CN116102940B - High-crosslinking-degree acrylate film-spraying waterproof material and preparation method thereof - Google Patents
High-crosslinking-degree acrylate film-spraying waterproof material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000005507 spraying Methods 0.000 title claims abstract description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 229920003180 amino resin Polymers 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- 239000002518 antifoaming agent Substances 0.000 claims description 20
- 239000003755 preservative agent Substances 0.000 claims description 20
- 230000002335 preservative effect Effects 0.000 claims description 20
- 239000007921 spray Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000000080 wetting agent Substances 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 239000004640 Melamine resin Substances 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229940080117 triethanolamine sulfate Drugs 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008961 swelling Effects 0.000 abstract description 3
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical class [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 16
- 239000003513 alkali Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 5
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 hydroxyl ions Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D151/08—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 macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/002—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers modified by after-treatment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention relates to the technical field of film spraying waterproof materials, and in particular discloses an acrylate film spraying waterproof material with high crosslinking degree, which is prepared from the following raw materials in parts by weight: 80-120 parts of modified acrylic acid salt aqueous solution, 0.5-2 parts of oxidant, 0.5-2 parts of reducing agent, 20-50 parts of filler and 3-12 parts of auxiliary agent, wherein the modified acrylic acid salt aqueous solution is obtained by modifying water-soluble amino resin hexaacrylamide. The high-crosslinking-degree acrylate film-spraying waterproof material disclosed by the invention has excellent chemical corrosion resistance, does not generate dissolution and swelling in a solution with a wider pH range (pH is 2-13), and keeps the existing high strength and high elongation.
Description
Technical Field
The invention belongs to the technical field of film-spraying waterproof materials, and particularly relates to an acrylate film-spraying waterproof material with high crosslinking degree and a preparation method thereof.
Background
The waterproof material is used as a protective layer in buildings, tunnels and underground engineering to prevent rainwater, snow water, underground water and the like from penetrating, and also to prevent the erosion of moisture, other harmful gases and liquid in the air, and the waterproof means of the tunnels and the underground engineering are mostly to lay and hang a layer of polymer waterproof board between a concrete primary support and a mould injection concrete secondary lining, but the actual waterproof effect is poor, leakage occurs after the use, and the normal use of the tunnels and the safety of the structure are affected. The waterproof technology of the spray film is a novel waterproof technology, and can effectively solve the problem of serious water leakage of tunnels and underground engineering, wherein the waterproof material of the acrylic acid salt spray film is an important novel elastic waterproof material of the spray film, has the advantages of convenient construction, good mechanical property, good bonding effect with a base surface and the like, and is widely applied to various underground engineering waterproofing in recent years.
The acrylate film-spraying waterproof material has some problems in the practical application process, so that the comprehensive popularization and application of the material are limited, for example, when the relative humidity of a construction environment is lower than ninety percent, the brittleness of a waterproof film layer formed by the acrylate film-spraying material at a treated base surface is high, and the waterproof layer is easy to fail due to dry cracking; after a second lining or a concrete protective layer is poured, the contact time between alkaline solution precipitated by concrete and the sprayed film waterproof layer is long, so that the sprayed film layer is easy to swell, and the bonding effect of the sprayed film layer and the protective layer is seriously affected; due to the effects and influences of dissolution of some rock and soil and dissolution of gas, certain chemical components such as ionic chloride ions, sulfate ions, hydroxyl ions and the like exist in underground water to different degrees, and due to the acid-base difference resistance of the sprayed film waterproof layer, the chemical components can have an erosive corrosion effect on the sprayed film waterproof layer, so that the normal use of underground engineering is influenced, the service life of the underground engineering is shortened and the like. At present, the problem of dry cracking of the spray film is improved, but the chemical corrosion resistance of the acrylate spray film is not solved, and the problem of poor acid and alkali resistance is shown that the spray film can be nearly dissolved under an acidic condition and can swell and lose strength under an alkaline condition, so that a waterproof layer is invalid and water leakage is generated, and tunnel safety is seriously affected. The root cause of poor corrosion resistance of the spray film is also that the crosslinking degree of the molecular structure of the spray film is relatively low, the structure is not compact, and active groups in the molecular structure of the spray film are corroded by acid and alkali. Therefore, the improvement of the acid and alkali resistance and the durability of the acrylate film-spraying waterproof material has important significance for promoting the comprehensive application of the acrylate film-spraying waterproof material.
