of BYK chemical aqueous dispersant BYK2010
700 parts by weight of 800 mesh heavy calcium carbonate
300 parts by weight of 600 mesh heavy calcium carbonate
3.5 parts by weight of Colayne water-based color paste Colanyl Blue B2G 131-CN
7.2 parts by weight of Pickering chemical association thickener OPTIFLO L100
3.5 parts by weight of Kathon's aqueous preservative GY-Kathon
6.0 parts by weight of BYK chemical water-based silicone defoamer BYK037
100 parts by weight of ethylene glycol
The preparation method comprises the following steps:
(1) Adding Versalink P2000 into a reactor, heating to 60-80 ℃ to melt the Versalink P2000, continuously stirring and heating to 110-120 ℃, dehydrating in vacuum for 2 hours under the condition of vacuum degree of-0.08 to-0.09 MPa, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether N210, polyether N220, polyether N204, polyether N330, PTMEG-1000, PTMEG-2000 and fluorine-containing hydroxyl terminated polysiloxane with average molecular weight of 550 into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa;
(3) When the temperature is reduced to 55-65 ℃, MDI-50 is slowly added, the temperature of the materials in the feeding process is not over 85 ℃, and then the reaction is carried out for 4 hours at the temperature of 80-90 ℃;
(4) Adding dehydrated Versalink P2000, and reacting for 1.5 hours at the temperature of 80-90 ℃;
(5) Adding acetone, dimethylolpropionic acid and stannous octoate, reacting for 2 hours at the temperature of 80-90 ℃, and cooling to below 55 ℃;
(6) Adding triethylamine and deionized water, dispersing at high speed for 1 hour at 1000-2000r/min, heating to 50 ℃, and removing the solvent in vacuum for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa to obtain aqueous polyurethane emulsion;
(7) And sequentially adding a water-based dispersant BYK2010, 800-mesh heavy calcium carbonate, 600-mesh heavy calcium carbonate, a Craine water-based color paste Colanyl Blue B2G 131-CN, a thickener OPTIFLO L100, a water-based preservative GY-Kathon, a water-based organic silicon defoamer BYK037 and ethylene glycol into the water-based polyurethane emulsion, and dispersing and stirring for 2.0 hours to obtain the single-component water-based polyurethane waterproof coating.
Embodiment 2, a one-component waterborne polyurethane waterproof coating, comprising the following components:
100 parts by weight of polyether N210
300 parts by weight of polyether N220
60 parts by weight of polyether N204
50 parts by weight of polyether 330N
30 parts by weight of PTMEG-2000
30 parts by weight of fluorine-containing hydroxyl terminated polysiloxane (average molecular weight 550)
60 parts by weight of fluorine-containing hydroxyl terminated polysiloxane (average molecular weight 1750)
115 parts by weight of HDI
20 parts by weight of Versalink P2000
80 parts by weight of butanone
10 parts by weight of dimethylolbutyric acid
1.8 parts by weight of dibutyltin dilaurate
5.0 parts by weight AMP-95
1000 parts by weight of deionized water
3.0 parts by weight dispersopen LFS as an aqueous dispersion of Kelaien
700 parts by weight of 800 mesh heavy calcium carbonate
3.0 parts by weight of Colayne water-based color paste Colanyl Blue B2G 131-CN
6.6 parts by weight of Pickering chemical association thickener OPTIFLO L100
4.5 weight portions of Decome and water-based antiseptic bactericide DMHE
7.0 parts by weight of Pico chemical water-based antifoaming agent BYK011
110 parts by weight of diethylene glycol
The preparation method comprises the following steps:
(1) Adding Versalink P2000 into a reactor, heating to 60-80 ℃ to melt the Versalink P2000, continuously stirring and heating to 110-120 ℃, dehydrating for 2 hours in vacuum under the condition of vacuum degree of-0.08-0.09 MPa, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether N210, polyether N220, polyether N204, fluorine-containing hydroxyl-terminated polysiloxane with average molecular weight of 550 and 1750, polyether 330N and polyether PTMEG-2000 into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa;
(3) Slowly adding HDI when the temperature is reduced to 55-65 ℃, keeping the temperature of the materials not to exceed 85 ℃ in the feeding process, and then keeping the temperature at 80-90 ℃ for reaction for 3 hours;
(4) Adding the Versalink P2000, and reacting for 1.5 hours at the temperature of 80-90 ℃;
(5) Adding butanone, dimethylolbutyric acid and dibutyltin dilaurate, reacting at 80-90 ℃ for 2 hours, and cooling to below 55 ℃;
(6) Adding AMP-95 and deionized water, dispersing at high speed for 1 hour at 1000-2000r/min, heating to 55 ℃, and removing the solvent in vacuum for 2 hours under the condition of vacuum degree of-0.08-0.09 MPa to obtain aqueous polyurethane emulsion;
(7) And sequentially adding a Clarian aqueous dispersant DISPERSON LFS, 800-mesh heavy calcium carbonate, clarian aqueous color paste Colanyl Green GG 131-CN, a Pickle chemical association type thickener OPTIFLO L100, a Dermata and aqueous antiseptic bactericide DMHE, a Pickle chemical aqueous defoamer BYK011 and diethylene glycol into the aqueous polyurethane emulsion, and dispersing and stirring for 2.0 hours to obtain the single-component aqueous polyurethane waterproof coating.
