CN111944378A - Polymer-based waterproof film, preparation method and application thereof - Google Patents
Polymer-based waterproof film, preparation method and application thereof Download PDFInfo
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- CN111944378A CN111944378A CN202010574668.2A CN202010574668A CN111944378A CN 111944378 A CN111944378 A CN 111944378A CN 202010574668 A CN202010574668 A CN 202010574668A CN 111944378 A CN111944378 A CN 111944378A
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- 229920000642 polymer Polymers 0.000 title claims abstract 12
- 238000002360 preparation method Methods 0.000 title abstract 3
- 229920001661 Chitosan Polymers 0.000 claims abstract 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000000843 powder Substances 0.000 claims abstract 8
- 239000000243 solution Substances 0.000 claims abstract 8
- 238000003756 stirring Methods 0.000 claims abstract 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000000839 emulsion Substances 0.000 claims abstract 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000007864 aqueous solution Substances 0.000 claims abstract 4
- 239000011344 liquid material Substances 0.000 claims abstract 4
- 238000002156 mixing Methods 0.000 claims abstract 4
- 239000006004 Quartz sand Substances 0.000 claims abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract 3
- UYZLQWUFBLEIAJ-UHFFFAOYSA-N [hydroxy(dimethyl)silyl] 2-hydroxybenzoate Chemical compound C[Si](C)(O)OC(=O)C1=CC=CC=C1O UYZLQWUFBLEIAJ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002518 antifoaming agent Substances 0.000 claims abstract 3
- 229960005070 ascorbic acid Drugs 0.000 claims abstract 3
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract 3
- 239000011668 ascorbic acid Substances 0.000 claims abstract 3
- 229920003086 cellulose ether Polymers 0.000 claims abstract 3
- 239000004568 cement Substances 0.000 claims abstract 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract 3
- 239000002270 dispersing agent Substances 0.000 claims abstract 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract 3
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract 3
- 229940023561 silanediol salicylate Drugs 0.000 claims abstract 3
- 241000276489 Merlangius merlangus Species 0.000 claims abstract 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims abstract 2
- 238000004078 waterproofing Methods 0.000 claims 9
- 239000012528 membrane Substances 0.000 claims 8
- 238000000034 method Methods 0.000 claims 6
- 238000000576 coating method Methods 0.000 claims 4
- 239000011248 coating agent Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 2
- 229960000583 acetic acid Drugs 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000006260 foam Substances 0.000 claims 1
- 239000012362 glacial acetic acid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a polymer-based waterproof film, a preparation method and application thereof, and relates to the technical field of waterproof films. The preparation method of the polymer-based waterproof film comprises the following steps: adding ascorbic acid, hydrogen peroxide and silanediol salicylate into the chitosan solution, and reacting to obtain a modified chitosan solution; mixing a sodium dodecyl sulfate aqueous solution, a modified chitosan solution and a vinyl acetate monomer, dropwise adding an ammonium persulfate aqueous solution, and reacting at constant temperature to obtain a modified polyvinyl acetate emulsion; adding water, a defoaming agent, a dispersing agent and a film-forming auxiliary agent into the emulsion, and uniformly stirring to obtain a liquid material; uniformly mixing cement, coarse whiting, quartz sand, a water reducing agent and cellulose ether powder to prepare powder; the powder and the liquid are mixed and then coated to form a film. The waterproof film has the advantages of high flexibility, high elasticity and good aging resistance, and has better tensile strength and water resistance and good adhesion with a base layer. Meanwhile, the paint also has the advantages of no toxicity, no smell and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of waterproof films, and particularly relates to a polymer-based waterproof film, and a preparation method and application thereof.
Background
Waterproofing has long been no longer a fresh topic, and is not negligible in tunnels, bridges, dams, roads, buildings and houses where people live in daily life. The waterproof material is a functional material which can protect buildings, structures and components thereof from being corroded and damaged by water and can be lacked in the class of normal use of the buildings and the structures. For the waterproof building material alone, the use history of the waterproof building material has been thousands of years in China, and the waterproof building material has been rapidly developed in recent decades. But the engineering quality problem is still outstanding, and particularly the quality of the building waterproof engineering still cannot meet the requirements of production and life.
As for the national building waterproof coating, although the development is rapid, the coating still has some defects, such as strict requirement on the cleanness degree of a waterproof base layer, high requirement on a roll coating construction process and difficulty in controlling the thickness; the material has insufficient flexibility, low elongation at break, low tensile strength, low aging resistance and the like, and does not meet the requirements of environmental protection and sustainable development and the like. The method is especially important for vigorously developing the waterproof coating with excellent performance, high flexibility, high durability, environmental protection and environmental friendliness.
