CN114410146A - Novel high-water-resistance polymer cement waterproof coating and preparation method thereof - Google Patents
Novel high-water-resistance polymer cement waterproof coating and preparation method thereof Download PDFInfo
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- CN114410146A CN114410146A CN202210007062.XA CN202210007062A CN114410146A CN 114410146 A CN114410146 A CN 114410146A CN 202210007062 A CN202210007062 A CN 202210007062A CN 114410146 A CN114410146 A CN 114410146A
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Images
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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
- C09D1/08—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement with organic additives
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention discloses a novel high water-resistant polymer cement waterproof coating and a preparation method thereof, wherein the used liquid raw materials comprise 70-90 parts of polymer emulsion, 10-30 parts of deionized water, 0-5 parts of defoaming agent, 0-2 parts of dispersing agent, 1-3.5 parts of film-forming auxiliary agent, 0-5 parts of thickening agent and 0-10 parts of urea-formaldehyde resin coated carbodiimide; the powder raw materials comprise 20-30 parts of cement, 20-30 parts of quartz powder, 40-50 parts of calcium powder, 0-5 parts of water reducing agent and 0-1 part of cellulose ether. The urea-formaldehyde resin coated carbodiimide is urea-formaldehyde resin coated polycarbodiimide microcapsules prepared by a two-step method of prepolymerization reaction and polycondensation reaction. The urea-formaldehyde resin coated carbodiimide reinforced polymer cement waterproof coating provided by the invention can prolong the storage time of a liquid product and prolong the service life of a coating, improves the solvent resistance, water resistance and antifouling property of the coating, has excellent wear resistance and light resistance and higher hardness, and is used in an environment which needs to be in contact with water for a long time and be soaked in water for a long time in a humid manner.
Description
Technical Field
The invention relates to the technical field of waterproof coatings, in particular to a novel high-water-resistance polymer cement waterproof coating and a preparation method thereof.
Background
The building waterproof engineering is a very important part of modern building engineering, the most applied indoor waterproof is the water-based polymer cement waterproof coating at present, and the water-based polymer cement waterproof coating is a waterproof material which is compounded by polymer emulsion, cement and other inorganic materials, has certain flexibility and rigidity and high environmental protection performance.
However, after the existing water-based polymer cement waterproof coating forms a film, substances are dissolved out after long-term soaking, the overall waterproof performance is affected, and the environmental application such as a swimming pool, a water pool and the like which needs to be contacted with water for a long time and be soaked in water for a long time is difficult to meet. Therefore, in order to solve the problem, a high water-resistant polymer cement waterproof coating which is resistant to long-term water erosion, resistant to cracking, high in strength and good in flexibility needs to be researched.
The polycarbodiimide crosslinking agent has the advantages of excellent coating performance, fast and efficient curing, long slurry storage time and the like, the crosslinked coating has good solvent resistance, water resistance and antifouling property, excellent wear resistance and light resistance and higher hardness, but the polycarbodiimide has more active performance and is easy to react with active groups in polymer emulsion.
Disclosure of Invention
In order to achieve the purpose, the invention provides the following technical scheme:
a novel high water-resistant polymer cement waterproof coating comprises the following raw materials: liquid materials and powder materials, wherein,
the liquid material raw materials comprise 70-90 parts of polymer emulsion, 10-30 parts of deionized water, 0-5 parts of defoaming agent, 0-2 parts of dispersing agent, 1-3.5 parts of film-forming additive, 0-5 parts of thickening agent and 0-10 parts of urea-formaldehyde resin coated carbodiimide;
the powder raw materials comprise 20-30 parts of cement, 20-30 parts of quartz powder, 40-50 parts of calcium powder, 0-5 parts of water reducing agent and 0-1 part of cellulose ether.
Preferably, the liquid material raw material and the powder material raw material are weighed according to mass percentage.
Preferably, the raw materials of the urea resin coated carbodiimide microcapsule comprise: urea, formaldehyde, deionized water and carbodiimide; the urea-formaldehyde resin coated carbodiimide microcapsule comprises carbodiimide and urea-formaldehyde resin, wherein the urea-formaldehyde resin surrounds the carbodiimide.
Preferably, the polymer emulsion comprises one or more of, but is not limited to, styrene-acrylic emulsion, styrene-butadiene emulsion, and vinyl acetate copolymer emulsion.
