CN111808518A - High-stability single-component polyurethane waterproof coating and preparation method thereof - Google Patents
High-stability single-component polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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Abstract
The invention belongs to the technical field of polyurethane waterproof coatings, and particularly relates to a high-stability single-component polyurethane waterproof coating and a preparation method thereof. The method comprises the steps of preparing hydroxyl acrylic acid water-absorbing resin; preparing hydroxyl acrylic acid water-absorbent resin to adsorb magnesium sulfate; preparing an ultrafine water absorbing material; adding the superfine water absorbing material, polyether glycol and pigment filler into a dispersion machine, dispersing at 2000-2800 r/min for 1-2 hours, sealing at 300-400 r/min, stirring, heating to 100-130 ℃, and carrying out vacuum dehydration at-0.08 MPa to-0.1 MPa for 1-2 hours; cooling to 60-80 ℃, introducing nitrogen, adding 10-20 parts of isocyanate, uniformly mixing, adding 0.04-0.1 part of catalyst, and continuously reacting for 2-4 hours; and (3) cooling to 30-50 ℃, continuously adding 0.3-1 part of latent curing agent, 3-10 parts of plasticizer and 0.2-1.4 parts of auxiliary agent, stirring and mixing for 1-2 hours, then cooling to 25-35 ℃, discharging under the protection of nitrogen, and thus obtaining the acrylic modified polyurethane waterproof coating. The invention can improve the stability of the single-component polyurethane waterproof coating.
Description
Technical Field
The invention belongs to the technical field of polyurethane waterproof coatings, and particularly relates to a high-stability single-component polyurethane waterproof coating and a preparation method thereof.
Background
The polyurethane waterproof paint belongs to a chemical reaction type waterproof paint, is a rubber-like high-elasticity coating film after being cured, has no seam on the whole coating film, is called as a liquid coiled material in the industry because of the excellent comprehensive performance, is widely applied in the world, and is particularly suitable for waterproofing special-shaped parts. The polyurethane waterproof coating is divided into a single-component polyurethane waterproof coating and a multi-component polyurethane waterproof coating according to the composition and the curing mechanism of the polyurethane waterproof coating. As the multi-component polyurethane waterproof coating needs to be proportioned according to a certain proportion during field construction and is mechanically stirred, foaming and inaccurate proportioning are introduced in the stirring process, the construction quality is influenced by uneven stirring, and the caused waterproof quality accidents happen occasionally; the single-component polyurethane waterproof coating is a single component, can be used immediately after being opened, does not need stirring, is reliable in construction, and is widely applied. However, the storage stability is greatly affected by the presence of moisture in minute amounts during the preparation and storage of the one-component waterproof coating material, and therefore, it is important to control the moisture in the system.
There are two main methods to control moisture at present: chemical methods and physical methods. The chemical method is to adopt the reaction of chemical absorbent and water content to control the trace water content in the system. The chemical absorbent mainly used comprises monofunctional isocyanate, triethyl orthoformate and the like. However, the chemical absorption method inevitably produces by-products, which affect the properties after film formation, such as tear strength and the like. The physical method mainly adopts a molecular sieve method. However, the molecular sieve is troublesome to treat and troublesome to use in production.
The Chinese patent application with the application number of 201811627825.0 discloses the application of acrylic acid water-absorbing resin in single-component polyurethane waterproof paint, the single-component polyurethane waterproof paint and a preparation method thereof, wherein the acrylic acid water-absorbing resin is at least one of the following polymers which are partially crosslinked: sodium polyacrylate, acrylic acid-acrylamide copolymer and acrylic acid-maleic anhydride copolymer, wherein the cross-linked polymer accounts for 1-10% of the total amount of the acrylic acid water-absorbing resin. The invention can effectively solve the problem of residual moisture of the polyurethane waterproof material, effectively solve the phenomena of excessive increase of the viscosity and excessive reduction of extension of the waterproof material in the storage process, and form the single-component polyurethane waterproof coating which can be stably stored for a long time. In the invention, the influence of moisture on the polyurethane waterproof coating in the preparation and storage processes is solved by utilizing the water absorption performance of the crosslinked acrylic acid water-absorbent resin, but the stability of the polyurethane is still influenced because the moisture still exists in the water-absorbent resin after the acrylic acid water-absorbent resin absorbs water.