Disclosure of Invention
The invention aims to provide an acrylate film-spraying waterproof material with high crosslinking degree and a preparation method thereof, which are used for improving the acid and alkali resistance of the acrylate film-spraying waterproof material and prolonging the service life of a film.
In order to achieve the aim, the invention provides an acrylate film-spraying waterproof material with high crosslinking degree, which is prepared from the following raw materials in parts by weight: 80-120 parts of modified acrylic acid salt aqueous solution, 0.5-2 parts of oxidant, 0.5-2 parts of reducing agent, 20-50 parts of filler and 3-12 parts of auxiliary agent, wherein the modified acrylic acid salt aqueous solution is obtained by modifying water-soluble amino resin hexaacrylamide.
Preferably, in the high-crosslinking-degree acrylate film-spraying waterproof material, the water-soluble amino resin hexaacrylamide is: 1 part of hexamethoxy methyl melamine resin and 4 to 6 parts of acrylamide are reacted for 6 to 8 hours at a temperature of between 75 and 90 ℃ in the presence of 0.005 to 0.012 parts of catalyst.
Preferably, in the high-crosslinking-degree acrylate film-spraying waterproof material, the water-soluble amino resin hexaacrylamide is: 1 part of hexamethoxy methyl melamine resin and 4-6 parts of acrylamide are reacted for 8 hours at 85 ℃ in the presence of 0.01 part of catalyst, wherein the catalyst is methyl sulfonic acid.
Preferably, in the high-crosslinking-degree acrylate film-spraying waterproof material, the modified acrylate aqueous solution is a modified magnesium acrylate aqueous solution.
Preferably, in the high-crosslinking-degree acrylate film-spraying waterproof material, the oxidant is ammonium persulfate, sodium persulfate or potassium persulfate, and the reducing agent is ferrous sulfate, ferric ammonium sulfate, triethanolamine or sodium thiosulfate.
Preferably, in the high-crosslinking-degree acrylate film-spraying waterproof material, the auxiliary agent comprises an anti-settling agent, a dispersing agent, a wetting agent, a defoaming agent, a preservative and the like, and the filler is one or more of calcium carbonate, fly ash, kaolin and silica micropowder.
The invention also provides a preparation method of the high-crosslinking-degree acrylate film-spraying waterproof material, which comprises the following steps:
(1) Acrylic acid salt synthesis: adding 50-70 parts of water and 20 parts of acrylic acid into a reaction kettle, then adding 5-15 parts of amino resin hexaacrylamide, and then adding 0.01 part of polymerization inhibitor, and stirring and dissolving uniformly; slowly adding 10 parts of magnesia powder, starting a cooling circulating water device when the temperature is raised to 40 ℃, controlling the reaction temperature to be 45-48 ℃ and the reaction time to be 4-5 hours; regulating the pH value to be in the range of 6.0-6.5 to obtain a homogeneous monomolecular modified acrylate aqueous solution;
(2) Mixing the monomolecular modified acrylate solution obtained in the step (1), a filler and an auxiliary agent, performing high-speed dispersion, equally dividing the mixture into A, B parts, and respectively adding a reducing agent and an oxidizing agent into A, B for mixing;
(3) And (3) spraying out the A, B double components by using spraying equipment, wherein all the components in the two components are impacted and mixed in the air to form the elastic spray film waterproof material.
Preferably, in the method for preparing the high-crosslinking-degree acrylate film-spraying waterproof material, in the step (2), the technological parameters of high-speed dispersion are as follows: the stirring speed is 1500-2000 r/min, and the stirring time is 30-60 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the high-crosslinking-degree acrylate film-spraying waterproof material disclosed by the invention has excellent chemical corrosion resistance, does not generate dissolution and swelling in a solution with a wider pH range (pH is 2-13), and keeps the existing high strength and high elongation.