Preferably, the defoaming agent comprises but is not limited to one or more of silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
Preferably, the dispersant comprises one or more of but not limited to polyethylene glycol, hydroxypropyl methacrylate, organic siloxane containing anionic wetting dispersant, anionic polymer dispersant and acrylic block copolymer.
Preferably, the coalescent includes, but is not limited to, one or more of propylene glycol, lauryl alcohol ester, propylene glycol ethyl ether, hexylene glycol butyl ether acetate.
Preferably, the thickener includes, but is not limited to, one or more of silica gel, sodium alginate, cellulose ether, and chitosan.
Preferably, the water reducing agent comprises one or more of a naphthalene water reducing agent, a resin water reducing agent and a lignin water reducing agent.
A preparation method of a novel high-water-resistance polymer cement waterproof coating comprises the following steps:
preparing a urea-formaldehyde resin coated polycarbodiimide microcapsule;
weighing liquid raw materials and powder raw materials for later use;
uniformly mixing the polymer emulsion, the defoaming agent, the film-forming assistant and the dispersing agent, adding deionized water, stirring for 10-30 minutes to prepare a mixed solution, and finally adding the urea-formaldehyde resin-coated polycarbodiimide microcapsules to prepare a mixed solution material for later use;
white cement, quartz sand, calcium powder, cellulose ether and a water reducing agent are uniformly mixed to prepare mixed powder for later use;
and stirring and mixing the mixed liquid material and the mixed powder material according to the ratio of 1:1.4 for 5-15 minutes to obtain the high-water-resistance polymer waterproof paint.
Preferably, the preparation of the urea-formaldehyde resin coated polycarbodiimide microcapsule comprises the preparation of a urea-formaldehyde resin prepolymer, the preparation of an oil/water emulsion and the preparation of the urea-formaldehyde resin coated polycarbodiimide microcapsule, and the preparation method comprises the following specific steps of:
the preparation of the urea-formaldehyde resin prepolymer comprises the steps of adding urea, formaldehyde and deionized water in a certain ratio into a reaction kettle provided with a thermometer and a stirring device, mixing and dissolving, adjusting the pH to 8.5-9.5 by using a sodium hydroxide solution, heating to 70 ℃ under the stirring of 300r/min, reacting for 1-2h to obtain a prepolymer aqueous solution, and cooling for later use;
the preparation of the oil/water emulsion comprises weighing a certain amount of carbodiimide, heating and dissolving in a certain amount of oil phase solvent to obtain an oil phase, and cooling for later use; weighing a proper amount of water-soluble emulsifier, stirring and dissolving in deionized water to obtain a water phase; mixing oil and water phases, and shearing and emulsifying at 9000-;
the preparation of the urea-formaldehyde resin coated polycarbodiimide microcapsule comprises the steps of uniformly stirring the emulsion and the prepolymer aqueous solution, dropwise adding hydrochloric acid to gradually adjust the pH to 8.5-9.5, heating to 60 ℃, and preserving heat for 3-5 hours; after the polycondensation reaction is finished, adjusting the pH of the mixed solution to 6-7 by using a sodium hydroxide solution to obtain the urea-formaldehyde resin coated polycarbodiimide microcapsule suspension.
The urea-formaldehyde resin coated carbodiimide reinforced polymer cement waterproof coating product provided by the invention has the following technical effects and advantages:
1. the carbodiimide can be effectively protected, the reaction between the carbodiimide and the polymer emulsion is avoided, the storage time of a liquid material product can be effectively prolonged, and the service life of a coating can be effectively prolonged;
2. the solvent resistance, water resistance and antifouling property of the coating can be effectively improved, and the coating has excellent wear resistance and light resistance and higher hardness;
3. can meet the environmental application that needs long-term contact with water and long-term wet immersion, such as swimming pools, water pools and the like.
In summary, the polycarbodiimide is introduced into the polymer cement waterproof coating in a mode of coating the polycarbodiimide by the urea-formaldehyde resin, so as to obtain the high water resistance polymer cement waterproof coating with long-term water erosion resistance, cracking resistance, high strength and good flexibility. The method for preparing the high-water-resistance polymer cement waterproof coating by introducing the polycarbodiimide into the polymer cement waterproof coating is the subject of the invention, because the polycarbodiimide crosslinking agent has the advantages of excellent coating performance, fast and efficient curing, long slurry storage time and the like, the crosslinked coating has good solvent resistance, water resistance and antifouling property, excellent wear resistance and light resistance and higher hardness.