The Chinese patent application with the application number of 201410350004.2 discloses a hydrophilic single-component water-curing polyurethane and a preparation method thereof, wherein an anionic ring-opening polymerization means is adopted, polyethylene glycol is taken as initial dihydric alcohol, and the initial dihydric alcohol and propylene oxide are subjected to ring-opening polymerization in the presence of KOH, and polyols with different molecular weights and the lengths of hydrophilic and hydrophobic chain segments are synthesized by adjusting the molecular weight of the polyethylene glycol, the addition amount of the polyethylene glycol and the addition amount of the propylene oxide; reacting polyol with isocyanate under the action of a catalyst, and adding a proper amount of plasticizer, antioxidant and ultraviolet absorbent to prepare a polyurethane prepolymer with an end group of-NCO; and mixing the prepolymer with water in a certain proportion to obtain the single-component water-cured polyurethane. The method is simple, the operation is simple, the obtained product has high solid content, high curing speed, high water retention capacity, good storage stability, good flexibility, weather resistance and acid and alkali resistance, and has wide application prospect in the aspects of treating water and soil loss, preparing waterproof materials and the like.
The Chinese patent application with the application number of 201811044550.8 discloses a quick-drying waterproof coating which is prepared by mixing a component A and a component B according to the mass ratio of 4:3, wherein the component A comprises the following components in parts by mass: 60-80 parts of silicone-acrylic emulsion, 10-15 parts of acrylic emulsion, 5-10 parts of hydroxyethyl methyl cellulose, 3-5 parts of liquid tea saponin, 5-10 parts of fly ash, 3-6 parts of sodium polyacrylate, 4-6 parts of sulpho-alumina cement, 2-3 parts of propylene glycol and 20-30 parts of chlorinated paraffin; 3-5 parts of a defoaming agent and 6-8 parts of a film-forming assistant; the component B comprises the following components in parts by weight: 80-100 parts of ethylene-vinyl acetate copolymer emulsion, 30-50 parts of polysiloxane, 10-15 parts of silica sol, 10-20 parts of waterborne polyurethane, 15-22 parts of mica powder, 50-70 parts of waterborne fluorocarbon emulsion, 3-8 parts of barium metaborate, 4-5 parts of inositol, 3-5 parts of dispersant and 5-10 parts of desiccant.
The Chinese patent application with the application number of 201410470857.X discloses a waterproof woodware polyurethane coating, which comprises 25 parts of polyurethane emulsion, 12 parts of bentonite, 5 parts of urea-formaldehyde resin, 6 parts of silicon dioxide, 5 parts of ethanol, 8 parts of epoxy resin, 4 parts of polyvinyl alcohol, 2 parts of formaldehyde, 2 parts of magnesium sulfate, 23 parts of talcum powder, 2 parts of a flame retardant and 12 parts of titanium dioxide. It also comprises 3 parts of defoaming agent. Compared with the prior art, the invention has excellent elasticity, low-temperature flexibility, low-temperature resistance, aging resistance and high-temperature non-flowing property, thereby improving the product quality and expanding the use temperature range of the product.
Chinese patent application with application number 201710969243.X discloses a polyurethane coating, which is prepared from the following raw materials in parts by weight: hydroxy acrylic resin: 30-40 parts; ethyl 3-ethoxypropionate: 40-50 parts; titanium dioxide: 25-35 parts; antirust pigment: 5-10 parts; solvent: 20-30 parts of a solvent; 20-40 parts of talcum powder; auxiliary agent: 2-5 parts; a production method of a polyurethane coating comprises the following steps: s1; stirring under normal pressure; s2: grinding; and S3 packaging. The polyurethane coating has wide application range, and can be classified into acrylic polyurethane, alkyd polyurethane, polyester polyurethane, polyether polyurethane, epoxy polyurethane and the like according to the difference of hydroxyl-containing components. Generally has good mechanical properties, higher solid content and better properties in all aspects. Is a paint variety with development prospect at present. The main application directions are wood coatings, automobile repairing coatings, anticorrosive coatings, floor coatings, electronic coatings, special coatings, polyurethane waterproof coatings and the like.
Chinese patent application No. 201810138387.5 discloses a polyurethane waterproof paint comprising polyurethane resin, petroleum pitch, MDI, propylene glycol, polyether polyol, carbon black, high-activity fluorine titanium, filler retention agent, methyl parathion, plasticizer, dispersant, curing agent and ultraviolet absorber; the molecular weight of the polyether polyol is 2000-5000, and the hydroxyl value is 110-240 mgKOH/g; the preparation method comprises the steps of reaction and gradient cooling, wherein the reaction has the stirring speed of 100-200rad/min and the pressure of 0.6-0.8 MPa; the temperature is reduced in a gradient manner, wherein the gradient temperature reduction is 2-5 ℃/min, and the temperature is reduced to 110 +/-5 ℃; the waterproof coating disclosed by the invention has the advantages that the components in the formula generate synergistic effect, the low-temperature bending property, the tensile strength, the waterproof performance and other properties are excellent, the flame retardant effect is good, the problem of fire caused by fire in the using process is avoided, and the application prospect is wide.
Disclosure of Invention
Aiming at the problem that the stability of the polyurethane coating is affected because moisture still exists after acrylic resin is directly added into the polyurethane waterproof coating to absorb water at present, the invention provides the high-stability single-component polyurethane waterproof coating.