Polymer modified water-repellent coatings are a hot spot and trend of research in recent years. In particular, the polymer cement-based waterproof coating integrates the flexibility of a high molecular polymer and the rigidity of cement, overcomes the defects of the high molecular polymer and the cement, has two advantages, and improves the impermeability and the stability of a system. And the method also has the advantages of environmental protection, low comprehensive cost, construction and the like.
Disclosure of Invention
The invention aims to provide a polymer-based waterproof film, a preparation method and application thereof, wherein the waterproof film has the advantages of high flexibility, high elasticity and good aging resistance, and has better tensile strength and water resistance and good adhesion with a base layer.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method of making a polymer-based waterproofing membrane comprising:
s1: adding ascorbic acid and hydrogen peroxide into the chitosan solution, stirring until the ascorbic acid and the hydrogen peroxide are completely dissolved, adding silanediol salicylate, and stirring for reaction to obtain a modified chitosan solution;
s2: mixing the sodium dodecyl sulfate aqueous solution, the modified chitosan solution and the vinyl acetate monomer, and carrying out water bath and stirring until the monomers are fully emulsified; then dropping ammonium persulfate aqueous solution, reacting at constant temperature, and cooling to obtain modified polyvinyl acetate emulsion;
s3: adding water, a defoaming agent, a dispersing agent and a film-forming assistant into the emulsion obtained in the step S2, and uniformly stirring to obtain a liquid material;
s4: uniformly mixing cement, coarse whiting, quartz sand, a water reducing agent and cellulose ether powder to prepare powder;
s5: and (3) gradually adding the powder into the liquid material, stirring until solid particles disappear, then mechanically stirring, breaking bubbles, stirring again, standing, coating and drying to obtain the waterproof film.
The polymer emulsion as the main film forming matter in the waterproof polymer cement paint system determines the basic physical and mechanical performance of the waterproof paint. The chitosan is easy to prepare into a film, and has good adhesion, permeability and certain tensile strength. The antioxidant capacity of the silanediol salicylate and the ascorbic acid modified chitosan is obviously improved, and the anti-aging performance of the waterproof coating film can be improved by absorbing ultraviolet rays. The modified chitosan is used for modifying the vinyl acetate emulsion, and the structure of the modified chitosan is rich in-NH2and-OH is easier to form hydrogen bonds with C ═ O in vinyl acetate, namely the modified chitosan plays a role in crosslinking, and the tensile strength of the waterproof film can be further improved. The modified chitosan is insoluble in water, participates in the reaction to form a copolymer, and hydrogen bonds exist among molecules, so that the system is in a three-dimensional cross-linked network structure, the permeation of water molecules can be effectively inhibited, and the water resistance of the waterproof film is improved. Meanwhile, the adhesion of the chitosan can enable the waterproof coating film to be better attached to the surface of a building, and the construction can be directly carried out on the base surfaces of various materials such as dry or damp, uneven and the like. Compared with the prior artThe tensile strength, the water resistance and the aging resistance of the composite material are greatly improved.
Preferably, in the step S1, the mass ratio of the chitosan to the silanediol salicylate is 1: 0.6-0.8, and the solvent of the chitosan solution is glacial acetic acid solution with the volume fraction of 2-3%. The chitosan and the silanediol salicylate in the mass ratio range can be well subjected to graft copolymerization reaction, and show better oxidation resistance and ultraviolet absorption performance.
Preferably, the content of the modified chitosan in the step S2 is 1.2-1.3% of the total amount of the vinyl acetate monomer. The modified chitosan-silanediol salicylate graft added in the mass ratio has more-NH in the structure2and-OH is easier to form hydrogen bonds with C ═ O in vinyl acetate, namely the modified chitosan plays a role in crosslinking and can improve the tensile strength. The modified chitosan is insoluble in water, and participates in the reaction to form a copolymer, and meanwhile, hydrogen bonds exist among the combined molecules, so that the system is in a stable three-dimensional cross-linked network structure, the permeation of water molecules can be effectively inhibited, and the water resistance of the waterproof coating film is further improved. The modified chitosan has better oxidation resistance and ultraviolet absorption performance, so that the coating film has better aging resistance.
Preferably, the mass ratio of the ascorbic acid to the chitosan in the step S1 is: 0.8-1: 10; the mass fraction of the hydrogen peroxide is 28-30 percent; the reaction temperature is 23-25 ℃, and the reaction time is 23-24 h.
Preferably, the water bath temperature in the step S2 is 65-70 ℃; setting the constant temperature reaction temperature to be 80 ℃, and setting the reaction time to be 7-8 h; the cooling temperature was 50 ℃. The reaction conditions are set to ensure the normal progress of the polymerization reaction.
Preferably, the content of the sodium dodecyl sulfate in the step S2 is 7-9% of the total amount of the vinyl acetate monomer; the content of ammonium persulfate is 0.5-0.7% of the total amount of the vinyl acetate monomer.