Although the polycarbodiimide has more active performance and is easy to react with active groups in the polymer emulsion, aiming at the characteristic that the polycarbodiimide is easy to react with the active groups in the polymer emulsion so as to be decomposed, the direct contact between the polycarbodiimide and the polymer emulsion is prevented by adopting a mode of preparing the microcapsule by coating the polycarbodiimide with urea-formaldehyde resin, so that the polycarbodiimide is prevented from being consumed before the polymer emulsion is compounded with inorganic materials such as cement and the like. The physical properties of the urea-formaldehyde resin are unstable, and the urea-formaldehyde resin is easy to crack when being stirred and sheared by the outside, so that the polycarbodiimide serving as the inner core is released to play a role when liquid and powder are stirred.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
FIG. 1 is a scanning electron microscope image of a urea resin-coated polycarbodiimide microcapsule.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The building waterproof engineering is a very important part of modern building engineering, the most applied indoor waterproof is the water-based polymer cement waterproof coating at present, and the water-based polymer cement waterproof coating is a waterproof material which is compounded by polymer emulsion, cement and other inorganic materials, has certain flexibility and rigidity and high environmental protection performance. However, after the existing water-based polymer cement waterproof coating forms a film, substances are dissolved out after long-term soaking, the overall waterproof performance is affected, and the environmental application such as a swimming pool, a water pool and the like which needs to be contacted with water for a long time and be soaked in water for a long time is difficult to meet. Therefore, in order to solve the problem, a high water-resistant polymer cement waterproof coating which is resistant to long-term water erosion, resistant to cracking, high in strength and good in flexibility needs to be researched.
In order to solve the defects of the prior art, the invention introduces the polycarbodiimide into the polymer cement waterproof coating in a mode of coating the polycarbodiimide by the urea-formaldehyde resin so as to obtain the high water-resistant polymer cement waterproof coating with long-term water erosion resistance, cracking resistance, high strength and good flexibility. The invention discloses a novel high water-resistant polymer cement waterproof coating and a preparation method thereof, wherein the novel high water-resistant polymer cement waterproof coating comprises the following raw materials: the liquid material comprises 70-90 parts of polymer emulsion, 10-30 parts of deionized water, 0-5 parts of defoaming agent, 0-2 parts of dispersing agent, 1-3.5 parts of film-forming assistant, 0-5 parts of thickening agent and 0-10 parts of urea-formaldehyde resin coated carbodiimide; the powder raw materials comprise 20-30 parts of white cement, 20-30 parts of quartz powder, 40-50 parts of calcium powder, 0-5 parts of water reducing agent and 0-1 part of cellulose ether.
Further, the urea-formaldehyde resin coated carbodiimide adopts a two-step method to prepare the urea-formaldehyde resin microcapsule by urea, formaldehyde, deionized water and carbodiimide, the process is mainly divided into two stages of prepolymerization reaction and polycondensation reaction, and the polycondensation stage can be subdivided into an acidification process and a curing process, corresponding to the formation and the molding of the capsule wall. As shown in fig. 1, the urea resin coated carbodiimide microcapsule is irregular spherical and includes carbodiimide and urea resin, wherein the urea resin surrounds the carbodiimide.
Further, the polymer emulsion comprises one or more of, but is not limited to, styrene-acrylic emulsion, styrene-butadiene emulsion, and vinyl acetate copolymer emulsion.
Further, the defoaming agent includes, but is not limited to, one or more of silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, and polydimethylsiloxane.
Further, the dispersing agent comprises one or more of but not limited to polyethylene glycol, hydroxypropyl methacrylate, organic siloxane containing anionic wetting dispersing agent, anionic polymer dispersing agent and acrylic block copolymer.
Further, the film forming auxiliary agent comprises one or more of propylene glycol, dodecyl alcohol ester, propylene glycol ethyl ether and hexanediol butyl ether acetate.
Further, the thickening agent comprises one or more of but not limited to silica gel, sodium alginate, cellulose ether and chitosan.