In order to achieve the aim, the preparation method of the high-stability single-component polyurethane waterproof coating comprises the following steps:
(1) mixing, stirring and uniformly mixing acrylic acid and water, dropwise adding a sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to 65-75%, then continuously adding acrylamide and hydroxyacrylic acid, keeping stirring and heating to 60-80 ℃, slowly dropwise adding an initiator and a cross-linking agent, stirring and reacting at constant temperature for 2-3 hours after dropwise adding, drying in vacuum, crushing, and sieving with a 300-400-mesh sieve to obtain the hydroxyacrylic acid water-absorbent resin;
(2) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (1) into a magnesium sulfate solution at the temperature of 60-70 ℃, starting stirring to enable the hydroxyl acrylic acid water-absorbent resin to be completely absorbed and swelled, continuing stirring for 1-2 hours, filtering and separating, and drying and dehydrating at the temperature of 120-140 ℃ to obtain hydroxyl acrylic acid water-absorbent resin absorbed magnesium sulfate;
(3) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (2) to adsorb magnesium sulfate into a superfine grinding machine for grinding, and sieving the obtained powder with a 1000-1500-mesh sieve to obtain a superfine water-absorbent material;
(4) adding 2-4 parts by weight of the superfine water absorbing material obtained in the step (3), 20-30 parts by weight of polyether polyol and 10-30 parts by weight of pigment and filler into a dispersion machine, dispersing for 1-2 hours at the rotating speed of 2000-2800 r/min, then adding into a closed reaction kettle, stirring at a high speed and heating to 100-130 ℃, stirring at a speed of 300-400 r/min, starting vacuum dehydration, wherein the vacuum degree is-0.08 MPa-0.1 MPa, and the dehydration time is 1-2 hours;
(5) reducing the temperature of the reaction kettle in the step (4) to 60-80 ℃ according to the parts by weight, introducing nitrogen to protect vacuum, then adding 10-20 parts of isocyanate, stirring at a high speed and mixing uniformly, adding 0.04-0.1 part of catalyst, and continuing to react for 2-4 hours;
(6) cooling the reaction kettle in the step (5) to 30-50 ℃, continuously adding 0.3-1 part of latent curing agent, 3-10 parts of plasticizer and 0.2-1.4 parts of auxiliary agent, stirring and mixing for 1-2 hours, then cooling to 25-35 ℃, discharging under the protection of nitrogen, and obtaining the high-stability single-component polyurethane waterproof coating.
Further preferably, the mass fraction of the sodium hydroxide solution in the step (1) is 10-15%;
further preferably, the initiator in the step (1) is a redox system initiator, and the initiator is further preferably a potassium persulfate-sodium bisulfite redox system;
the cross-linking agent in the step (1) is preferably N, N-methylene-bisacrylamide;
the hydroxy acrylic acid in the step (1) is preferably one of hydroxyethyl acrylate, 4-hydroxy butyl acrylate and hydroxyethyl methacrylate;
in the step (1), the acrylic acid, the sodium hydroxide solution, the acrylamide, the hydroxyacrylic acid, the initiator, the cross-linking agent and the water are in parts by weight: 10 to 20 parts, 1 to 3 parts, 10 to 20 parts, 3 to 5 parts, 0.06 to 0.4 part, 0.08 to 0.3 part, 100 to 150 parts.
More preferably, the mass fraction of the magnesium sulfate solution in the step (2) is 20-30%.
More preferably, the superfine mill in the step (3) is selected from ZYM three-ring fine mill of Zhuya machine, and more preferably, the model is ZYM80 three-ring fine mill, the rotation speed of a main shaft is set to be 235-240 r/min, and the grain size of the finished product is 10-15 um;
the disperser in the step (4) is selected from a hydraulic lifting disperser produced by Dongguan Code machinery, and the preferable model is HFS-220 hydraulic lifting disperser.
Further preferably, the polyether polyol in the step (4) is at least one of PPG polyether polyol, POP polymer polyether polyol and polytetrahydrofuran polyether polyol, polyether polyol 2000D, polyether polyol N330 and polyether polyol 3050, and further preferably the polyether polyol has a molecular weight of 500-5000;
in the step (4), the pigment and filler is preferably one or a mixture of more than one of carbon black, titanium dioxide, iron yellow, kaolin, wollastonite and talcum powder, and the more preferred pigment and filler has a sieve mesh number of 1000-1500 meshes.
Further preferably, in the step (5), the isocyanate is selected from one of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
More preferably, the catalyst in the step (5) is one of stannous octoate, lead isooctanoate, aliphatic amine tertiary amine, alicyclic amine tertiary amine and aromatic amine tertiary amine.
Further preferably, the plasticizer in step (6) is one or more of dioctyl sebacate, dibutyl phthalate, diisononyl phthalate, chlorinated paraffin and citric acid ester.
