CN116082912B - Vapor-permeable waterproof coating - Google Patents
Vapor-permeable waterproof coating Download PDFInfo
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- CN116082912B CN116082912B CN202211626136.4A CN202211626136A CN116082912B CN 116082912 B CN116082912 B CN 116082912B CN 202211626136 A CN202211626136 A CN 202211626136A CN 116082912 B CN116082912 B CN 116082912B
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- water
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- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000839 emulsion Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 82
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 54
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 22
- 239000002562 thickening agent Substances 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 19
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 19
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000000872 buffer Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000013530 defoamer Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- -1 ethoxylated alkyl sodium sulfate Chemical compound 0.000 claims description 3
- 239000008055 phosphate buffer solution Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000007974 sodium acetate buffer Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000001038 titanium pigment Substances 0.000 claims description 2
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009413 insulation Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000008363 phosphate buffer Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000009456 molecular mechanism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- C09D151/08—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
- C09D151/085—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 on to polysiloxanes
-
- 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
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a vapor-permeable waterproof coating, which relates to the technical field of coatings, and develops a special emulsion with steric hindrance and gas conduction effect by designing and synthesizing a new emulsion; the water-proof and vapor-permeable coating capable of preventing liquid water from permeating gaseous water is realized by matching emulsion with inorganic filler, the blank of the product in domestic market is filled, and the water-proof and vapor-permeable coating is finally applied to an external heat-insulating and waterproof system of a building external wall, thereby providing an effective scheme for the energy-saving effect and long-term durability of the external heat insulation of the external wall.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a breathable waterproof coating.
Background
Humidity is a key factor affecting durability, stability and health of an outer wall structure of a building, and the design of the outer wall of the building in China mainly focuses on decoration, heat preservation and other aspects at present, but omits the water resistance of an outer wall heat preservation system; when the humidity in the wall body is higher, the heat conductivity coefficient of the heat insulation material is higher, and the heat insulation effect is poorer, so that the heat insulation energy-saving effect and long-term durability are affected; in the existing domestic standards, the water vapor transmission rate (wet flow density) is not specified in the polymer emulsion building waterproof coating standard. At present, no corresponding product standard exists in China, and foreign materials are defined to be completely permeable, wherein the effective permeability is more than or equal to 10 permas (which is equivalent to that the domestic wet flow density is more than or equal to 5.21 g/(m) 2 h) The outer wall steam-permeable material is designed, and engineering practice and verification are carried out in foreign civil houses; at present, the national air permeability standard for the outer wall is more than or equal to 0.85 g/(m) 2 h) Far below foreign levels and lacks engineering verification. Therefore, waterproof and vapor-permeable paint has been desired.
At present, the water-proof paint which is commercially available at home and takes acrylic ester as a main material and is prepared from acrylic acid as a single component or polymer cement water-proof paint (JS) as a main material cannot meet the requirement of meeting the real water vapor transmission capacity of an external wall external heat insulation system, so that the water vapor transmission capacity of the water-proof paint is required to be redesigned from the molecular structure of emulsion (colloid) fundamentally, and meanwhile, the water vapor transmission capacity is endowed and meanwhile, the water-proof (liquid water-proof) and other capacities are balanced.
According to studies, the mechanism by which water vapor can permeate through polymers is divided into two types: 1. absorption and release of moisture: water is a polar molecule, and the polarity of a material, such as a polymer, through which polar molecules are carried is a major cause of strong interactions between water vapor molecules and polymer groups. Therefore, the high molecular material containing more polar groups such as-COO-, -CO-NH-and-OH has strong water absorption, absorbs water vapor, and then releases water under the action of temperature difference and humidity difference to form a vapor permeation function. However, this method causes high water absorption and swelling of the polymer, affecting adhesion to interfaces and other application properties; 2. hydrophobic micro-domain channel conduction: through the micro-nano hydrophobic pore structure in the polymer, the migration of water molecules can be effectively and rapidly conducted, the low water absorption capacity and the volume expansion of the polymer are ensured, and the bonding with an interface and other application performances are not influenced. Therefore, the acrylate emulsion can be modified appropriately, and a molecular mechanism capable of providing effective hydrophobic micro-areas is added to form the acrylate emulsion with steric hindrance and a vapor conduction channel, so that the water absorption rate and the volume expansion rate of the emulsion are not increased.