Further, the water reducing agent includes, but is not limited to, one or more of a naphthalene water reducing agent, a resin water reducing agent, and a lignin water reducing agent.
The preparation method of the novel high-water-resistance polymer cement waterproof coating comprises the following steps: preparing a urea-formaldehyde resin coated polycarbodiimide microcapsule; weighing all the raw materials for later use; uniformly mixing the polymer emulsion, the defoaming agent, the film-forming assistant, the dispersing agent and the like, adding deionized water, stirring for 10-30 minutes to prepare a mixed solution, and finally adding the urea-formaldehyde resin-coated polycarbodiimide microcapsules to prepare a mixed solution material for later use; white cement, quartz sand, calcium powder, cellulose ether and a water reducing agent are uniformly mixed to prepare mixed powder for later use; and stirring and mixing the mixed liquid material and the mixed powder material according to the ratio of 1:1.4 for 5-15 minutes to obtain the high-water-resistance polymer waterproof paint.
The method for preparing the high-water-resistance polymer cement waterproof coating by introducing the polycarbodiimide into the polymer cement waterproof coating is the subject of the invention. The polycarbodiimide crosslinking agent has the advantages of excellent coating performance, fast and efficient curing, long slurry storage time and the like. The crosslinked coating has good solvent resistance, water resistance and antifouling property, excellent wear resistance and light resistance and higher hardness.
However, polycarbodiimide is relatively active in performance and is easy to react with active groups in polymer emulsion. Aiming at the characteristic that the polycarbodiimide is easy to react with active groups in the polymer emulsion so as to be decomposed, the direct contact between the polycarbodiimide and the polymer emulsion is prevented by adopting a mode of preparing the microcapsule by coating the polycarbodiimide with urea-formaldehyde resin, so that the polycarbodiimide is prevented from being consumed before the polymer emulsion is compounded with inorganic materials such as cement. The physical properties of the urea-formaldehyde resin are unstable, and the urea-formaldehyde resin is easy to crack when being stirred and sheared by the outside, so that the polycarbodiimide serving as the inner core is released to play a role when liquid and powder are stirred.
Further, the method for preparing the urea-formaldehyde resin coated polycarbodiimide microcapsule comprises the steps of preparing a urea-formaldehyde resin prepolymer, preparing an oil/water emulsion and preparing the urea-formaldehyde resin coated polycarbodiimide microcapsule, and comprises the following specific steps:
the preparation of the urea-formaldehyde resin prepolymer comprises the steps of adding urea, formaldehyde and deionized water in a certain ratio into a reaction kettle provided with a thermometer and a stirring device, mixing and dissolving, adjusting the pH to 8.5-9.5 by using a sodium hydroxide solution, heating to 70 ℃ under the stirring of 300r/min, reacting for 1-2h to obtain a prepolymer aqueous solution, and cooling for later use.
The preparation of the oil/water emulsion comprises weighing a certain amount of carbodiimide, heating and dissolving in a certain amount of oil phase solvent to obtain an oil phase, and cooling for later use; weighing a proper amount of water-soluble emulsifier, stirring and dissolving in deionized water to obtain a water phase; mixing oil and water, and shearing and emulsifying at 9000-12000r/min for 5-15min to obtain the emulsion.
The preparation of the urea-formaldehyde resin coated polycarbodiimide microcapsule comprises the steps of uniformly stirring the emulsion and the prepolymer aqueous solution, dropwise adding hydrochloric acid to gradually adjust the pH to 8.5-9.5, heating to 60 ℃, and preserving heat for 3-5 hours; after the polycondensation reaction is finished, adjusting the pH of the mixed solution to 6-7 by using a sodium hydroxide solution to obtain the urea-formaldehyde resin coated polycarbodiimide microcapsule suspension.
Furthermore, the urea-formaldehyde resin coated polycarbodiimide microcapsules are introduced into the polymer cement waterproof coating, so that the polymer cement waterproof coating with high water resistance, long-term water erosion resistance, cracking resistance, high strength and good flexibility can be formed.
The invention will be further illustrated by means of specific examples.
Example 1
The liquid material raw material of the embodiment comprises 90 parts of polymer emulsion, 10 parts of deionized water, 3 parts of defoaming agent, 1 part of dispersing agent, 2 parts of film-forming assistant, 2 parts of thickening agent and 3 parts of urea-formaldehyde resin coated carbodiimide.