Further preferably, the auxiliaries in the step (6) are a defoaming agent, a dispersing agent and an antioxidant, wherein the auxiliaries are common auxiliaries for the coating sold in the market at present;
the latent curing agent in the step (6) is an imine latent curing agent.
The second object to be achieved by the present invention is to provide a high-stability one-component polyurethane waterproof coating.
To achieve the second object of the present invention, the high-stability one-component polyurethane waterproof coating is prepared according to the above method.
Has the advantages that:
the invention utilizes the principle that magnesium sulfate has drying property, the magnesium sulfate is fixed in the water-absorbent resin, the water-absorbent resin is quickly dried by the magnesium sulfate after absorbing water so as to prevent the influence of moisture on the stability of the polyurethane coating, the material is dried at about 130 ℃ so as to be beneficial to the loss of crystallization water of the magnesium sulfate, thereby improving the drying property of the magnesium sulfate, the magnesium sulfate after absorbing the water-absorbent resin absorbs water and crystallizes in the water-absorbent resin, thereby avoiding the precipitation of the water-absorbent crystallization in the polyurethane coating caused by the direct addition of the magnesium sulfate, and the water-absorbent resin is combined with the polyurethane prepolymer by utilizing the hydroxyl functional group on the water-absorbent resin, thereby effectively protecting the polyurethane waterproof coating from the interference of trace moisture, and further improving the stability of the single-component polyurethane waterproof coating in the production and transportation processes.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Mixing 15 parts by weight of acrylic acid and 120 parts by weight of water, stirring and uniformly mixing, dropwise adding a 12% sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to 70%, then continuously adding 15 parts by weight of acrylamide and 4 parts by weight of hydroxyethyl acrylate, keeping stirring and heating to 70 ℃, slowly dropwise adding 0.3 part by weight of potassium persulfate-sodium bisulfite redox system initiator and 0.2 part by weight of N, N-methylene bisacrylamide crosslinking agent, stirring and reacting at constant temperature for 3 hours after dropwise adding, drying in vacuum, crushing, and sieving with a 300-mesh sieve to obtain a hydroxyacrylic acid water-absorbent resin;
(2) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (1) into a magnesium sulfate solution with the mass fraction of 25% at 70 ℃, starting stirring to enable the hydroxyl acrylic acid water-absorbent resin to be completely adsorbed and swelled, continuing stirring for 2 hours, filtering and separating, and drying and dehydrating at 130 ℃ to obtain the hydroxyl acrylic acid water-absorbent resin adsorbed magnesium sulfate;
(3) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (2) to adsorb magnesium sulfate into a ZYM80 three-ring micro-powder mill superfine pulverizer of Zhuya machinery, setting the rotation speed of a main shaft to be 235-240 r/min, grinding the material with the granularity of 10-15 um, and sieving the obtained powder with a 1200-mesh sieve to obtain a superfine water-absorbent material;
(4) adding 3 parts by weight of the superfine water absorbing material obtained in the step (3), 25 parts by weight of PPG polyether polyol with the molecular weight of 3000 and 20 parts by weight of carbon black pigment filler with the mesh number of 1200 into a hydraulic lifting dispersion machine which is produced by Dongguan Kod machinery and has the model of HFS-220, dispersing for 1.5 hours at the rotating speed of 2500r/min, then adding into a closed reaction kettle, stirring at a high speed and heating to 120 ℃, stirring at a speed of 350r/min, starting vacuum dehydration, wherein the vacuum degree is-0.08 MPa-0.09 MPa, and the dehydration time is 1.5 hours;
(5) reducing the temperature of the reaction kettle in the step (4) to 70 ℃, introducing nitrogen to protect and break vacuum, then adding 15 parts of toluene diisocyanate, stirring at high speed and mixing uniformly, adding 0.08 part of stannous octoate catalyst, and continuing to react for 3 hours;
(6) and (3) cooling the reaction kettle in the step (5) to 40 ℃ according to the parts by weight, continuously adding 0.6 part of imine latent curing agent, 8 parts of dioctyl sebacate plasticizer and 0.5 part of defoaming agent, stirring and mixing for 1.5 hours, then cooling to 30 ℃, discharging under the protection of nitrogen, and obtaining the high-stability single-component polyurethane waterproof coating.