POSS is an inorganic core composed of Si-O alternately connected silica frameworks, and the shape of the POSS is similar to that of a cage, so that the POSS is named as cage polysilsesquioxane, the three-dimensional size of the POSS is between 1.3nm and three times that of water molecules (0.4 nm), the distance between Si atoms is 0.5nm, and the distance between R groups is 1.5nm; the use of POSS in polymers is largely dependent on the variation of the R groups, which may be reactive groups such as alkenyl groups, epoxy groups, amino groups, etc., which may be grafted or polymerized with the polymer to create chemical bonding between the polymers.
The cage type frame structure of the cage type frame POSS makes the cage type frame structure have good dielectric property and optical property to pay attention to, and inorganic cores formed by the silica frameworks alternately connected with the inorganic cores Si-O can inhibit chain movement of polymer molecules so as to endow the hybrid material with good thermal stability, mechanical property, flame retardance and the like. However, modification grafting of cage polysilsesquioxane onto acrylate, using steric hindrance to form microscopic water vapor channels, has not been studied, resulting in good water vapor transmission capacity of acrylic acid.
Disclosure of Invention
The invention provides a vapor-permeable waterproof coating with excellent waterproof and vapor-permeable capabilities, aiming at the problems existing in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a waterproof coating, which comprises the following raw materials: acrylic emulsion, powder and auxiliary agent;
the raw materials of the acrylic emulsion comprise: n-butyl acrylate, methacrylic acid, ethyl acrylate, methyl methacrylate, styrene, acrylic acid, divinylbenzene, acrylic acid-based cage polysilsesquioxane, 1, 4-butanediol diacrylate, initiator, buffer, and surfactant.
Further, the raw materials of the acrylic emulsion comprise, by weight: 2-4 parts of n-butyl acrylate, 0.5-2 parts of methacrylic acid, 0.01-0.04 part of divinylbenzene, 0.01-0.05 part of acrylic group-cage polysilsesquioxane, 10-20 parts of ethyl acrylate, 0.5-2.5 parts of methyl methacrylate, 10-15 parts of styrene, 0.2-1.0 part of acrylic acid, 0.2-0.8 part of 1, 4-butanediol diacrylate, 0.01-0.04 part of initiator, 0.01-0.08 part of buffer solution, 0.1-0.5 part of surfactant and 50-70 parts of water.
Preferably, the raw materials of the acrylic emulsion comprise, by weight: 3 parts of n-butyl acrylate, 1 part of methacrylic acid, 0.02 part of divinylbenzene, 0.02 part of acrylic group-cage polysilsesquioxane, 14 parts of ethyl acrylate, 1 part of methyl methacrylate, 12 parts of styrene, 1 part of acrylic acid, 0.5 part of 1, 4-butanediol diacrylate, 0.03 part of an initiator, 0.03 part of a buffer, 0.4 part of a surfactant and 67 parts of water.
Further, the waterproof coating comprises the following raw materials in parts by weight: 25-45 parts of acrylic emulsion, 30-50 parts of powder, 1-5 parts of auxiliary agent and 10-20 parts of water.
Preferably, the waterproof paint comprises the following raw materials in parts by weight: 40 parts of acrylic emulsion, 40 parts of powder, 5 parts of auxiliary agent and 15 parts of water.
Further, the initiator comprises one or more of ammonium persulfate, potassium sulfate, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide; ammonium persulfate is preferred.
Further, the buffer solution comprises one or more of sodium acetate buffer solution, boric acid buffer solution and phosphate buffer solution; dipotassium hydrogen phosphate buffer is preferred.
Further, the surfactant comprises one or more of sodium dodecyl benzene sulfonate, ethoxylated sulfated sodium alkyl sulfate and ammonium dodecyl sulfate; ammonium lauryl sulfate is preferred.
Further, the weight ratio of divinylbenzene to acrylic-cage polysilsesquioxane is (3-6): (4-7); preferably 1:1.
Further, the auxiliary agent comprises: one or more of defoamer, preservative, dispersant, buffer, titanium pigment and thickener.
Preferably, the auxiliary agents include defoamers, dispersants, and thickeners.