Example 3, a one-component waterborne polyurethane waterproof coating comprises the following components:
150 parts by weight of polyether N210
300 parts by weight of polyether N220
80 parts by weight of polyether N204
50 parts by weight of polyether N330
10 parts by weight of PTMEG-3000
30 parts by weight of PTMEG-2000
100 parts by weight of fluorine-containing hydroxyl terminated polysiloxane (average molecular weight 1750)
150 parts by weight of TDI-80
10 parts by weight of Versalink P650
50 parts by weight of Versalink P1000
70 parts by weight of N, N-dimethylformamide
10 parts by weight of dimethylolpropionic acid
2.3 pbw of stannous octoate
5.2 pbw of triethylamine
1100 parts by weight of deionized water
4.0 parts by weight of Basff dispersant Tamol NN 8906
900 parts by weight of 600 mesh heavy calcium carbonate
2.1 parts by weight of Colayne water-based color paste Colanyl Blue B2G 131-CN
8.1 parts by weight of Bike chemical association thickener OPTIFLO L150
2.9 parts by weight of kasong aqueous antiseptic bactericide KF-88
6.3 parts by weight of Silok-4600
100 parts by weight of diethylene glycol
The preparation method comprises the following steps:
(1) Adding Versalink P650 and Versalink P1000 into a reactor, wherein the mass ratio of the Versalink P650 to the Versalink P1000 is 1, the total mass is more than 60 parts by mass, heating to 60-80 ℃ to complete melting, continuously stirring and heating to 110-120 ℃, carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether N210, polyether N220, polyether N204, fluorine-containing hydroxyl-terminated polysiloxane, polyether N330, PTMEG-2000 and PTMEG-3000 into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa;
(3) When the temperature is reduced to 55-65 ℃, beginning to slowly add TDI-80, wherein the temperature of the materials in the feeding process does not exceed 85 ℃, and then keeping the temperature at 80-90 ℃ for reaction for 4 hours;
(4) Adding the mixture of Versalink P1000 and Versalink P650 which are subjected to dehydration treatment, and reacting for 1.5 hours at the temperature of 80-90 ℃;
(5) Adding N, N-dimethylformamide, dimethylolpropionic acid and stannous octoate, reacting for 2 hours at the temperature of 80-90 ℃, and cooling to below 55 ℃;
(6) Adding triethylamine and deionized water, dispersing at a high speed of 1000-2000r/min for 1 hour, heating to 60 ℃, and removing the solvent in vacuum under the condition that the vacuum degree is-0.08-0.09 MPa for 2 hours to obtain the aqueous polyurethane emulsion;
(7) In the aqueous polyurethane emulsion, a Pasteur dispersant Tamol NN 8906, 600-mesh heavy calcium carbonate, a Clariant aqueous color paste Colanyl Black N131-CN, a bisque chemical association type thickener OPTIFLO L150, an aqueous antiseptic bactericide KF-88, a Silok-4600 and diethylene glycol are sequentially dispersed and stirred for 2.0 hours to obtain the single-component aqueous polyurethane waterproof paint.