Example 2
(1) Mixing 20 parts by weight of acrylic acid and 120 parts by weight of water, stirring and uniformly mixing, dropwise adding a 12% sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to 70%, then continuously adding 10 parts by weight of acrylamide and 5 parts by weight of 4-hydroxybutyl acrylate, keeping stirring and heating to 70 ℃, slowly dropwise adding 0.3 part by weight of potassium persulfate-sodium bisulfite redox system initiator and 0.2 part by weight of N, N-methylene bisacrylamide crosslinking agent, stirring and reacting at constant temperature for 3 hours after dropwise adding, drying in vacuum, crushing, and sieving with a 300-mesh sieve to obtain the hydroxyacrylic acid water-absorbent resin;
(2) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (1) into a magnesium sulfate solution with the mass fraction of 25% at 70 ℃, starting stirring to enable the hydroxyl acrylic acid water-absorbent resin to be completely adsorbed and swelled, continuing stirring for 2 hours, filtering and separating, and drying and dehydrating at 130 ℃ to obtain the hydroxyl acrylic acid water-absorbent resin adsorbed magnesium sulfate;
(3) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (2) to adsorb magnesium sulfate into a ZYM80 three-ring micro-powder mill superfine pulverizer of Zhuya machinery, setting the rotation speed of a main shaft to be 235-240 r/min, grinding the material with the granularity of 10-15 um, and sieving the obtained powder with a 1200-mesh sieve to obtain a superfine water-absorbent material;
(4) adding 3 parts by weight of the superfine water absorbing material obtained in the step (3), 25 parts by weight of PPG polyether polyol with the molecular weight of 3000 and 20 parts by weight of carbon black pigment filler with the mesh number of 1200 into a hydraulic lifting dispersion machine which is produced by Dongguan Kod machinery and has the model of HFS-220, dispersing for 1.5 hours at the rotating speed of 2500r/min, then adding into a closed reaction kettle, stirring at a high speed and heating to 120 ℃, stirring at a speed of 350r/min, starting vacuum dehydration, wherein the vacuum degree is-0.08 MPa-0.09 MPa, and the dehydration time is 1.5 hours;
(5) reducing the temperature of the reaction kettle in the step (4) to 70 ℃, introducing nitrogen to protect and break vacuum, then adding 15 parts of toluene diisocyanate, stirring at high speed and mixing uniformly, adding 0.08 part of stannous octoate catalyst, and continuing to react for 3 hours;
(6) and (3) cooling the reaction kettle in the step (5) to 40 ℃ according to the parts by weight, continuously adding 0.6 part of imine latent curing agent, 8 parts of dioctyl sebacate plasticizer and 0.5 part of defoaming agent, stirring and mixing for 1.5 hours, then cooling to 30 ℃, discharging under the protection of nitrogen, and obtaining the high-stability single-component polyurethane waterproof coating.
Comparative example 1
(1) Adding acrylic acid water-absorbent resin into a magnesium sulfate solution with the mass fraction of 25% at 70 ℃, starting stirring to enable the hydroxyl acrylic acid water-absorbent resin to completely absorb and swell, continuing stirring for 2 hours, filtering and separating, and drying and dehydrating at 130 ℃ to obtain acrylic acid water-absorbent resin absorbed magnesium sulfate;
(2) adding the obtained acrylic acid water-absorbent resin adsorbed magnesium sulfate into a ZYM80 three-ring micro-powder mill superfine mill of Zhuya machinery, setting the rotation speed of a main shaft to be 235-240 r/min, grinding the material with the granularity of 10-15 um, and sieving the obtained powder with a 1200-mesh sieve to obtain a superfine water-absorbent material;
(3) according to the weight parts, adding an ultrafine water absorbing material, 25 parts of polyether glycol with the molecular weight of 3000PPG and 20 parts of carbon black pigment filler with the mesh number of 1200 into a hydraulic lifting dispersion machine which is produced by Dongguan Kode machinery and has the model of HFS-220, dispersing for 1.5 hours at the rotating speed of 2500r/min, then adding into a closed reaction kettle, stirring at a high speed and heating to 120 ℃, the stirring speed is 350r/min, starting vacuum dehydration, the vacuum degree is-0.08 MPa-0.09 MPa, and the dehydration time is 1.5 hours;
(4) reducing the temperature of the reaction kettle to 70 ℃ according to the parts by weight, introducing nitrogen to protect and break vacuum, then adding 15 parts of toluene diisocyanate, stirring at high speed and mixing uniformly, adding 0.08 part of stannous octoate catalyst, and continuing to react for 3 hours;
(5) and (3) cooling the reaction kettle in the step (4) to 40 ℃ according to the parts by weight, continuously adding 0.6 part of imine latent curing agent, 8 parts of dioctyl sebacate plasticizer and 0.5 part of defoaming agent, stirring and mixing for 1.5 hours, then cooling to 30 ℃, discharging under the protection of nitrogen, and obtaining the high-stability single-component polyurethane waterproof coating.