Further, the powder comprises one or more of ground calcium carbonate, barium sulfate and quartz powder.
Preferably, the heavy calcium carbonate is 400-1600 meshes of heavy calcium carbonate, and the barium sulfate is 400-1600 meshes of barium sulfate.
Further, the invention also provides a preparation method of the waterproof paint, which comprises the following steps:
(1) Kernel synthesis: mixing n-butyl acrylate, methacrylic acid, divinylbenzene and acrylic acid group-cage polysilsesquioxane to obtain a comonomer mixture, adding the comonomer mixture into water containing a surfactant, a buffer solution and an initiator, and stirring to obtain seed dispersion;
(2) And (3) shell synthesis: mixing ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate, adding the mixture into the seed dispersion liquid obtained in the step (1), and dialyzing to remove redundant monomers to obtain an acrylic emulsion;
(3) Mixing the acrylic emulsion, the auxiliary agent and the powder, and uniformly stirring to obtain the acrylic emulsion.
In some specific embodiments, the method for preparing the waterproof coating comprises the following steps:
(1) Kernel synthesis: first, a mixed comonomer solution containing n-butyl acrylate, methacrylic acid, divinylbenzene and methylpropenyl-cage polysilsesquioxane was prepared, and a part of the comonomer mixture was added to water containing a surfactant, a buffer and an initiator for seed formation. Mechanically stirring at 80 ℃ under nitrogen atmosphere for 40 minutes to form seed dispersion;
(2) And (3) shell synthesis: a comonomer solution containing ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate was added to the seed dispersion uniformly by pump at a rate of 1.0 g/min. After the completion of the feed, the temperature was maintained at 80℃for another 2.5 hours. Finally, the product is dialyzed in water for 7 days to remove redundant monomers, so as to obtain acrylic emulsion;
(3) Adding water into the beaker, respectively adding acrylic emulsion, defoamer, preservative, dispersing agent and buffer into the beaker under stirring, adding titanium dioxide and powder after stirring uniformly, and accelerating the stirring speed until the powder is uniform into slurry. Reducing the stirring speed, and sequentially adding the thickening agents and stirring uniformly.
The invention has the technical effects that:
according to the invention, the acrylic emulsion modified by cage Polysilsesquioxane (POSS) is designed and synthesized for the first time, and the emulsion with different porosities and different water vapor throughputs is obtained by controlling the proportion of the POSS in a colloid inner core structure and a cross-linking agent; the waterproof paint with waterproof and vapor-permeable capacity is formed by physical combination with conventional powder and auxiliary agents.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is to be noted that the acrylic group-cage polysilsesquioxane used in the present invention is purchased from Shanghai microphone Biochemical technology Co., ltd. Model A909178, and the remaining raw materials are all common commercial products, so that the sources thereof are not particularly limited.
In addition, BYK-022 used in the present invention is specifically a Pick BYK-022 silicone defoamer, NOPCO-NXZ is specifically a NoPCO-NXZ defoamer of the Nortaceae family, 165A is specifically a Dow 165A dispersant, 1850E is specifically a Dow 1850E dispersant, ASE-60 is specifically a Rogowski ASE-60 thickener, and U505 is specifically a Wanhua chemistry U505 thickener.
Example 1
The waterproof coating comprises the following raw materials in parts by weight: 25 parts of acrylic emulsion, 30 parts of powder (specifically 21 parts of heavy calcium carbonate, 3 parts of barium sulfate and 6 parts of quartz powder), 1 part of auxiliary agent (specifically defoamer 0.36 parts of BYK-022 and 0.4 part of NOPCO-NXZ), dispersant (0.1 part of 165A and 0.1 part of 1850E), thickener (0.02 part of ASE-60 and 0.02 part of U505) and 10 parts of water.
Wherein, the raw materials of the acrylic emulsion comprise the following components in parts by weight: 2 parts of n-butyl acrylate, 0.5 part of methacrylic acid, 0.01 part of divinylbenzene, 0.01 part of acrylic acid group-cage polysilsesquioxane, 10 parts of ethyl acrylate, 0.5 part of methyl methacrylate, 10 parts of styrene, 0.2 part of acrylic acid, 0.2 part of 1, 4-butanediol diacrylate, 0.01 part of an initiator (specifically ammonium persulfate), 0.01 part of a buffer (specifically dipotassium hydrogen phosphate buffer), 0.1 part of a surfactant (specifically ammonium dodecyl sulfate) and 50 parts of deionized water.