2. According to the high-crosslinking-degree acrylate film spraying waterproof material, the water-soluble amino resin hexaacrylamide is adopted to modify the acrylate, and because the amino resin hexaacrylamide structure contains 4-6 unsaturated bonds, the water-soluble amino resin hexaacrylamide and the acrylate molecules are copolymerized to form a more compact crosslinked three-dimensional network molecular structure during film spraying, the molecular structure is higher in crosslinking, the amino resin macromolecules provide great steric hindrance and shielding effect, and ester bonds and active groups in the acrylate molecular structure can be prevented from being corroded by acid and alkali ions, so that the acrylate film spraying waterproof material has excellent acid and alkali resistance and durability.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments.
Example 1
The high-crosslinking-degree acrylate film-spraying waterproof material comprises the following raw materials in parts by weight: 100 parts of modified magnesium acrylate aqueous solution, 1.5 parts of oxidant, 1.5 parts of reducing agent, 20 parts of heavy calcium carbonate and 11 parts of auxiliary agent. The modified magnesium acrylate aqueous solution is obtained by modifying water-soluble amino resin hexaacrylamide. The oxidant is ammonium persulfate, and the reducing agent is ferrous sulfate. The auxiliary agent consists of 1 part of anti-settling agent, 2 parts of dispersing agent, 3 parts of wetting agent, 4 parts of defoaming agent and 1 part of preservative. The anti-settling agent is fumed silica, the dispersing agent is sodium polyacrylate, the wetting agent is a nonionic surfactant, the defoaming agent is an organosilicon defoaming agent, and the preservative is a benzisothiazolinone preservative.
The water-soluble amino resin hexaacrylamide is: 1 part of hexamethoxymethyl melamine resin and 5 parts of acrylamide are reacted at 85℃for 8 hours in the presence of 0.01 part of catalyst (methanesulfonic acid).
The preparation method of the high-crosslinking-degree acrylate film-spraying waterproof material comprises the following steps:
(1) Adding 50 parts of water and 20 parts of acrylic acid into a reaction kettle, then adding 5 parts of amino resin hexaacrylamide, and then adding 0.01 part of polymerization inhibitor, wherein the polymerization inhibitor is hydroquinone, and stirring and dissolving uniformly; slowly adding 10 parts of magnesium oxide powder, starting a cooling circulating water device when the temperature is increased to 40 ℃, controlling the reaction temperature to 45 ℃, controlling the reaction time to 5 hours, and regulating the pH value to 6.0 to obtain a homogeneous monomolecular modified magnesium acrylate aqueous solution;
(2) Adding the single-molecule modified magnesium acrylate aqueous solution, the anti-settling agent, the dispersing agent, the wetting agent, the defoaming agent and the preservative obtained in the step (1) into a dispersing cylinder, stirring and dissolving, adding heavy calcium carbonate, and dispersing at a high speed of 2000r/min for 30min; after the dispersion was completed, the mixture was equally divided into A, B parts. When spraying, respectively adding the reducing agent and the oxidant into A, B, and uniformly stirring for later use;
(3) The A, B double-component is sprayed by special high-pressure airless spraying equipment, and each component in the two components is impacted and mixed in the air to form the elastic spray film waterproof material.
Example 2
The high-crosslinking-degree acrylate film-spraying waterproof material comprises the following raw materials in parts by weight: 100 parts of modified magnesium acrylate aqueous solution, 1.0 part of oxidant, 1.0 part of reducing agent, 15 parts of heavy calcium carbonate and 8 parts of auxiliary agent. The modified magnesium acrylate aqueous solution is obtained by modifying water-soluble amino resin hexaacrylamide. The auxiliary agent consists of 1 part of anti-settling agent, 1.5 parts of dispersing agent, 2 parts of wetting agent, 3 parts of defoaming agent and 0.5 part of preservative. The oxidant is ammonium persulfate, and the reducing agent is ferrous sulfate. The anti-settling agent is fumed silica, the dispersing agent is sodium polyacrylate, the wetting agent is a nonionic surfactant, the defoaming agent is an organosilicon defoaming agent, and the preservative is a benzisothiazolinone preservative.
The water-soluble amino resin hexaacrylamide is: 1 part of hexamethoxymethyl melamine resin and 5 parts of acrylamide are reacted at 85℃for 8 hours in the presence of 0.01 part of catalyst (methanesulfonic acid).