Comparative example 2
(1) Mixing 15 parts by weight of acrylic acid and 120 parts by weight of water, stirring and uniformly mixing, dropwise adding a 12% sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to 70%, then continuously adding 15 parts by weight of acrylamide and 4 parts by weight of hydroxyethyl acrylate, keeping stirring and heating to 70 ℃, slowly dropwise adding 0.3 part by weight of potassium persulfate-sodium bisulfite redox system initiator and 0.2 part by weight of N, N-methylene bisacrylamide crosslinking agent, stirring and reacting at constant temperature for 3 hours after dropwise adding, drying in vacuum, crushing, and sieving with a 300-mesh sieve to obtain a hydroxyacrylic acid water-absorbent resin;
(2) adding the obtained hydroxyl acrylic acid water-absorbent resin into a ZYM80 three-ring micro-powder-mill superfine mill of Zhuya machinery, setting the rotation speed of a main shaft to be 235-240 r/min, grinding the material with the granularity of 10-15 um, and sieving the obtained powder with a 1200-mesh sieve to obtain a superfine water-absorbent material;
(3) adding 3 parts by weight of the superfine water absorbing material obtained in the step (2), 25 parts by weight of PPG polyether polyol with the molecular weight of 3000 and 20 parts by weight of carbon black pigment filler with the mesh number of 1200 into a hydraulic lifting dispersion machine which is produced by Dongguan Kode machinery and has the model of HFS-220, dispersing for 1.5 hours at the rotating speed of 2500r/min, then adding into a closed reaction kettle, stirring at a high speed and heating to 120 ℃, stirring at a speed of 350r/min, starting vacuum dehydration, wherein the vacuum degree is-0.08 MPa-0.09 MPa, and the dehydration time is 1.5 hours;
(4) reducing the temperature of the reaction kettle in the step (3) to 70 ℃, introducing nitrogen to protect and break vacuum, then adding 15 parts of toluene diisocyanate, stirring at high speed and mixing uniformly, adding 0.08 part of stannous octoate catalyst, and continuing to react for 3 hours;
(5) and (3) cooling the reaction kettle in the step (4) to 40 ℃ according to the parts by weight, continuously adding 0.6 part of imine latent curing agent, 8 parts of dioctyl sebacate plasticizer and 0.5 part of defoaming agent, stirring and mixing for 1.5 hours, then cooling to 30 ℃, discharging under the protection of nitrogen, and obtaining the high-stability single-component polyurethane waterproof coating.
The test method comprises the following steps:
the waterproof coatings of comparative example 1 and examples 1 to 2 were stored in an environment of 25 ℃ and 50% humidity without lid for 7 days, 14 days, 21 days and 28 days, and were coated according to the coating requirements in GB/T19250-2003 "polyurethane waterproof coating", cured for 7 days under standard conditions, and then the elongation after coating was measured.
Table 1 shows the results of the elongation property test of the polyurethane waterproof coating in this test
| Item | Comparative example 1 elongation | Comparative example 2 elongation | Example 1 elongation |
| Initial Properties | 902% | 904% | 905% |
| 50 ℃/7 days | 796% | 821% | 850% |
| 50 ℃/14 days | 781% | 780% | 814% |
| 50 ℃/21 days | 721% | 713% | 775% |
| 50 ℃/28 days | 689% | 667% | 734% |
Table 2 shows the viscosity test results of the polyurethane waterproofing paint in this test
| item/mPa.s | Comparative example 1 viscosity | Comparative example 2 viscosity | Example 1 viscosity |
| Initial Properties | 5040 | 5045 | 5030 |
| 50 ℃/7 days | 7530 | 6830 | 6750 |
| 50 ℃/14 days | 8700 | 7940 | 7990 |
| 50 ℃/21 days | 9980 | 9290 | 8600 |
| 50 ℃/28 days | 12100 | 10340 | 10320 |
As can be seen from tables 1 and 2, in comparative example 1, since no active hydroxyl group is added, the acrylic water-absorbent resin is only a water absorbent in the polyurethane system, and since the system is different, phase separation occurs slowly during storage, the protection effect of the acrylic water-absorbent resin on the polyurethane prepolymer is weakened, so that the active groups in the polyurethane prepolymer react, the viscosity is increased, and the elongation is reduced, in comparative example 2, since the magnesium sulfate water-absorbent resin is not added, the water-absorbent resin absorbs water and is stored in the polyurethane prepolymer in a moisture form, and is easily separated out and combined with isocyanate functional groups under the influence of temperature, so that the stability of the coating is influenced. Therefore, the water-absorbent resin prepared by the invention adsorbs magnesium sulfate as a water absorbent to be fixed on the polyurethane prepolymer, so that the polyurethane waterproof coating has good stability, and can be still in a stable state without chemical reaction in the presence of a small amount of moisture, thereby improving the storage stability and the waterproof performance of the waterproof coating.