Preferably, the liquid material component comprises: 90-95 parts of modified polyvinyl acetate emulsion, 0.5-0.9 part of defoaming agent, 0.6-1 part of dispersing agent, 0.9-1.1 part of film-forming assistant and the balance of water by weight; the powder material comprises the following components: by weight, 28-35 parts of cement, 5-8 parts of nano zirconia, 3-6 parts of N, N dimethylacridine nitrate, 36-40 parts of quartz sand, 0.3-0.5 part of water reducing agent, 0.5-0.7 part of cellulose ether and the balance of 200-400-mesh heavy calcium carbonate; the ratio of liquid to powder is 1-1.2: 1.
Preferably, the nano zirconia powder and the N, N-dimethylacridine nitrate are added into the powder. The nano zirconia and the N, N-dimethylacridine nitrate are added and uniformly dispersed in the polymer as the filler, the polymer has the advantages of small particle size, strong stability, acid resistance, alkali resistance, corrosion resistance and high temperature resistance, the corrosion resistance of the waterproof film can be improved, and the ageing resistance of the waterproof film can be further improved.
Preferably, in the step S5, the mechanical stirring time is 1-2 min, and the foam breaking time is: 1-2 min and standing for 2-3 min. So that the liquid material and the powder material are fully mixed to obtain the waterproof coating.
Preferably, the step S5 is performed in the following manner: forming films in two times vertically and horizontally, wherein the time interval of the two-time coating is 12-14 h. When the film is formed in multiple times, the coating process is favorable for destroying bubbles in the coating, the compactness and uniformity of the coating are ensured, the moisture is increased quickly, and the film forming performance is better; the film is formed in a criss-cross mode, and the tensile strength of the film is higher.
Preferably, the thickness of the waterproof film is 1.3-1.7 mm. The waterproof film within the thickness range has better physical property and mechanical property, and meets the requirement of practical application.
The invention also discloses a polymer-based waterproof film prepared by the preparation method.
The invention also discloses an application of the polymer-based waterproof film in a waterproof coating for a building.
The invention adopts the chitosan modified polyvinyl acetate emulsion with surface modification and the added filler, thereby having the following advantages
Has the advantages that:
the modified chitosan has obviously improved oxidation resistance, can absorb ultraviolet rays, and can improve the aging resistance and the tensile strength of the waterproof film by modifying the vinyl acetate emulsion by utilizing the modified chitosan, effectively inhibit the permeation of water molecules and improve the water resistance of the waterproof film. In addition, the modified chitosan can also enable the waterproof coating film to be better attached to the surface of a building, and the construction can be directly carried out on the base surfaces of various materials such as dry or damp and uneven materials; the addition of the nano material and the N, N-dimethylacridine nitrate enables the waterproof film of the invention to have better corrosion resistance and aging resistance. Compared with the prior art, the waterproof film has the advantages that the tensile strength, the water resistance, the aging resistance and the bonding strength are greatly improved.
Therefore, the invention provides a polymer-based waterproof film, a preparation method and application thereof, and the waterproof film has the advantages of high flexibility, high elasticity and good aging resistance, and has better tensile strength and water resistance and good adhesion with a base layer.
Drawings
FIG. 1 is a graph showing the comparison of tensile strength and elongation at break of comparative example 1, comparative example 2 and the waterproof film of example 1 according to the present invention;
FIG. 2 is a comparison of the bonding strength of the waterproof films of comparative example 1, comparative example 2 and example 1 according to the present invention;
FIG. 3 is a graph showing a comparison between the tensile strength and the rate of decrease in elongation at break of the waterproof film in test example 3 of the present invention;
FIG. 4 is a graph showing the comparison of the rate of decrease in tensile strength of the waterproof film in test example 4 of the present invention;
FIG. 5 is a graph showing the comparison of the reduction rate of elongation at break of the waterproof film in test example 4 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
preparation of a polymer-based waterproofing membrane:
s1: weighing 1g of chitosan, adding the chitosan into 90ml of glacial acetic acid solution with the volume fraction of 3%, fully stirring the mixture by using a stirrer until the chitosan is completely dissolved, then adding 0.1g of ascorbic acid and 0.3ml of hydrogen peroxide with the mass fraction of 30%, stirring the mixture for 30min, and then slowly adding the silanediol salicylate into the mixture by using a dropping funnel so that the mass ratio of the chitosan to the silanediol salicylate is 1: 0.8; and (3) stopping the reaction for 24 hours at the temperature of 25 ℃ under the stirring condition to obtain the modified chitosan solution.