The preparation method of the high-crosslinking-degree acrylate film-spraying waterproof material comprises the following steps:
(1) Adding 60 parts of water and 20 parts of acrylic acid into a reaction kettle, then adding 10 parts of amino resin hexaacrylamide, and then adding 0.01 part of polymerization inhibitor, wherein the polymerization inhibitor is hydroquinone, and stirring and dissolving uniformly; slowly adding 10 parts of magnesium oxide powder, starting a cooling circulating water device when the temperature is increased to 40 ℃, controlling the reaction temperature to be 45 ℃, reacting for 5 hours, and regulating the pH value to be 6.5 to obtain a homogeneous monomolecular modified magnesium acrylate aqueous solution;
(2) Adding the single-molecule modified magnesium acrylate aqueous solution, the anti-settling agent, the dispersing agent, the wetting agent, the defoaming agent and the preservative obtained in the step (1) into a dispersing cylinder, stirring and dissolving, adding heavy calcium carbonate, and dispersing at a high speed of 2000r/min for 30min; after the dispersion was completed, the mixture was equally divided into A, B parts. When spraying, respectively adding the reducing agent and the oxidant into A, B, and uniformly stirring for later use;
(3) The A, B double-component is sprayed by special high-pressure airless spraying equipment, and each component in the two components is impacted and mixed in the air to form the elastic spray film waterproof material.
Example 3
The high-crosslinking-degree acrylate film-spraying waterproof material comprises the following raw materials in parts by weight: 110 parts of modified magnesium acrylate aqueous solution, 1.5 parts of oxidant, 1.5 parts of reducing agent, 20 parts of heavy calcium carbonate and 10 parts of auxiliary agent; the modified magnesium acrylate aqueous solution is obtained by modifying water-soluble amino resin hexaacrylamide. The oxidant is ammonium persulfate, and the reducing agent is ferrous sulfate. The auxiliary agent consists of 1 part of anti-settling agent, 2 parts of dispersing agent, 2 parts of wetting agent, 4 parts of defoaming agent and 1 part of preservative. The anti-settling agent is fumed silica, the dispersing agent is sodium polyacrylate, the wetting agent is a nonionic surfactant, the defoaming agent is an organosilicon defoaming agent, and the preservative is a benzisothiazolinone preservative.
The preparation method of the high-crosslinking-degree acrylate film-spraying waterproof material comprises the following steps:
(1) 67 parts of water and 20 parts of acrylic acid are added into a reaction kettle, then 15 parts of amino resin hexaacrylamide is added, and then 0.01 part of polymerization inhibitor, namely hydroquinone, is added, and stirring and dissolving are carried out uniformly; slowly adding 10 parts of magnesium oxide powder, and starting a cooling circulating water device when the temperature is raised to 40 ℃, wherein the reaction temperature is controlled to be 45 ℃ and the reaction time is 5 hours. The PH value is regulated to 6.0, thus obtaining homogeneous single-molecule modified magnesium acrylate aqueous solution;
(2) And (3) adding the single-molecule modified acrylate solution, the anti-settling agent, the dispersing agent, the wetting agent, the defoaming agent and the preservative obtained in the step (1) into a dispersing cylinder, stirring and dissolving, and then adding heavy calcium carbonate for high-speed dispersion. After the dispersion is finished, the mixture is equally divided into A, B parts; when spraying, respectively adding the reducing agent and the oxidant into A, B, and uniformly stirring for later use;
(3) The A, B double-component is sprayed by special high-pressure airless spraying equipment, and each component in the two components is impacted and mixed in the air to form the elastic spray film waterproof material.
Comparative example 1
The acrylate film-spraying waterproof material of the comparative example comprises the following raw materials in parts by weight: 100 parts of 40% magnesium acrylate aqueous solution, 1.5 parts of oxidant, 1.5 parts of reducing agent, 20 parts of heavy calcium carbonate and 11 parts of auxiliary agent. The oxidant is ammonium persulfate, and the reducing agent is ferrous sulfate. The auxiliary agent consists of 1 part of anti-settling agent, 2 parts of dispersing agent, 3 parts of wetting agent, 4 parts of defoaming agent and 1 part of preservative. The anti-settling agent is fumed silica, the dispersing agent is sodium polyacrylate, the wetting agent is a nonionic surfactant, the defoaming agent is an organosilicon defoaming agent, and the preservative is a benzisothiazolinone preservative.