Example 4, a one-component waterborne polyurethane waterproof coating comprises the following components:
150 parts of polyether N210
200 parts of polyether N220
100 parts of polyether N204
70 parts of polyether N330
30 parts of PTMEG-2000
10 parts of PTMEG-3000
200 parts of fluorine-containing hydroxyl terminated polysiloxane (average molecular weight 4200)
205 parts of IPDI
50 parts of Versalink P1000
100 parts of Versalink P2000
80 parts of acetone
8.0 parts AMP-95
14 parts of dimethylolbutanoic acid
2.5 parts of dibutyltin dilaurate
1200 parts of deionized water
3.5 parts of dispersopen LFS as a water-based dispersion of Kelaien
900 parts of 600 mesh heavy calcium carbonate
2.7 parts of Colayne aqueous color paste Colanyl Oxide Yellow R132-CN
5.8 parts of Bick chemical association thickener OPTIFLO L150
4.9 parts of Zhongbei Weilan antiseptic bactericide ZB101
9.0 parts KYC Keying chemistry 710
100 parts of diethylene glycol
The preparation method comprises the following steps:
(1) Adding Versalink P1000 and Versalink P2000 into a reactor, wherein the mass ratio of the Versalink P1000 to the Versalink P2000 is 1, the total mass is more than 150 parts by weight, heating to 60-80 ℃ to complete melting, continuously stirring and heating to 110-120 ℃, carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether N210, polyether N220, polyether N204, fluorine-containing hydroxyl terminated polysiloxane with the average molecular weight of 4200, polyether N330, PTMEG-2000 and PTMEG-3000 into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is-0.08 to-0.09 MPa;
(3) When the temperature is reduced to 55-65 ℃, slowly adding IPDI, wherein the material temperature in the feeding process does not exceed 85 ℃, and then carrying out heat preservation reaction for 4 hours at 80-90 ℃;
(4) Adding 150 parts by weight of the mixture of Versalink P1000 and Versalink P2000 after dehydration treatment, and reacting for 2.0 hours at the temperature of 80-90 ℃;
(5) Adding acetone, dimethylolbutyric acid and dibutyltin dilaurate, reacting at 80-90 ℃ for 1.5 hours, and cooling to below 55 ℃;
(6) Adding AMP-95 and deionized water, dispersing at high speed for 1 hour at 1000-2000r/min, heating to 60 ℃, and removing the solvent in vacuum for 2 hours under the condition of vacuum degree of-0.08-0.09 MPa to obtain aqueous polyurethane emulsion;
(7) And sequentially adding a Cerine aqueous dispersant DISPERSON LFS, 600-mesh heavy calcium carbonate, cerine aqueous color paste Colanyl Oxide Yellow R132-CN, a Pickering chemical association type thickener OPTIFLO L150, a middle-north Chinese toilet blue anti-corrosion bactericide ZB101, KYC Keying chemical 710 and diethylene glycol into the aqueous polyurethane emulsion, and dispersing and stirring for 2.0 hours to obtain the single-component aqueous polyurethane waterproof coating.
Comparative example 1
Comparative example 1 is compared with example 1, with the only difference that the fluorine-containing hydroxyl terminated polysiloxane having an average molecular weight of 550 in example 1 is replaced by polyether N204 having the same functionality and a similar molecular weight, and the remainder is unchanged.
Comparative example 2
Comparative example 2 is compared with example 1, except that instead of Versalink P2000 in example 1 being replaced by PTMEG-2000 of the same functionality and similar molecular weight, a conventional prepolymerization is carried out simultaneously with the other polyethers, the remainder being unchanged.
Comparative example 3
Comparative example 3 is compared with example 1, except that Versalink P2000 is added to the reaction vessel together with the other monomers for dehydration and polymerization, and the remainder is unchanged.
The above-mentioned compositions were formed into films, and the properties were measured and summarized in Table 1.
TABLE 1 Performance test results of the one-component waterborne polyurethane waterproofing paint
In the embodiment 1, the dosage proportion of three monomers, namely MDI-50, polytetrahydrofuran ether glycol and aromatic diamine containing polytetrahydrofuran ether chain segments is large, the contents of crystallizable polytetrahydrofuran ether chain segments, rigid benzene rings and carbamido groups of the main chain of the prepared polymer are high, and the finished coating film has high tensile strength and high extensibility due to the comprehensive action of the crystallizable chain segments and the rigid groups; in example 2, HDI for isocyanate was an aliphatic diisocyanate having the smallest rigidity, and the ratio of the two types of monomers, namely polytetrahydrofuran ether glycol and aromatic diamine containing a polytetrahydrofuran ether segment was low, and the crystallinity and rigidity of the polymer were small and the flexibility was large as compared with those of example 1, so that the strength of the finished coating film was low and the elongation at break was very large. The raw material ratio and the mechanical property detection index conditions of the finished products designed in the examples 3 and 4 are respectively between the two examples 1 and 2. In four examples, the fluorine-containing hydroxyl terminated polysiloxane of example 4 is used in the largest proportion, the polysiloxane segment and the fluorine-containing alkyl group are provided in the main chain and the measurement respectively in very high proportion, and the polysiloxane segment is more easily wound to wrap the outer surface or the upper surface of the coating, so that the prepared coating has the best water resistance and the lowest water absorption rate.