S2: heating in a water bath to a temperature of 70 ℃, following sodium dodecyl sulfate: modified chitosan: adding the lauryl sodium sulfate aqueous solution, the modified chitosan solution obtained from S1 and 30% of vinyl acetate monomer into a three-neck flask according to the mass ratio of the vinyl acetate monomer to be 0.08:0.12:1, stirring for 10min to fully emulsify the monomers, and timely replenishing the residual monomers according to the reflux condition; then dropwise adding an ammonium persulfate aqueous solution (the content of ammonium persulfate is 0.5 percent of the total amount of the vinyl acetate monomer) within 2h, reacting for 6h at the temperature of 80 ℃, and cooling to 50 ℃ to obtain a polymer emulsion;
s3: adding 4 parts of water and then 1 part of dispersing agent into 92 parts of S2 emulsion by weight, and stirring for 5 min; then adding 1 part of film-forming assistant, continuously stirring for 3min, and adding 0.6 part of defoaming agent to obtain a liquid material;
s4: uniformly mixing 45 parts of cement, 25 parts of 400-mesh heavy calcium carbonate, 29 parts of quartz sand, 0.3 part of water reducing agent and 0.7 part of cellulose ether powder material in parts by weight to obtain powder material;
s5: placing the liquid material and the powder material at 23 + -2 deg.C and relative humidity of 50 + -10% for two days, gradually adding the powder material into the liquid material (liquid-powder ratio is 1:1), stirring while adding, mechanically stirring with an egg beater after the solid particles disappear, stirring for 2min, and standing for 3min to break the bubbles; stirring for 2min, and standing for 3 min; then coating to form a film, smearing the film twice longitudinally and transversely, and coating the film twice at an interval of 10 hours to obtain a waterproof film with the thickness of 1.5 mm.
Example 2:
preparing nano zirconium oxide powder:
preparing a zirconium oxychloride solution with the concentration of 2mol/L, dripping ammonia water as a precipitator in a stirring state, controlling the pH to be about 9, filtering and washing after precipitation is finished until chloride ions can not be detected by a washing solution with 0.1mol/L silver nitrate solution, mixing the prepared precursor, namely zirconium hydroxide hydrate and a proper amount of deionized water, placing the mixture in a reaction kettle, heating in a closed manner at the heating speed of 4 ℃/min at the reaction temperature of 150-250 ℃ and the pressure of 0.7-1.3 MPa, keeping the temperature for 3 hours, taking out a product, carrying out solid-liquid separation and drying to obtain nano zirconium oxide powder for later use.
Preparation of a polymer-based waterproofing membrane:
s1: weighing 1g of chitosan, adding the chitosan into 90ml of glacial acetic acid solution with the volume fraction of 3%, fully stirring the mixture by using a stirrer until the chitosan is completely dissolved, then adding 0.1g of ascorbic acid and 0.3ml of hydrogen peroxide with the mass fraction of 30%, stirring the mixture for 30min, and then slowly adding the silanediol salicylate into the mixture by using a dropping funnel so that the mass ratio of the chitosan to the silanediol salicylate is 1: 0.8; and (3) stopping the reaction for 24 hours at the temperature of 25 ℃ under the stirring condition to obtain the modified chitosan solution.
S2: heating in a water bath to a temperature of 70 ℃, following sodium dodecyl sulfate: modified chitosan: adding the lauryl sodium sulfate aqueous solution, the modified chitosan solution obtained from S1 and 30% of vinyl acetate monomer into a three-neck flask according to the mass ratio of the vinyl acetate monomer to be 0.08:0.12:1, stirring for 10min to fully emulsify the monomers, and timely replenishing the residual monomers according to the reflux condition; then dropwise adding an ammonium persulfate aqueous solution (the content of ammonium persulfate is 0.5 percent of the total amount of the vinyl acetate monomer) within 2h, reacting for 6h at the temperature of 80 ℃, and cooling to 50 ℃ to obtain a polymer emulsion;
s3: adding 4 parts of water and then 1 part of dispersing agent into 92 parts of S2 emulsion by weight, and stirring for 5 min; then adding 1 part of film-forming assistant, continuously stirring for 3min, and adding 0.6 part of defoaming agent to obtain a liquid material;
s4: uniformly mixing 35 parts of cement, 6 parts of nano-zirconia, 4 parts of N, N dimethylacridine nitrate, 25 parts of 400-mesh heavy calcium carbonate, 29 parts of quartz sand, 0.3 part of water reducing agent and 0.7 part of cellulose ether powder material in parts by weight to obtain powder material;
s5: placing the liquid material and the powder material at 23 + -2 deg.C and relative humidity of 50 + -10% for two days, gradually adding the powder material into the liquid material (liquid-powder ratio is 1:1), stirring while adding, mechanically stirring with an egg beater after the solid particles disappear, stirring for 2min, and standing for 3min to break the bubbles; stirring for 2min, and standing for 3 min; then coating to form a film, smearing the film twice longitudinally and transversely, and coating the film twice at an interval of 10 hours to obtain a waterproof film with the thickness of 1.5 mm.