Claims (10)
1. A preparation method of a high-stability single-component polyurethane waterproof coating is characterized by comprising the following steps:
(1) mixing, stirring and uniformly mixing acrylic acid and water, dropwise adding a sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to 65-75%, then continuously adding acrylamide and hydroxyacrylic acid, keeping stirring and heating to 60-80 ℃, slowly dropwise adding an initiator and a cross-linking agent, stirring and reacting at constant temperature for 2-3 hours after dropwise adding, drying in vacuum, crushing, and sieving with a 300-400-mesh sieve to obtain the hydroxyacrylic acid water-absorbent resin;
(2) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (1) into a magnesium sulfate solution at the temperature of 60-70 ℃, starting stirring to enable the hydroxyl acrylic acid water-absorbent resin to be completely absorbed and swelled, continuing stirring for 1-2 hours, filtering and separating, and drying and dehydrating at the temperature of 120-140 ℃ to obtain hydroxyl acrylic acid water-absorbent resin absorbed magnesium sulfate;
(3) adding the hydroxyl acrylic acid water-absorbent resin obtained in the step (2) to adsorb magnesium sulfate into a superfine grinding machine for grinding, and sieving the obtained powder with a 1000-1500-mesh sieve to obtain a superfine water-absorbent material;
(4) adding 2-4 parts by weight of the superfine water absorbing material obtained in the step (3), 20-30 parts by weight of polyether polyol and 10-30 parts by weight of pigment and filler into a dispersion machine, dispersing for 1-2 hours at the rotating speed of 2000-2800 r/min, then adding into a closed reaction kettle, stirring at a high speed and heating to 100-130 ℃, stirring at a speed of 300-400 r/min, starting vacuum dehydration, wherein the vacuum degree is-0.08 MPa-0.1 MPa, and the dehydration time is 1-2 hours;
(5) reducing the temperature of the reaction kettle in the step (4) to 60-80 ℃ according to the parts by weight, introducing nitrogen to protect vacuum, then adding 10-20 parts of isocyanate, stirring at a high speed and mixing uniformly, adding 0.04-0.1 part of catalyst, and continuing to react for 2-4 hours;
(6) cooling the reaction kettle in the step (5) to 30-50 ℃, continuously adding 0.3-1 part of latent curing agent, 3-10 parts of plasticizer and 0.2-1.4 parts of auxiliary agent, stirring and mixing for 1-2 hours, then cooling to 25-35 ℃, discharging under the protection of nitrogen, and obtaining the high-stability single-component polyurethane waterproof coating.
2. The preparation method of the high-stability single-component polyurethane waterproof paint according to claim 1, wherein the mass fraction of the sodium hydroxide solution in the step (1) is 10-15%; the initiator is a potassium persulfate-sodium bisulfite redox system; the cross-linking agent is preferably N, N-methylene bisacrylamide; the hydroxy acrylic acid is preferably one of hydroxyethyl acrylate, 4-hydroxy butyl acrylate and hydroxyethyl methacrylate; the acrylic acid, the sodium hydroxide solution, the acrylamide, the hydroxyacrylic acid, the initiator, the cross-linking agent and the water are in parts by weight: 10 to 20 parts, 1 to 3 parts, 10 to 20 parts, 3 to 5 parts, 0.06 to 0.4 part, 0.08 to 0.3 part, 100 to 150 parts.
3. The preparation method of the high-stability single-component polyurethane waterproof coating material according to claim 1, wherein the mass fraction of the magnesium sulfate solution in the step (2) is 20-30%.
4. The preparation method of the high-stability single-component polyurethane waterproof paint as claimed in claim 1, wherein in the step (3), the superfine pulverizer is selected from ZYM80 three-ring micronizers of Zhuya machinery, the rotation speed of a main shaft is set to 235-240 r/min, and the particle size of the finished product is 10-15 um; the disperser is a HFS-220 hydraulic lifting disperser which is produced by Dongguan Kode machinery.
5. The method for preparing the high-stability one-component polyurethane waterproof coating material according to claim 1, wherein the polyether polyol in the step (4) is at least one of PPG polyether polyol, POP polymer polyether polyol and polytetrahydrofuran polyether polyol, polyether polyol 2000D, polyether polyol N330 and polyether polyol 3050; the pigment and filler is preferably one or a mixture of more than one of carbon black, titanium dioxide, iron yellow, kaolin, wollastonite and talcum powder.
6. The method for preparing the high-stability one-component polyurethane waterproof coating material according to claim 1, wherein the isocyanate in the step (5) is one selected from toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, and isophorone diisocyanate.
7. The method for preparing the high-stability single-component polyurethane waterproof coating material as claimed in claim 1, wherein the catalyst in the step (5) is one of stannous octoate, lead isooctanoate, aliphatic amine tertiary amine, alicyclic amine tertiary amine and aromatic amine tertiary amine.
8. The method for preparing the high-stability one-component polyurethane waterproof coating according to claim 1, wherein the plasticizer in the step (6) is one or more of dioctyl sebacate, dibutyl phthalate, diisononyl phthalate, chlorinated paraffin and citric acid ester.