The preparation method of the acrylate film-spraying waterproof material of the comparative example comprises the following steps:
(1) Mixing the magnesium acrylate aqueous solution, the heavy calcium carbonate and the auxiliary agent, performing high-speed dispersion, equally dividing into A, B parts, and respectively adding a reducing agent and an oxidizing agent into A, B for mixing;
(3) The A, B double-component is sprayed by special high-pressure airless spraying equipment, and each component in the two components is impacted and mixed in the air to form the elastic spray film waterproof material.
Comparative example 2
The acrylate film-spraying waterproof material of the comparative example comprises the following raw materials in parts by weight: 100 parts of 40% magnesium acrylate aqueous solution, 8 parts of 1, 4-butanediol diacrylate, 1.5 parts of oxidant, 1.5 parts of reducer, 20 parts of heavy calcium carbonate and 11 parts of auxiliary agent. The oxidant is ammonium persulfate, and the reducing agent is ferrous sulfate. The auxiliary agent consists of 1 part of anti-settling agent, 2 parts of dispersing agent, 3 parts of wetting agent, 4 parts of defoaming agent and 1 part of preservative. The anti-settling agent is fumed silica, the dispersing agent is sodium polyacrylate, the wetting agent is a nonionic surfactant, the defoaming agent is an organosilicon defoaming agent, and the preservative is a benzisothiazolinone preservative.
The preparation method of the acrylate film-spraying waterproof material of the comparative example comprises the following steps:
(1) Mixing magnesium acrylate aqueous solution, 1, 4-butanediol diacrylate, heavy calcium carbonate and auxiliary agent, dispersing at high speed, equally dividing into A, B parts, and respectively adding a reducing agent and an oxidizing agent into A, B for mixing;
(3) The A, B double-component is sprayed by special high-pressure airless spraying equipment, and each component in the two components is impacted and mixed in the air to form the elastic spray film waterproof material.
The performance of the acrylate spray film waterproof materials of examples 1 to 3 and comparative examples 1 to 2 was tested according to the test method in GB/T16777-2008 test method for building waterproof paint, and the test results are shown in Table 1.
As can be seen from table 1, the acid resistance and alkali resistance of the acrylate spray film waterproof material of the embodiment of the invention are obviously higher than those of the comparative example, the retention rate of the tensile strength after alkali treatment is more than 90%, the retention rate of the tensile strength after acid treatment is more than 80%, the elongation at break of the acrylate spray film waterproof material of the comparative example is increased after acid treatment or alkali treatment, but the waterproof effect is lost after swelling deformation or near dissolution after acid treatment or alkali treatment; the above description shows that the adoption of the amino resin hexaacrylamide modified acrylate can remarkably improve the corrosion resistance of the acrylate film-spraying waterproof material and improve the applicability of the film-spraying waterproof material.
Table 1 test data for performance of sprayed film waterproof material
| Performance index | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Tensile Strength/MPa | 2.2 | 2.8 | 3.0 | 1.5 | 1.8 |
| Tensile strength retention/%after alkali treatment | 90.3 | 92.5 | 91.6 | 43.6 | 68.7 |
| Tensile strength retention/%after acid treatment | 82.1 | 84.7 | 83.9 | / | 38.4 |
| Elongation at break/% | 305 | 280 | 254 | 315 | 420 |
| Elongation at break/% | 405 | 345 | 285 | 850 | 548 |
| Elongation at break/% | 480 | 403 | 340 | / | 762 |
| Appearance of the coating film after alkali treatment | The coating film is complete | The coating film is complete | The coating film is complete | Deformation of coating film | Deformation of coating film |
| Appearance of the coating film after acid treatment | The coating film is complete | The coating film is complete | The coating film is complete | The coating film is nearly dissolved | Deformation of coating film |
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (6)
1. The high-crosslinking-degree acrylate film-spraying waterproof material is characterized by comprising the following raw materials in parts by weight: 80-120 parts of modified acrylic acid salt aqueous solution, 0.5-2 parts of oxidant, 0.5-2 parts of reducing agent, 20-50 parts of pigment and 3-12 parts of auxiliary agent, wherein the modified acrylic acid salt aqueous solution is obtained by modifying water-soluble amino resin hexaacrylamide;
the water-soluble amino resin hexaacrylamide is as follows: 1 part of hexamethoxy methyl melamine resin and 4 to 6 parts of acrylamide are reacted for 6 to 8 hours at a temperature of between 75 and 90 ℃ in the presence of 0.005 to 0.012 parts of catalyst;
the synthesis method of the modified acrylic acid salt aqueous solution comprises the following steps: adding 50-70 parts of water and 20 parts of acrylic acid into a reaction kettle, then adding 5-15 parts of amino resin hexaacrylamide, and then adding 0.01 part of polymerization inhibitor, and stirring and dissolving uniformly; slowly adding 10 parts of magnesia powder, starting a cooling circulating water device when the temperature is raised to 40 ℃, controlling the reaction temperature to be 45-48 ℃ and the reaction time to be 4-5 hours; and regulating the pH value to be in the range of 6.0-6.5 to obtain the modified acrylic acid salt aqueous solution.