Comparative example 1:
preparation of a polymer-based waterproofing membrane:
s1: adding 4 parts of water into 92 parts of polyvinyl acetate emulsion, then adding 1 part of dispersing agent, and stirring for 5 min; then adding 1 part of film-forming assistant, continuously stirring for 3min, and adding 0.6 part of defoaming agent to obtain a liquid material;
s2: uniformly mixing 45 parts of cement, 25 parts of 400-mesh heavy calcium carbonate, 29 parts of quartz sand, 0.3 part of water reducing agent and 0.7 part of cellulose ether powder material in parts by weight to obtain powder material;
s3: placing the liquid material and the powder material at 23 + -2 deg.C and relative humidity of 50 + -10% for two days, gradually adding the powder material into the liquid material (liquid-powder ratio is 1:1), stirring while adding, mechanically stirring with an egg beater after the solid particles disappear, stirring for 2min, and standing for 3min to break the bubbles; stirring for 2min, and standing for 3 min; then coating to form a film, smearing the film twice longitudinally and transversely, and coating the film twice at an interval of 10 hours to obtain a waterproof film with the thickness of 1.5 mm.
Comparative example 2:
s1: dissolving chitosan in 3% acetic acid solution, and stirring to dissolve chitosan; heating in a water bath to a temperature of 70 ℃, following sodium dodecyl sulfate: and (3) chitosan: adding a sodium dodecyl sulfate aqueous solution, a chitosan solution and 30% of vinyl acetate monomer into a three-neck flask, stirring for 10min to fully emulsify the monomers, and timely replenishing the residual monomers according to the reflux condition, wherein the mass ratio of the vinyl acetate monomer is 0.08:0.12: 1; then dropwise adding an ammonium persulfate aqueous solution (the content of ammonium persulfate is 0.5 percent of the total amount of the vinyl acetate monomer) within 2h, reacting for 6h at the temperature of 80 ℃, and cooling to 50 ℃ to obtain a polymer emulsion;
s2: adding 4 parts by weight of water to 92 parts by weight of the emulsion obtained in the step S1, then adding 1 part by weight of a dispersing agent, and stirring for 5 min; then adding 1 part of film-forming assistant, continuously stirring for 3min, and adding 0.6% of defoaming agent to obtain a liquid material;
s3: uniformly mixing 45 parts of cement, 25 parts of 400-mesh heavy calcium carbonate, 29 parts of quartz sand, 0.3 part of water reducing agent and 0.7 part of cellulose ether powder material in parts by weight to obtain powder material;
s4: placing the liquid material and the powder material at 23 + -2 deg.C and relative humidity of 50 + -10% for two days, gradually adding the powder material into the liquid material (liquid-powder ratio is 1:1), stirring while adding, mechanically stirring with an egg beater after the solid particles disappear, stirring for 2min, and standing for 3min to break the bubbles; stirring for 2min, and standing for 3 min; then coating to form a film, coating the film twice longitudinally and transversely, and obtaining a waterproof film with the thickness of 1.5mm when the coating time interval of the two times is 10 hours.
Comparative example 3:
preparation of a polymer-based waterproofing membrane:
s1: weighing 1g of chitosan, adding the chitosan into 90ml of glacial acetic acid solution with the volume fraction of 3%, fully stirring the mixture by using a stirrer until the chitosan is completely dissolved, then adding 0.1g of ascorbic acid and 0.3ml of hydrogen peroxide with the mass fraction of 30%, stirring the mixture for 30min, and then slowly adding the silanediol salicylate into the mixture by using a dropping funnel so that the mass ratio of the chitosan to the silanediol salicylate is 1: 0.8; and (3) stopping the reaction for 24 hours at the temperature of 25 ℃ under the stirring condition to obtain the modified chitosan solution.
S2: heating in a water bath to a temperature of 70 ℃, following sodium dodecyl sulfate: modified chitosan: adding the lauryl sodium sulfate aqueous solution, the modified chitosan solution obtained from S1 and 30% of vinyl acetate monomer into a three-neck flask according to the mass ratio of the vinyl acetate monomer to be 0.08:0.12:1, stirring for 10min to fully emulsify the monomers, and timely replenishing the residual monomers according to the reflux condition; then dropwise adding an ammonium persulfate aqueous solution (the content of ammonium persulfate is 0.5 percent of the total amount of the vinyl acetate monomer) within 2h, reacting for 6h at the temperature of 80 ℃, and cooling to 50 ℃ to obtain a polymer emulsion;
s3: adding 4 parts of water and then 1 part of dispersing agent into 92 parts of S2 emulsion by weight, and stirring for 5 min; then adding 1 part of film-forming assistant, continuously stirring for 3min, and adding 0.6 part of defoaming agent to obtain a liquid material;
s4: uniformly mixing powder materials of 35 parts of cement, 6 parts of nano zirconia, 25 parts of 400-mesh heavy calcium carbonate, 29 parts of quartz sand, 0.3 part of water reducing agent and 0.7 part of cellulose ether in parts by weight to obtain powder;
s5: placing the liquid material and the powder material at 23 + -2 deg.C and relative humidity of 50 + -10% for two days, gradually adding the powder material into the liquid material (liquid-powder ratio is 1:1), stirring while adding, mechanically stirring with an egg beater after the solid particles disappear, stirring for 2min, and standing for 3min to break the bubbles; stirring for 2min, and standing for 3 min; then coating to form a film, smearing the film twice longitudinally and transversely, and coating the film twice at an interval of 10 hours to obtain a waterproof film with the thickness of 1.5 mm.