The powder raw material of the embodiment: 52.5 parts of white cement, 20 parts of quartz powder, 60 parts of calcium powder, 5 parts of water reducing agent and 0.5 part of cellulose ether.
Uniformly mixing the polymer emulsion, the defoaming agent, the film-forming assistant, the dispersing agent and the like, adding deionized water, stirring for 10-30 minutes to prepare a mixed solution, and finally adding the urea-formaldehyde resin-coated polycarbodiimide microcapsules to prepare a mixed solution material for later use.
Mixing 52.5 white cement, quartz sand, calcium powder, cellulose ether and a water reducing agent uniformly to prepare mixed powder for later use.
And stirring and mixing the mixed liquid material and the mixed powder material according to the ratio of 1:1.4 for 5-15 minutes to obtain the high-water-resistance polymer waterproof paint.
The experiment is verified according to the proportion, and the experimental result is as follows: the tensile strength was 2.3MPa, the elongation at break was 117%, and the water absorption was 4.5%.
Example 2
Liquid raw material of this example: 80 parts of polymer emulsion, 20 parts of deionized water, 4 parts of defoaming agent, 1.5 parts of dispersing agent, 3 parts of film-forming additive, 3 parts of thickening agent and 6 parts of urea-formaldehyde resin coated carbodiimide.
The powder raw material of the embodiment: 52.5 parts of white cement, 20 parts of quartz powder, 60 parts of calcium powder, 5 parts of water reducing agent and 0.5 part of cellulose ether.
Uniformly mixing the polymer emulsion, the defoaming agent, the film-forming assistant, the dispersing agent and the like, adding deionized water, stirring for 10-30 minutes to prepare a mixed solution, and finally adding the urea-formaldehyde resin-coated polycarbodiimide microcapsules to prepare a mixed solution material for later use.
Mixing 52.5 white cement, quartz sand, calcium powder, cellulose ether and a water reducing agent uniformly to prepare mixed powder for later use.
And stirring and mixing the mixed liquid material and the mixed powder material according to the ratio of 1:1.4 for 5-15 minutes to obtain the high-water-resistance polymer waterproof paint.
The experiment is verified according to the proportion, and the experimental result is as follows: the tensile strength was 2.1MPa, the elongation at break was 109% and the water absorption was 3.8%.
Example 3
Liquid raw material of this example: 70 parts of polymer emulsion, 30 parts of deionized water, 3 parts of defoaming agent, 1 part of dispersing agent, 2 parts of film-forming additive, 2 parts of thickening agent and 9 parts of urea-formaldehyde resin coated carbodiimide.
The powder raw material of the embodiment: 52.5 parts of white cement, 20 parts of quartz powder, 60 parts of calcium powder, 5 parts of water reducing agent and 0.5 part of cellulose ether.
Uniformly mixing the polymer emulsion, the defoaming agent, the film-forming assistant, the dispersing agent and the like, adding deionized water, stirring for 10-30 minutes to prepare a mixed solution, and finally adding the urea-formaldehyde resin-coated polycarbodiimide microcapsules to prepare a mixed solution material for later use.
Mixing 52.5 white cement, quartz sand, calcium powder, cellulose ether and a water reducing agent uniformly to prepare mixed powder for later use.
And stirring and mixing the mixed liquid material and the mixed powder material according to the ratio of 1:1.4 for 5-15 minutes to obtain the high-water-resistance polymer waterproof paint.
The experiment is verified according to the proportion, and the experimental result is as follows: the tensile strength was 2.0MPa, the elongation at break was 105%, and the water absorption was 3.2%.
The following summary of the performance test results of the novel waterproof polymer cement coating prepared by the above 3 specific examples is shown in table 1:
TABLE 1 summary of the performance test results of cement waterproofing coatings
| Example 1 | Example 2 | Example 3 | |
| Tensile strength | 2.3MPa | 2.1MPa | 2.0MPa |
| Elongation at break | 117％ | 109％ | 105％ |
| Water absorption rate | 4.5％ | 3.8％ | 3.2％ |
From the above test results, according to the standard of the Q/SY YHF 0122-2019 water-resistant type water-based waterproof coating of the enterprise Standard of Beijing Oriental Rainbow waterproof technology, Inc., the tensile strength, elongation at break and water absorption of the novel high water-resistant polymer cement waterproof coating prepared in the three embodiments of the invention all meet the standard.