Compared with the example 1, the fluorine-containing hydroxyl-terminated polysiloxane is not added, and the hydrophilic chain segments provided by polyether, polytetrahydrofuran ether glycol, an aqueous chain extender and the like are all the hydrophilic chain segments except the isocyanate hydrophobic chain segment with lower content in the polymer chain segment, so that the finished product has poor water resistance and high water absorption rate.
Compared with the embodiment 1, the difference of the comparative example 2 is that the chain extension is carried out without adding the aromatic diamine containing the polytetrahydrofuran ether chain segment, but the PTMEG-2000 with the same functionality and similar molecular weight is used for carrying out the conventional prepolymerization with other polyethers at the same time, so the difference is two points, firstly, one-step chain extension reaction is lacked, the molecular weight of the polymer is smaller, and the tensile strength and the elongation of a formed film are influenced; and secondly, under the condition that the chain extension of the aromatic diamine containing the polytetrahydrofuran ether chain segment is not used, the rigid chain segment of the polymer is only provided by the benzene ring part of the isocyanate, the proportion is small, and the rigidity and the strength of the polymer are low. Therefore, after the aromatic diamine containing the polytetrahydrofuran ether chain segment participates in chain extension, the tensile strength and the elongation rate of the polyurethane film can be obviously improved, and excellent mechanical properties are endowed to the product.
Compared with the example 1, the raw material proportion is completely the same, and the difference is only that the aromatic diamine containing polytetrahydrofuran ether chain segment and other soft segment monomers are added simultaneously, and the gel appears in the experimental process and can not be continued. The reactivity of amino of the aromatic diamine containing the polytetrahydrofuran ether chain segment to isocyanate groups is higher than that of hydroxyl, after the isocyanate is added, the aromatic diamine containing the polytetrahydrofuran ether chain segment preferentially reacts with the isocyanate groups and the reaction rate is higher, so that the crosslinking density of the polymer is increased sharply, the reaction is exothermic, heat is not released in time in a short time, and a gel phenomenon or even implosion can be generated. Therefore, the multi-step polymerization-chain extension process adopted by the invention is necessary and advanced.
Claims (9)
1. A single-component waterborne polyurethane waterproof coating is characterized in that: the method comprises the following raw materials: 410-530 parts of polyether diol, 50-70 parts of polyether triol, 30-90 parts of polytetrahydrofuran ether glycol, 90-200 parts of fluorine-containing hydroxyl-terminated polysiloxane, 115-250 parts of diisocyanate, 20-150 parts of aromatic diamine containing polytetrahydrofuran ether chain segments, 10-14 parts of water-based chain extender, 5.0-8.0 parts of neutralizer, 65-80 parts of solvent, 1.5-2.3 parts of catalyst, 1000-1200 parts of deionized water, 3.0-4.0 parts of water-based dispersant, 900-1000 parts of powder filler, 2.1-3.5 parts of water-based color paste, 5.8-7.2 parts of thickener, 2.9-4.9 parts of antiseptic bactericide, 6.0-9.0 parts of defoaming agent and 100-110 parts of antifreezing agent;
the preparation method of the single-component water-based polyurethane waterproof coating comprises the following steps:
(1) Adding aromatic diamine containing polytetrahydrofuran ether chain segments into a reactor, heating to 60-80 ℃, melting, continuously stirring, heating to 110-120 ℃, dehydrating in vacuum under the vacuum condition of-0.08 MPa-0.09 MPa for 2 hours, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether diol, polyether triol, polytetrahydrofuran ether glycol and fluorine-containing hydroxyl terminated polysiloxane into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the vacuum condition of-0.08 MPa to-0.09 MPa;
(3) When the temperature is reduced to 55-65 ℃, slowly adding diisocyanate, wherein the temperature of the materials in the feeding process cannot exceed 85 ℃, and then carrying out heat preservation reaction at 80-90 ℃ for 3-4 hours;
(4) Adding the aromatic diamine containing the polytetrahydrofuran ether chain segment metered in the step (1), and reacting for 1-2 hours at the temperature of 80-90 ℃;
(5) Adding a solvent, a water-based chain extender and a catalyst, carrying out heat preservation reaction at 80-90 ℃ for 2 hours, and cooling to below 55 ℃;
(6) Adding a neutralizing agent and deionized water, dispersing at a high speed of 1000-2000r/min for 1 hour, heating to 50-60 ℃, and removing the solvent in vacuum under the conditions of vacuum degree of-0.08 MPa to-0.09 MPa for 2 hours to obtain an aqueous polyurethane emulsion;
(7) Sequentially adding a water-based dispersing agent, a powder filler, a water-based color paste, a thickening agent, an anti-corrosion bactericide, a defoaming agent and an antifreezing agent into the water-based polyurethane emulsion obtained in the step (6), and dispersing and stirring for 1.0-3.0 hours to obtain a single-component water-based polyurethane waterproof coating;
the aromatic diamine containing the polytetrahydrofuran ether chain segment is one or a mixture of more than two of Versalink P650, versalink P1000 and Versalink P2000 which are products of winning companies.