Comparative example 4:
preparation of a polymer-based waterproofing membrane:
s1: weighing 1g of chitosan, adding the chitosan into 90ml of glacial acetic acid solution with the volume fraction of 3%, fully stirring the mixture by using a stirrer until the chitosan is completely dissolved, then adding 0.1g of ascorbic acid and 0.3ml of hydrogen peroxide with the mass fraction of 30%, stirring the mixture for 30min, and then slowly adding the silanediol salicylate into the mixture by using a dropping funnel so that the mass ratio of the chitosan to the silanediol salicylate is 1: 0.8; and (3) stopping the reaction for 24 hours at the temperature of 25 ℃ under the stirring condition to obtain the modified chitosan solution.
S2: heating in a water bath to a temperature of 70 ℃, following sodium dodecyl sulfate: modified chitosan: adding the lauryl sodium sulfate aqueous solution, the modified chitosan solution obtained from S1 and 30% of vinyl acetate monomer into a three-neck flask according to the mass ratio of the vinyl acetate monomer to be 0.08:0.12:1, stirring for 10min to fully emulsify the monomers, and timely replenishing the residual monomers according to the reflux condition; then dropwise adding an ammonium persulfate aqueous solution (the content of ammonium persulfate is 0.5 percent of the total amount of the vinyl acetate monomer) within 2h, reacting for 6h at the temperature of 80 ℃, and cooling to 50 ℃ to obtain a polymer emulsion;
s3: adding 4 parts of water and then 1 part of dispersing agent into the emulsion of S2 according to the parts by weight, and stirring for 5 min; then adding 1 part of film-forming assistant, continuously stirring for 3min, and adding 0.6 part of defoaming agent to obtain a liquid material;
s4: uniformly mixing 35 parts of cement, 4 parts of N, N dimethylacridine nitrate, 25 parts of 400-mesh heavy calcium carbonate, 29 parts of quartz sand, 0.3 part of water reducing agent and 0.7 part of cellulose ether powder material in parts by weight to obtain powder;
s5: placing the liquid material and the powder material at 23 + -2 deg.C and relative humidity of 50 + -10% for two days, gradually adding the powder material into the liquid material (liquid-powder ratio is 1:1), stirring while adding, mechanically stirring with an egg beater after the solid particles disappear, stirring for 2min, and standing for 3min to break the bubbles; stirring for 2min, and standing for 3 min; then coating to form a film, smearing the film twice longitudinally and transversely, and coating the film twice at an interval of 10 hours to obtain a waterproof film with the thickness of 1.5 mm.
Test example 1:
the waterproof films obtained in examples and comparative examples were cured under standard conditions (temperature 23. + -.2 ℃ C., relative humidity 50. + -.10%) for 96 hours, and released from the mold. The demolded sample was placed with the reverse side up in a 40 ℃ dry box for 48h, removed and placed under standard test conditions for 4 h. Then cut into corresponding test pieces for testing.
1. Tensile Strength test
According to the regulations in the test method for waterproof building coatings GB/T16777- & 2008 and the test method for waterproof polymer cement coatings GB/T23445- & 2009, the coatings are subjected to non-treatment, alkali treatment, heat treatment, water treatment and ultraviolet aging treatment, cut into dumbbell-shaped test pieces and tested, and the tensile strength and the elongation at break of the coatings are recorded.
2. Low temperature flexibility
Coating film samples were prepared and subjected to low temperature flexibility tests as specified in GB/T16777-2008 and GB/T23445-2009. And observing the surface of the test piece by naked eyes to see whether cracks and fractures appear.
3. Adhesive strength
The non-treated, moisture-treated, alkali-treated bond strengths of the coatings were measured as specified in GB/T16777-2008 and GB/T23445-2009.
The bond strength should be calculated as follows:
f＝F/A
wherein f is the tensile bonding strength (MPa) of the polymer cement waterproof coating; f is the load (N) when the test piece is damaged; a is the bonding area (mm)2)。
4. Water impermeability
The water impermeability refers to the ability of the coating film to bear water pressure, and the water impermeability is qualified under a certain water pressure. Samples were prepared as specified and the water permeation of the test pieces was observed. The water permeability of the test piece is generally represented as: the water pressure suddenly drops or the non-upstream surface of the test piece permeates water.