The preparation method of the paint comprises the following steps:
(1) Kernel synthesis: mixing n-butyl acrylate, methacrylic acid, divinylbenzene and acrylic acid group-cage polysilsesquioxane to obtain a comonomer mixture, adding the comonomer mixture into water containing a surfactant, a buffer solution and an initiator, stirring, and mechanically stirring for 40 minutes at 80 ℃ under a nitrogen atmosphere to obtain a seed dispersion;
(2) And (3) shell synthesis: ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate were mixed and then added uniformly to the seed dispersion obtained in step (1) by a pump at a rate of 1.0 g/min. After the feeding is completed, the temperature is kept at 80 ℃ for 2.5 hours, and finally, the product is dialyzed in water for 7 days to remove redundant monomers, so as to obtain acrylic emulsion;
(3) Adding water into the beaker, adding acrylic emulsion and auxiliary agent respectively under stirring, adding titanium white powder and powder after stirring uniformly, and accelerating the stirring speed until the powder is uniform into slurry. Reducing the stirring speed, and sequentially adding the thickening agents and stirring uniformly.
Example 2
The waterproof coating comprises the following raw materials in parts by weight: 45 parts of acrylic emulsion, 50 parts of powder (specifically 35 parts of heavy calcium carbonate, 5 parts of barium sulfate and 10 parts of quartz powder), 5 parts of auxiliary agent (specifically 1.8 parts of defoamer BYK-022 and 2 parts of NOPCO-NXZ), dispersing agent (0.5 part of 165A and 0.5 part of 1850E), thickening agent (0.1 part of ASE-60 and 0.1 part of U505) and 20 parts of water.
Wherein, the raw materials of the acrylic emulsion comprise the following components in parts by weight: 4 parts of n-butyl acrylate, 2 parts of methacrylic acid, 0.04 part of divinylbenzene, 0.05 part of acrylic acid-cage polysilsesquioxane, 20 parts of ethyl acrylate, 2.5 parts of methyl methacrylate, 15 parts of styrene, 1.0 part of acrylic acid, 0.8 part of 1, 4-butanediol diacrylate, 0.04 part of an initiator (particularly ammonium persulfate), 0.08 part of a buffer (particularly dipotassium hydrogen phosphate buffer), 0.5 part of a surfactant (particularly ammonium dodecyl sulfate) and 70 parts of deionized water.
The preparation method of the paint comprises the following steps:
(1) Kernel synthesis: mixing n-butyl acrylate, methacrylic acid, divinylbenzene and acrylic acid group-cage polysilsesquioxane to obtain a comonomer mixture, adding the comonomer mixture into water containing a surfactant, a buffer solution and an initiator, stirring, and mechanically stirring for 40 minutes at 80 ℃ under a nitrogen atmosphere to obtain a seed dispersion;
(2) And (3) shell synthesis: ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate were mixed and then added uniformly to the seed dispersion obtained in step (1) by a pump at a rate of 1.0 g/min. After the feeding is completed, the temperature is kept at 80 ℃ for 2.5 hours, and finally, the product is dialyzed in water for 7 days to remove redundant monomers, so as to obtain acrylic emulsion;
(3) Adding water into the beaker, adding acrylic emulsion and auxiliary agent respectively under stirring, adding titanium white powder and powder after stirring uniformly, and accelerating the stirring speed until the powder is uniform into slurry. Reducing the stirring speed, and sequentially adding the thickening agents and stirring uniformly.
Example 3
The waterproof coating comprises the following raw materials in parts by weight: 40 parts of acrylic emulsion, 40 parts of powder (specifically 28 parts of heavy calcium carbonate, 4 parts of barium sulfate and 8 parts of quartz powder), 5 parts of auxiliary agent (specifically 1.8 parts of defoamer BYK-022 and 2 parts of NOPCO-NXZ), dispersing agent (0.5 part of 165A and 0.5 part of 1850E), thickening agent (0.1 part of ASE-60 and 0.1 part of thickening agent U505) and 15 parts of water.