In conclusion, the polycarbodiimide is introduced into the polymer cement waterproof coating in a mode of coating the polycarbodiimide by the urea-formaldehyde resin, so that the polymer cement waterproof coating with high water resistance, long-term water erosion resistance, cracking resistance, high strength and good flexibility is obtained, and the novel polymer cement waterproof coating with high water resistance is provided.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (11)
1. The novel high-water-resistance polymer cement waterproof coating is characterized by comprising the following raw materials: liquid materials and powder materials, wherein,
the liquid material raw materials comprise 70-90 parts of polymer emulsion, 10-30 parts of deionized water, 0-5 parts of defoaming agent, 0-2 parts of dispersing agent, 1-3.5 parts of film-forming additive, 0-5 parts of thickening agent and 0-10 parts of urea-formaldehyde resin coated carbodiimide;
the powder raw materials comprise 20-30 parts of cement, 20-30 parts of quartz powder, 40-50 parts of calcium powder, 0-5 parts of water reducing agent and 0-1 part of cellulose ether.
2. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the liquid raw material and the powder raw material are weighed according to mass percentage.
3. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the urea resin coated carbodiimide microcapsule comprises the following raw materials: urea, formaldehyde, deionized water and carbodiimide;
the urea-formaldehyde resin coated carbodiimide microcapsule comprises carbodiimide and urea-formaldehyde resin, wherein the urea-formaldehyde resin surrounds the carbodiimide.
4. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the polymer emulsion comprises one or more of, but is not limited to, styrene-acrylic emulsion, styrene-butadiene emulsion and vinyl acetate copolymer emulsion.
5. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the defoaming agent comprises but is not limited to one or more of emulsified silicone oil, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
6. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the dispersing agent comprises one or more of but not limited to polyethylene glycol, hydroxypropyl methacrylate, organic siloxane containing anionic wetting dispersing agent, anionic polymer dispersing agent and acrylic block copolymer.
7. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the film forming aid includes, but is not limited to, one or more of propylene glycol, lauryl alcohol ester, propylene glycol ethyl ether, and hexylene glycol butyl ether acetate.
8. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the thickening agent comprises one or more of but not limited to silica gel, sodium alginate, cellulose ether and chitosan.
9. The novel high water resistance polymer cement waterproofing coating according to claim 1,
the water reducing agent comprises one or more of but not limited to a naphthalene water reducing agent, a resin water reducing agent and a lignin water reducing agent.
10. A method for preparing a novel high water resistance polymer cement waterproofing coating according to any of claims 1 to 9, characterized in that the method comprises the steps of:
preparing a urea-formaldehyde resin coated polycarbodiimide microcapsule;
weighing liquid raw materials and powder raw materials for later use;
uniformly mixing the polymer emulsion, the defoaming agent, the film-forming assistant and the dispersing agent, adding deionized water, stirring for 10-30 minutes to prepare a mixed solution, and finally adding the urea-formaldehyde resin-coated polycarbodiimide microcapsules to prepare a mixed solution material for later use;
white cement, quartz sand, calcium powder, cellulose ether and a water reducing agent are uniformly mixed to prepare mixed powder for later use;
and stirring and mixing the mixed liquid material and the mixed powder material according to the ratio of 1:1.4 for 5-15 minutes to obtain the high-water-resistance polymer waterproof paint.