The samples of example 1 were subjected to the above 4 performance tests, and the test results are shown in Table 1. As can be seen from the table, the tensile strength of the waterproof film prepared in example 1 is more than 1.2MPa, which meets the national standard requirement, and is 2.23 times of the national standard value, and the waterproof film has high strength and good coating performance. After alkali treatment, the alkalinity in the system is enhanced, the tensile resistance of the coating is reduced, and the tensile strength and the elongation at break are reduced to different degrees. After heat treatment, the tensile strength and elongation at break of the coating film are reduced. The temperature rise makes the coating film softer, so that the coating film is easy to generate a crosslinking reaction after being heated, and the tensile strength of the coating is reduced; on the other hand, the temperature of the system is increased to accelerate cement hydration, but the emulsion is softened to play a main role, so that the rigidity of the coating film is also reduced. After the soaking treatment, the water absorbed by the coating film plays a role in plasticization. The water absorption swells, and the generated swelling stress destroys the network structure of the polymer so as to reduce the tensile property of the coating film. In addition, the tensile strength and the elongation at break of the polymer still keep good numerical values after ultraviolet aging treatment, and the large benzene ring conjugated structure in the polymer structure can dissipate the excitation energy emitted by ultraviolet light and inhibit and slow down the ultraviolet aging effect. Although the performance of the waterproof coating is reduced to different degrees after various treatments, the waterproof coating meets the requirements of national standards. In addition, the waterproof film prepared in example 1 also has good water impermeability and low-temperature flexibility.
Table 1 test results of various indexes
Test example 2:
the tensile strength and the adhesive strength of the samples of comparative example 1 and comparative example 2 were measured and compared with the corresponding values of example 1, and the results are shown in fig. 1 and 2. FIG. 1 is a comparison of tensile strengths of waterproof films prepared in example 1 and comparative examples 1 and 2, and it can be seen from the comparison that the tensile strength and elongation at break of the waterproof film prepared in example 1 are significantly higher than those of the waterproof films prepared in comparative examples 1 and 2, and the tensile strength and elongation at break of the waterproof film prepared in comparative example 2 are correspondingly higher than those of the waterproof film prepared in comparative example 1, and the experimental results show that the tensile strength of the waterproof film prepared by chitosan-modified polyvinyl acetate emulsion is improved to a certain extent; and then, modifying the chitosan by using silanediol salicylate, and then modifying the polyvinyl acetate emulsion to obtain the waterproof film with higher tensile strength and elongation at break and better mechanical property.
FIG. 2 is a graph showing the comparison of the bonding strength between the waterproof films obtained in example 1 and comparative examples 1 and 2, and it can be seen that the bonding strength of the waterproof film obtained in example 1 is 1.85MPa, which is better than 1.21MPa of comparative example 1, and slightly higher than 1.68MPa of comparative example 2. Experimental results show that the waterproof film prepared from the modified polyvinyl acetate emulsion has better bonding strength and can be well attached to the surface of a substrate.
Test example 3:
aging resistance
Ultraviolet aging test: maintaining the sample for 6 days according to the standard, cooling the sample by a dryer, putting the sample into an ultraviolet accelerated aging test box with the space temperature of (45 +/-2) DEG C, irradiating the sample for 240 hours at constant temperature, taking the sample out, standing the sample for 4 hours under the standard test condition, and testing the change of the mechanical property of the coating after the ultraviolet aging treatment.
The aging resistance test was carried out on comparative examples 2, 3 and 4, and examples 1 and 2, and the mechanical properties were measured after the treatment. The data before and after the aging treatment were processed to calculate the degree of decrease in tensile strength and elongation at break, respectively, and the comparison results are shown in fig. 3. As can be seen from the figure, the decrease degree of the tensile strength and the elongation at break of the waterproof film prepared in example 1 is smaller than that of the waterproof film prepared in comparative example 2, which shows that the waterproof film prepared by modifying chitosan with silanediol salicylate has better ageing resistance. The reduction degree of the tensile strength and the elongation at break of the waterproof film prepared in the embodiment 2 is smaller than those of the waterproof film prepared in the comparative examples 3 and 4, and the effect of simultaneously adding the nano-zirconia and the N, N-dimethylacridine nitrate is better than that of only adding one of the nano-zirconia and the N, N-dimethylacridine nitrate, so that the anti-aging performance of the waterproof film can be better improved.
Test example 4:
acid and alkali resistance:
respectively preparing a 10% sulfuric acid solution as an acid corrosion solution and a 3% NaOH solution (excessive calcium hydroxide) as an alkali corrosion solution. And soaking the sample in the solution, and determining the change of the mechanical property after the corrosion is finished.