Wherein, the raw materials of the acrylic emulsion comprise the following components in parts by weight: 3 parts of n-butyl acrylate, 1 part of methacrylic acid, 0.02 part of divinylbenzene, 0.02 part of acrylic acid-cage polysilsesquioxane, 14 parts of ethyl acrylate, 1 part of methyl methacrylate, 12 parts of styrene, 1 part of acrylic acid, 0.5 part of 1, 4-butanediol diacrylate, 0.03 part of an initiator (particularly ammonium persulfate), 0.03 part of a buffer (particularly dipotassium hydrogen phosphate buffer), 0.4 part of a surfactant (particularly ammonium lauryl sulfate) and 67 parts of deionized water.
The preparation method of the paint comprises the following steps:
(1) Kernel synthesis: mixing n-butyl acrylate, methacrylic acid, divinylbenzene and acrylic acid group-cage polysilsesquioxane to obtain a comonomer mixture, adding the comonomer mixture into water containing a surfactant, a buffer solution and an initiator, stirring, and mechanically stirring for 40 minutes at 80 ℃ under a nitrogen atmosphere to obtain a seed dispersion;
(2) And (3) shell synthesis: ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate were mixed and then added uniformly to the seed dispersion obtained in step (1) by a pump at a rate of 1.0 g/min. After the feeding is completed, the temperature is kept at 80 ℃ for 2.5 hours, and finally, the product is dialyzed in water for 7 days to remove redundant monomers, so as to obtain acrylic emulsion;
(3) Adding water into the beaker, adding acrylic emulsion and auxiliary agent respectively under stirring, adding titanium white powder and powder after stirring uniformly, and accelerating the stirring speed until the powder is uniform into slurry. Reducing the stirring speed, and sequentially adding the thickening agents and stirring uniformly.
Comparative example 1
The only difference from example 1 is that divinylbenzene is replaced by equivalent amounts of acrylic-cage polysilsesquioxane, i.e. the weight ratio of divinylbenzene to acrylic-cage polysilsesquioxane is 100:0, in particular: the waterproof coating comprises the following raw materials in parts by weight: 25 parts of acrylic emulsion, 30 parts of powder (specifically 21 parts of heavy calcium carbonate, 3 parts of barium sulfate and 6 parts of quartz powder), 1 part of auxiliary agent (specifically defoamer 0.36 parts of BYK-022 and 0.4 part of NOPCO-NXZ), dispersant (0.1 part of 165A and 0.1 part of 1850E), thickener (0.02 part of ASE-60 and 0.02 part of thickener U505) and 10 parts of water.
Wherein, the raw materials of the acrylic emulsion comprise the following components in parts by weight: 2 parts of n-butyl acrylate, 0.5 part of methacrylic acid, 0.02 part of divinylbenzene, 10 parts of ethyl acrylate, 0.5 part of methyl methacrylate, 10 parts of styrene, 0.2 part of acrylic acid, 0.2 part of 1, 4-butanediol diacrylate, 0.01 part of an initiator (particularly ammonium persulfate), 0.01 part of a buffer (particularly dipotassium hydrogen phosphate buffer), 0.1 part of a surfactant (particularly ammonium dodecyl sulfate) and 50 parts of deionized water.
The preparation was carried out in the same manner as in example 1 (without the addition of acrylic-cage polysilsesquioxane).
Comparative example 2
The only difference from example 1 is that the acrylic-cage polysilsesquioxane is replaced by an equivalent amount of divinylbenzene, i.e. a weight ratio of divinylbenzene to acrylic-cage polysilsesquioxane of 0:100 is: the waterproof coating comprises the following raw materials in parts by weight: 25 parts of acrylic emulsion, 30 parts of powder (specifically 21 parts of heavy calcium carbonate, 3 parts of barium sulfate and 6 parts of quartz powder), 1 part of auxiliary agent (specifically defoamer 0.36 parts of BYK-022 and 0.4 part of NOPCO-NXZ), dispersant (0.1 part of 165A and 0.1 part of 1850E), thickener (0.02 part of ASE-60 and 0.02 part of thickener U505) and 10 parts of water.