11. The preparation method of the novel high water-resistant polymer cement waterproof coating material as claimed in claim 10, wherein the preparation of the urea-formaldehyde resin coated polycarbodiimide microcapsule comprises the preparation of urea-formaldehyde resin prepolymer, the preparation of oil/water emulsion and the preparation of urea-formaldehyde resin coated polycarbodiimide microcapsule, and comprises the following steps:
the preparation of the urea-formaldehyde resin prepolymer comprises the steps of adding urea, formaldehyde and deionized water in a certain ratio into a reaction kettle provided with a thermometer and a stirring device, mixing and dissolving, adjusting the pH to 8.5-9.5 by using a sodium hydroxide solution, heating to 70 ℃ under the stirring of 300r/min, reacting for 1-2h to obtain a prepolymer aqueous solution, and cooling for later use;
the preparation of the oil/water emulsion comprises weighing a certain amount of carbodiimide, heating and dissolving in a certain amount of oil phase solvent to obtain an oil phase, and cooling for later use; weighing a proper amount of water-soluble emulsifier, stirring and dissolving in deionized water to obtain a water phase; mixing oil and water phases, and shearing and emulsifying at 9000-;
the preparation of the urea-formaldehyde resin coated polycarbodiimide microcapsule comprises the steps of uniformly stirring the emulsion and the prepolymer aqueous solution, dropwise adding hydrochloric acid to gradually adjust the pH to 8.5-9.5, heating to 60 ℃, and preserving heat for 3-5 hours; after the polycondensation reaction is finished, adjusting the pH of the mixed solution to 6-7 by using a sodium hydroxide solution to obtain the urea-formaldehyde resin coated polycarbodiimide microcapsule suspension.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521677A (en) * | 2022-05-26 | 2022-12-27 | 苏州百联节能科技股份有限公司 | Anti-aging stable environment-friendly waterproof coating |
| CN115572497A (en) * | 2022-10-13 | 2023-01-06 | 远大洪雨（唐山）防水材料有限公司 | High-water-resistance polymer cement waterproof coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050085616A1 (en) * | 2002-02-13 | 2005-04-21 | Basf Aktiengesellschaft | Aqueous dispersions consisting of polycarbodimides |
| JP2009241044A (en) * | 2008-03-31 | 2009-10-22 | Fujifilm Corp | Microcapsule and its manufacturing method |
| CN105062281A (en) * | 2015-08-17 | 2015-11-18 | 惠州东方雨虹建筑材料有限责任公司 | I-type environment-friendly two-component polymer cement waterproof paint and preparation method |
| US20160075600A1 (en) * | 2013-04-26 | 2016-03-17 | Sika Technology Ag | Fast curing composition for the manufacture of polyurethane cementitious hybrid flooring |
| CN111825417A (en) * | 2020-08-04 | 2020-10-27 | 卢俊杰 | Mildew-proof polymer cement waterproof coating and preparation method thereof |
| CN112251059A (en) * | 2020-10-20 | 2021-01-22 | 陕西煤业化工技术研究院有限责任公司 | Cement-based spraying material and preparation method and application thereof |
| CN113861764A (en) * | 2021-11-05 | 2021-12-31 | 宏源防水科技集团有限公司 | High-water-resistance polymer cement waterproof coating and preparation process thereof |
-
2022
- 2022-01-05 CN CN202210007062.XA patent/CN114410146A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050085616A1 (en) * | 2002-02-13 | 2005-04-21 | Basf Aktiengesellschaft | Aqueous dispersions consisting of polycarbodimides |
| JP2009241044A (en) * | 2008-03-31 | 2009-10-22 | Fujifilm Corp | Microcapsule and its manufacturing method |
| US20160075600A1 (en) * | 2013-04-26 | 2016-03-17 | Sika Technology Ag | Fast curing composition for the manufacture of polyurethane cementitious hybrid flooring |
| CN105062281A (en) * | 2015-08-17 | 2015-11-18 | 惠州东方雨虹建筑材料有限责任公司 | I-type environment-friendly two-component polymer cement waterproof paint and preparation method |
| CN111825417A (en) * | 2020-08-04 | 2020-10-27 | 卢俊杰 | Mildew-proof polymer cement waterproof coating and preparation method thereof |
| CN112251059A (en) * | 2020-10-20 | 2021-01-22 | 陕西煤业化工技术研究院有限责任公司 | Cement-based spraying material and preparation method and application thereof |
| CN113861764A (en) * | 2021-11-05 | 2021-12-31 | 宏源防水科技集团有限公司 | High-water-resistance polymer cement waterproof coating and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吕百龄等: "《实用工业助剂全书》", 31 August 2001, 化学工业出版社 * |
| 罗瑞林等: "《织物涂层》", 31 May 1994, 中国纺织出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521677A (en) * | 2022-05-26 | 2022-12-27 | 苏州百联节能科技股份有限公司 | Anti-aging stable environment-friendly waterproof coating |
| CN115572497A (en) * | 2022-10-13 | 2023-01-06 | 远大洪雨（唐山）防水材料有限公司 | High-water-resistance polymer cement waterproof coating and preparation method thereof |
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