The samples of comparative example 3, example 2 and example 1 were subjected to acid and alkali resistance tests, and the tensile strength and elongation at break data of the two samples were processed to obtain corresponding reduction rates, and the comparison results are shown in fig. 4 and 5. As can be seen from the figure, the reduction degree of tensile strength and elongation at break of the waterproof films prepared in comparative example 3 and example 2 is reduced by acid treatment and alkali treatment, but the reduction rate of the waterproof film in example 2 is lower. It is shown that the nano material and the N, N-dimethylacridine nitrate are stably dispersed in the polymer emulsion, and the corrosion resistance and the tensile strength of the waterproof coating film prepared in the embodiment 2 are improved under the combined action.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A method of making a polymer-based waterproofing membrane comprising:
s1: adding ascorbic acid and hydrogen peroxide into the chitosan solution, stirring until the ascorbic acid and the hydrogen peroxide are completely dissolved, adding silanediol salicylate, and stirring for reaction to obtain a modified chitosan solution;
s2: mixing the sodium dodecyl sulfate aqueous solution, the modified chitosan solution and the vinyl acetate monomer, and carrying out water bath and stirring until the monomers are fully emulsified; then dropping ammonium persulfate aqueous solution, reacting at constant temperature, and cooling to obtain modified polyvinyl acetate emulsion;
s3: adding water, a defoaming agent, a dispersing agent and a film-forming assistant into the emulsion obtained in the step S2, and uniformly stirring to obtain a liquid material;
s4: uniformly mixing cement, coarse whiting, quartz sand, a water reducing agent and cellulose ether powder to prepare powder;
s5: and (3) gradually adding the powder into the liquid material, stirring until solid particles disappear, then mechanically stirring, breaking bubbles, stirring again, standing, coating and drying to obtain the waterproof film.
2. The method of preparing a polymer-based waterproofing membrane according to claim 1, wherein: in the step S1, the mass ratio of the chitosan to the silanediol salicylate is 1: 0.6-0.8, and the solvent of the chitosan solution is glacial acetic acid solution with the volume fraction of 2-3%.
3. The method of preparing a polymer-based waterproofing membrane according to claim 1, wherein: the content of the modified chitosan in the step S2 is 1.2-1.3% of the total amount of the vinyl acetate monomer.
4. The method of preparing a polymer-based waterproofing membrane according to claim 1, wherein: the water bath temperature in the step S2 is 65-70 ℃; setting the constant temperature reaction temperature to be 80 ℃, and setting the reaction time to be 7-8 h; the cooling temperature was 50 ℃.
5. The method of preparing a polymer-based waterproofing membrane according to claim 1, wherein: the liquid material comprises the following components: 90-95 parts by weight of modified polyvinyl acetate emulsion, 0.5-0.9 part by weight of defoaming agent, 0.6-1 part by weight of dispersing agent, 0.9-1.1 part by weight of film forming additive and the balance of water; the powder material comprises the following components: 38-45 parts of cement, 36-40 parts of quartz sand, 0.3-0.5 part of water reducing agent, 0.5-0.7 part of cellulose ether and the balance of 200-400 meshes of heavy calcium carbonate in parts by weight; the ratio of liquid to powder is 1-1.2: 1.
6. The method for producing a waterproof film according to claim 1, characterized in that: in the step S5, the mechanical stirring time is 1-2 min, and the foam breaking time is as follows: 1-2 min and standing for 2-3 min.
7. The method of preparing a polymer-based waterproofing membrane according to claim 1, wherein: the coating mode in the step S5 is as follows: forming films in two times vertically and horizontally, wherein the time interval of the two-time coating is 12-14 h.
8. The method of preparing a polymer-based waterproofing membrane according to claim 1, wherein: the thickness of the waterproof film is 1.3-1.7 mm.
9. The polymer-based waterproof film obtained by the production method according to claim 1.
10. Use of the polymer-based waterproofing membrane according to claim 9 in waterproofing coatings for construction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286844A (en) * | 2022-08-22 | 2022-11-04 | 衢州顺天钙业有限公司 | Preparation method of calcium hydroxide/chitosan composite film |
| CN116396578A (en) * | 2023-05-10 | 2023-07-07 | 河北北和包装印刷有限公司 | Zero-waste liquid packaging film |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286844A (en) * | 2022-08-22 | 2022-11-04 | 衢州顺天钙业有限公司 | Preparation method of calcium hydroxide/chitosan composite film |
| CN115286844B (en) * | 2022-08-22 | 2023-10-20 | 衢州顺天钙业有限公司 | Preparation method of calcium hydroxide/chitosan composite film |
| CN116396578A (en) * | 2023-05-10 | 2023-07-07 | 河北北和包装印刷有限公司 | Zero-waste liquid packaging film |
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