Wherein, the raw materials of the acrylic emulsion comprise the following components in parts by weight: 2 parts of n-butyl acrylate, 0.5 part of methacrylic acid, 0.02 part of acrylic acid-cage polysilsesquioxane, 10 parts of ethyl acrylate, 0.5 part of methyl methacrylate, 10 parts of styrene, 0.2 part of acrylic acid, 0.2 part of 1, 4-butanediol diacrylate, 0.01 part of an initiator (particularly ammonium persulfate), 0.01 part of a buffer (particularly dipotassium hydrogen phosphate buffer), 0.1 part of a surfactant (particularly ammonium lauryl sulfate) and 50 parts of deionized water.
The preparation was carried out in the same manner as in example 1 (without divinylbenzene).
This comparative example failed to produce stable emulsion colloidal particles and therefore, no subsequent testing of water vapor transmission rate and water repellency was performed.
Comparative example 3
The only difference from example 1 is that the weight ratio of divinylbenzene to acrylic-based cage polysilsesquioxane is 2:8 (the total weight of both corresponds to example 1). The method comprises the following steps: the waterproof coating comprises the following raw materials in parts by weight: 25 parts of acrylic emulsion, 30 parts of powder (specifically 21 parts of heavy calcium carbonate, 3 parts of barium sulfate and 6 parts of quartz powder), 1 part of auxiliary agent (specifically defoamer 0.36 parts of BYK-022 and 0.4 part of NOPCO-NXZ), dispersant (0.1 part of 165A and 0.1 part of 1850E), thickener (0.02 part of ASE-60 and 0.02 part of thickener U505) and 10 parts of water.
Wherein, the raw materials of the acrylic emulsion comprise the following components in parts by weight: 2 parts of n-butyl acrylate, 0.5 part of methacrylic acid, 0.004 part of divinylbenzene, 0.016 part of acrylic group-cage polysilsesquioxane, 10 parts of ethyl acrylate, 0.5 part of methyl methacrylate, 10 parts of styrene, 0.2 part of acrylic acid, 0.2 part of 1, 4-butanediol diacrylate, 0.01 part of an initiator (specifically ammonium persulfate), 0.01 part of a buffer (specifically dipotassium hydrogen phosphate buffer), 0.1 part of a surfactant (specifically ammonium dodecyl sulfate) and 50 parts of deionized water.
The preparation method is the same as in example 1.
Comparative example 4
The only difference from example 1 is that the emulsion was used to prepare a water-resistant coating by selecting a conventional acrylic emulsion, specifically: the waterproof coating comprises the following raw materials in parts by weight: 25 parts of acrylic emulsion, 30 parts of powder (specifically 21 parts of heavy calcium carbonate, 3 parts of barium sulfate and 6 parts of quartz powder), 1 part of auxiliary agent (specifically defoamer 0.36 parts of BYK-022 and 0.4 part of NOPCO-NXZ), dispersant (0.1 part of 165A and 0.1 part of 1850E), thickener (0.02 part of ASE-60 and 0.02 part of thickener U505) and 10 parts of water.
The preparation method is the same as in example 1.
1. The method for testing the water vapor transmittance of the coating comprises the following steps:
according to GB/T864-2008, 5.4.2. The samples of each example were stirred separately and evenly,
the mixture was poured into a predetermined film die without mixing bubbles, and applied. For convenient demoulding, the surface of the die before coating can be treated by silicone oil or liquid wax, the test piece is prepared for secondary coating, the thickness reaches (1.0+/-0.3) mm, the prepared test piece is cured for 96 hours under standard test conditions, and after demoulding, the test piece is put into a drying box at the temperature of (40+/-2) ℃ for drying for 48 hours, and after being taken out, the test piece is placed for more than 4 hours under standard test conditions. And checking the appearance of the coating film, wherein the surface of the test piece is smooth and flat, and no obvious bubbles exist.
To measure the water vapor permeability of the film, the procedure described in ASTM E96 and JGT 309-2011, "determination and classification of water vapor permeability of exterior wall coating" was followed for the determination of water vapor permeability, according to the dry test method. In this method, an amount of anhydrous calcium chloride is placed in a glass container sealed with a polymeric film. The sample bottles were kept in a defined temperature and humidity environment, the environmental conditions for this test being laboratory conditions (temperature: 23.+ -. 0.6 ℃ C., humidity: 90.+ -. 2%) and a function of the weighing time in a balance with an error of 10 mg. Each sample was weighed three times and the average reported. Three independent experiments were performed for each coating. The results were counted in table 1.