9. The preparation method of the high-stability single-component polyurethane waterproof coating material as claimed in claim 1, wherein the auxiliaries in the step (6) are a defoaming agent, a dispersing agent and an antioxidant; the latent curing agent is an imine latent curing agent.
10. A high-stability single-component polyurethane waterproof paint, which is prepared by the method according to any one of claims 1 to 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276747A (en) * | 2022-01-06 | 2022-04-05 | 江苏凯伦建材股份有限公司 | Ultralow-temperature-resistant easy-construction single-component polyurethane waterproof coating and preparation method thereof |
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| CN116463045A (en) * | 2023-04-24 | 2023-07-21 | 广州碧家索建材有限公司 | Ash rubber waterproof coating and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0372981B1 (en) * | 1988-12-08 | 1995-09-13 | Nippon Shokubai Co., Ltd. | Method for production of absorbent resin excelling in durability |
| CN104353432A (en) * | 2014-08-27 | 2015-02-18 | 南京市荣达树脂有限公司 | Super absorbent resin-based absorbent and preparation method thereof |
| KR20160064387A (en) * | 2014-11-28 | 2016-06-08 | 한국건설생활환경시험연구원 | Self swelling compound composition and self-adhesive water-proof material |
| CN109705715A (en) * | 2018-12-28 | 2019-05-03 | 北京东方雨虹防水技术股份有限公司 | Application and mono-composition poyurethane water-proof paint and preparation method thereof of the acrylic absorbent resin in mono-composition poyurethane water-proof paint |
| CN109929426A (en) * | 2019-01-25 | 2019-06-25 | 北京东方雨虹防水技术股份有限公司 | A kind of latent curing agent type mono-composition poyurethane water-proof paint |
| CN110423308A (en) * | 2019-03-12 | 2019-11-08 | 北京市政建设集团有限责任公司 | The preparation method of a kind of super absorbent resin and in the application for reducing dregs moisture content |
-
2020
- 2020-07-28 CN CN202010737404.4A patent/CN111808518A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0372981B1 (en) * | 1988-12-08 | 1995-09-13 | Nippon Shokubai Co., Ltd. | Method for production of absorbent resin excelling in durability |
| CN104353432A (en) * | 2014-08-27 | 2015-02-18 | 南京市荣达树脂有限公司 | Super absorbent resin-based absorbent and preparation method thereof |
| KR20160064387A (en) * | 2014-11-28 | 2016-06-08 | 한국건설생활환경시험연구원 | Self swelling compound composition and self-adhesive water-proof material |
| CN109705715A (en) * | 2018-12-28 | 2019-05-03 | 北京东方雨虹防水技术股份有限公司 | Application and mono-composition poyurethane water-proof paint and preparation method thereof of the acrylic absorbent resin in mono-composition poyurethane water-proof paint |
| CN109929426A (en) * | 2019-01-25 | 2019-06-25 | 北京东方雨虹防水技术股份有限公司 | A kind of latent curing agent type mono-composition poyurethane water-proof paint |
| CN110423308A (en) * | 2019-03-12 | 2019-11-08 | 北京市政建设集团有限责任公司 | The preparation method of a kind of super absorbent resin and in the application for reducing dregs moisture content |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276747A (en) * | 2022-01-06 | 2022-04-05 | 江苏凯伦建材股份有限公司 | Ultralow-temperature-resistant easy-construction single-component polyurethane waterproof coating and preparation method thereof |
| CN114276747B (en) * | 2022-01-06 | 2023-02-10 | 江苏凯伦建材股份有限公司 | Ultralow-temperature-resistant easy-construction single-component polyurethane waterproof coating and preparation method thereof |
| CN115505317A (en) * | 2022-10-31 | 2022-12-23 | 中德新亚建筑材料有限公司 | Water-based epoxy asphalt waterproof and anticorrosive coating for inner wall of water tank and preparation method thereof |
| CN116535613A (en) * | 2022-11-16 | 2023-08-04 | 江苏奥斯佳材料科技股份有限公司 | Preparation method of polyurethane curing agent |
| CN116463045A (en) * | 2023-04-24 | 2023-07-21 | 广州碧家索建材有限公司 | Ash rubber waterproof coating and preparation method thereof |
| CN116463045B (en) * | 2023-04-24 | 2024-02-02 | 广州碧家索建材有限公司 | Ash rubber waterproof coating and preparation method thereof |
| CN116851627A (en) * | 2023-07-14 | 2023-10-10 | 东亚科技(苏州)有限公司 | Adhesive for cast aluminum resin and coating for cast aluminum resin sand mold |
| CN116851627B (en) * | 2023-07-14 | 2024-04-12 | 东亚科技(苏州)有限公司 | Coating for cast aluminum resin sand mold |
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