2. The one-component aqueous polyurethane waterproof paint as claimed in claim 1, wherein: the polyether diol is a mixture of two or more of polyether N210, polyether N220 and polyether N204; the polyether triol is one of polyether N330 and polyether 330N.
3. The one-component aqueous polyurethane waterproof paint as claimed in claim 1, wherein: the polytetrahydrofuran ether glycol is one or a mixture of more than two of PTMEG-1000, PTMEG-2000 and PTMEG-3000; the fluorine-containing hydroxyl-terminated polysiloxane is a product of Shanghai Silshan polymer material Co., ltd, and is selected from one or a mixture of more than two of 550, 1750 and 4200 in average molecular weight.
4. The one-component water-based polyurethane waterproof paint as claimed in claim 1, wherein the one-component water-based polyurethane waterproof paint comprises the following components in percentage by weight: the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and liquefied diphenylmethane diisocyanate.
5. The one-component aqueous polyurethane waterproof paint as claimed in claim 1, wherein: the solvent is one of acetone, butanone and N, N-dimethylformamide.
6. The one-component aqueous polyurethane waterproof paint as claimed in claim 1, wherein: the aqueous chain extender is one of dimethylolpropionic acid and dimethylolbutyric acid.
7. The one-component aqueous polyurethane waterproof paint as claimed in claim 1, wherein: the catalyst is one of dibutyltin dilaurate and stannous octoate.
8. The one-component aqueous polyurethane waterproof paint as claimed in claim 1, wherein: the neutralizing agent is one of triethylamine or 2-amino-2-methyl-1-propanol.
9. A method for preparing the one-component water-based polyurethane waterproof coating material of any one of claims 1 to 8, comprising the steps of:
(1) Adding aromatic diamine containing polytetrahydrofuran ether chain segments into a reactor, heating to 60-80 ℃, melting, continuously stirring, heating to 110-120 ℃, dehydrating in vacuum under the vacuum condition of-0.08 MPa-0.09 MPa for 2 hours, sealing, and cooling to 55-65 ℃ for later use;
(2) Adding polyether diol, polyether triol, polytetrahydrofuran ether glycol and fluorine-containing hydroxyl-terminated polysiloxane into a reactor, stirring and heating to 110-120 ℃, and carrying out vacuum dehydration for 2 hours under the conditions of vacuum of-0.08 MPa to-0.09 MPa;
(3) When the temperature is reduced to 55-65 ℃, slowly adding diisocyanate, wherein the temperature of the materials in the feeding process cannot exceed 85 ℃, and then carrying out heat preservation reaction at 80-90 ℃ for 3-4 hours;
(4) Adding the aromatic diamine containing polytetrahydrofuran ether chain segments metered in the step (1), and reacting for 1-2 hours at the temperature of 80-90 ℃;
(5) Adding a solvent, a water-based chain extender and a catalyst, carrying out heat preservation reaction for 2 hours at the temperature of 80-90 ℃, and cooling to below 55 ℃;
(6) Adding a neutralizing agent and deionized water, dispersing at a high speed of 1000-2000r/min for 1 hour, heating to 50-60 ℃, and removing the solvent in vacuum under the conditions of vacuum degree of-0.08 MPa to-0.09 MPa for 2 hours to obtain an aqueous polyurethane emulsion;
(7) And (4) sequentially adding the aqueous dispersing agent, the powder filler, the aqueous color paste, the thickening agent, the antiseptic bactericide, the defoaming agent and the antifreezing agent into the aqueous polyurethane emulsion obtained in the step (6), and dispersing and stirring for 1.0-3.0 hours to obtain the single-component aqueous polyurethane waterproof coating.
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