2. The high crosslinking degree acrylate film-spraying waterproof material according to claim 1, wherein the water-soluble amino resin hexaacrylamide is: 1 part of hexamethoxy methyl melamine resin and 4 to 6 parts of acrylamide are reacted for 8 hours at 85 ℃ in the presence of 0.01 part of catalyst, wherein the catalyst is methyl sulfonic acid.
3. The high-crosslinking-degree acrylate film-spraying waterproof material according to claim 1, wherein the oxidant is ammonium persulfate, sodium persulfate or potassium persulfate, and the reducing agent is ferrous sulfate, ferric ammonium sulfate, triethanolamine or sodium thiosulfate.
4. The high-crosslinking-degree acrylate film-spraying waterproof material according to claim 1, wherein the auxiliary agent comprises an anti-settling agent, a dispersing agent, a wetting agent, a defoaming agent and a preservative, and the pigment is one or more of calcium carbonate, fly ash, kaolin and silica micropowder.
5. The method for preparing the high-crosslinking-degree acrylate film-spraying waterproof material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Acrylic acid salt synthesis: adding 50-70 parts of water and 20 parts of acrylic acid into a reaction kettle, then adding 5-15 parts of amino resin hexaacrylamide, and then adding 0.01 part of polymerization inhibitor, and stirring and dissolving uniformly; slowly adding 10 parts of magnesia powder, starting a cooling circulating water device when the temperature is raised to 40 ℃, controlling the reaction temperature to be 45-48 ℃ and the reaction time to be 4-5 hours; regulating the pH value to be in the range of 6.0-6.5 to obtain a homogeneous single-molecule modified acrylic acid salt aqueous solution;
(2) Mixing the monomolecular modified acrylate solution obtained in the step (1), a filler and an auxiliary agent, performing high-speed dispersion, equally dividing the mixture into A, B parts, and respectively adding a reducing agent and an oxidizing agent into A, B for mixing;
(3) And (3) spraying out the A, B double components by using spraying equipment, wherein all the components in the two components are impacted and mixed in the air to form the elastic spray film waterproof material.
6. The method for preparing a high crosslinking degree acrylate film-spraying waterproof material according to claim 5, wherein in the step (2), the technological parameters of high-speed dispersion are as follows: the stirring speed is 1500-2000 r/min, and the stirring time is 30-60 min.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145662A (en) * | 1988-11-28 | 1990-06-05 | Toagosei Chem Ind Co Ltd | Composition for water-proofing flame-retardant coating film |
| JP2004115678A (en) * | 2002-09-26 | 2004-04-15 | Sk Kaken Co Ltd | Aqueous undercoat composition |
| CN104159865A (en) * | 2012-03-09 | 2014-11-19 | 帕雷克斯集团有限公司 | Use of at least one superabsorbent polymer (psa) (b), in a dry composition based on a mineral binder and used for preparing a hardenable moist formulation for the building industry |
| KR101512966B1 (en) * | 2014-11-13 | 2015-04-21 | (주)코메스코리아 | Elastomeric Mortar Composition and Constructing Methods Using Thereof |
| CN106497180A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of water-repellent paint of high viscosity environment-friendly type |
| CN107118650A (en) * | 2017-05-19 | 2017-09-01 | 华南理工大学 | Ludox/hydroxyl polyacrylate dispersion amino plastic baking varnish and preparation method thereof |
| CN108178940A (en) * | 2017-12-29 | 2018-06-19 | 北京东方雨虹防水技术股份有限公司 | High-performance acrylic acid salt spray film water-proofing material and preparation method thereof |
| CN108587266A (en) * | 2017-12-29 | 2018-09-28 | 北京东方雨虹防水技术股份有限公司 | Modified propylene hydrochlorate spray film water-proofing material and preparation method thereof |
| CN110317512A (en) * | 2019-06-14 | 2019-10-11 | 北京东方雨虹防水技术股份有限公司 | A kind of Tunnel Engineering spray film water-proofing material and preparation method thereof |
| CN110483708A (en) * | 2019-08-12 | 2019-11-22 | 北京东方雨虹防水技术股份有限公司 | A kind of underground engineering macromolecule spray film water-proofing material and preparation method thereof |
| CN112063257A (en) * | 2020-09-03 | 2020-12-11 | 广西青龙化学建材有限公司 | Durable water-based non-cured modified asphalt waterproof coating and preparation method thereof |
| CN113088112A (en) * | 2021-03-01 | 2021-07-09 | 上海无忧树新材料科技有限公司 | Acrylate spray film waterproof material with double-network structure |
| CN114163906A (en) * | 2021-12-30 | 2022-03-11 | 广西青龙化学建材有限公司 | Novel acrylate waterproof coating for toilet floor and preparation method thereof |
| CN115368795A (en) * | 2022-10-24 | 2022-11-22 | 江苏新历科技有限公司 | Water-based high-solid amino baking paint and preparation method thereof |
-
2022
- 2022-12-31 CN CN202211727610.2A patent/CN116102940B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145662A (en) * | 1988-11-28 | 1990-06-05 | Toagosei Chem Ind Co Ltd | Composition for water-proofing flame-retardant coating film |
| JP2004115678A (en) * | 2002-09-26 | 2004-04-15 | Sk Kaken Co Ltd | Aqueous undercoat composition |
| CN104159865A (en) * | 2012-03-09 | 2014-11-19 | 帕雷克斯集团有限公司 | Use of at least one superabsorbent polymer (psa) (b), in a dry composition based on a mineral binder and used for preparing a hardenable moist formulation for the building industry |
| KR101512966B1 (en) * | 2014-11-13 | 2015-04-21 | (주)코메스코리아 | Elastomeric Mortar Composition and Constructing Methods Using Thereof |
| CN106497180A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of water-repellent paint of high viscosity environment-friendly type |
| CN107118650A (en) * | 2017-05-19 | 2017-09-01 | 华南理工大学 | Ludox/hydroxyl polyacrylate dispersion amino plastic baking varnish and preparation method thereof |
| CN108178940A (en) * | 2017-12-29 | 2018-06-19 | 北京东方雨虹防水技术股份有限公司 | High-performance acrylic acid salt spray film water-proofing material and preparation method thereof |
| CN108587266A (en) * | 2017-12-29 | 2018-09-28 | 北京东方雨虹防水技术股份有限公司 | Modified propylene hydrochlorate spray film water-proofing material and preparation method thereof |
| CN110317512A (en) * | 2019-06-14 | 2019-10-11 | 北京东方雨虹防水技术股份有限公司 | A kind of Tunnel Engineering spray film water-proofing material and preparation method thereof |
| CN110483708A (en) * | 2019-08-12 | 2019-11-22 | 北京东方雨虹防水技术股份有限公司 | A kind of underground engineering macromolecule spray film water-proofing material and preparation method thereof |
| CN112063257A (en) * | 2020-09-03 | 2020-12-11 | 广西青龙化学建材有限公司 | Durable water-based non-cured modified asphalt waterproof coating and preparation method thereof |
| CN113088112A (en) * | 2021-03-01 | 2021-07-09 | 上海无忧树新材料科技有限公司 | Acrylate spray film waterproof material with double-network structure |
| CN114163906A (en) * | 2021-12-30 | 2022-03-11 | 广西青龙化学建材有限公司 | Novel acrylate waterproof coating for toilet floor and preparation method thereof |
| CN115368795A (en) * | 2022-10-24 | 2022-11-22 | 江苏新历科技有限公司 | Water-based high-solid amino baking paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CW520丙烯酸盐灌浆材料交联剂合成及其浆液性能研究;张健等;《长江科学院院报》;第29卷(第02期);第55-59页 * |
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