TABLE 1
| Examples | Wet flow density g (m) 2 h) |
| Example 1 | 10.1 |
| Example 2 | 10.6 |
| Example 3 | 11.5 |
| Comparative example 1 | 1.2 |
| Comparative example 3 | 19.8 |
| Comparative example 4 | 1.1 |
2. The method for testing the waterproof capability of the paint comprises the following steps:
to test the waterproof ability of the waterproof coating in each example, a pressure of 10kPa water column was specified with reference to foreign standards and domestic standards for waterproof vapor permeable membranes, without leakage and water permeation for 2 hours. The procedure was as in GB/T328.10-2007, method A, without the use of an indicator. The results were counted in table 2.
TABLE 2
In summary, it is clear that the coating of the present invention can effectively prevent water from being generated by the product of the present invention while ensuring a certain water vapor transmission rate after coating, and in contrast, the products of comparative examples 1 and 4 are not permeable to steam despite being waterproof, and the preparation method of comparative example 2 cannot obtain stable emulsion, and the product of comparative example 3 is not good in waterproof effect although being permeable to steam. The products of each comparative example are difficult to obtain excellent coatings, thereby realizing industrial production.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (13)
1. A waterproof coating, characterized in that: the raw materials comprise, by weight: 25-45 parts of acrylic emulsion, 30-50 parts of powder, 1-5 parts of auxiliary agent and 10-20 parts of water;
the raw materials of the acrylic emulsion comprise: n-butyl acrylate, methacrylic acid, ethyl acrylate, methyl methacrylate, styrene, acrylic acid, divinylbenzene, acrylic acid-cage polysilsesquioxane, 1, 4-butanediol diacrylate, initiator, buffer, surfactant; the weight ratio of the divinylbenzene to the acrylic group-cage polysilsesquioxane is (3-6): 4-7;
the preparation method of the acrylic emulsion comprises the following steps:
(1) Kernel synthesis: mixing n-butyl acrylate, methacrylic acid, divinylbenzene and acrylic acid group-cage polysilsesquioxane to obtain a comonomer mixture, adding the comonomer mixture into water containing a surfactant, a buffer solution and an initiator, and stirring to obtain seed dispersion;
(2) And (3) shell synthesis: mixing ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate, adding the mixture into the seed dispersion liquid obtained in the step (1), and dialyzing to remove redundant monomers to obtain acrylic emulsion.
2. The waterproof coating according to claim 1, wherein: the raw materials of the acrylic emulsion comprise the following components in parts by weight: 2-4 parts of n-butyl acrylate, 0.5-2 parts of methacrylic acid, 0.01-0.04 part of divinylbenzene, 0.01-0.05 part of acrylic group-cage polysilsesquioxane, 10-20 parts of ethyl acrylate, 0.5-2.5 parts of methyl methacrylate, 10-15 parts of styrene, 0.2-1.0 part of acrylic acid, 0.2-0.8 part of 1, 4-butanediol diacrylate, 0.01-0.04 part of initiator, 0.01-0.08 part of buffer solution, 0.1-0.5 part of surfactant and 50-70 parts of water.
3. The waterproof coating according to claim 2, characterized in that: the raw materials of the acrylic emulsion comprise the following components in parts by weight: 3 parts of n-butyl acrylate, 1 part of methacrylic acid, 0.02 part of divinylbenzene, 0.02 part of acrylic group-cage polysilsesquioxane, 14 parts of ethyl acrylate, 1 part of methyl methacrylate, 12 parts of styrene, 1 part of acrylic acid, 0.5 part of 1, 4-butanediol diacrylate, 0.03 part of an initiator, 0.03 part of a buffer, 0.4 part of a surfactant and 67 parts of water.
4. The waterproof coating according to claim 1, wherein: the initiator comprises one or more of ammonium persulfate, potassium sulfate, benzoyl peroxide tert-butyl peroxide and methyl ethyl ketone peroxide.
5. The waterproof coating according to claim 4, wherein: the initiator is ammonium persulfate.
6. The waterproof coating according to claim 1, wherein: the buffer solution comprises one or more of sodium acetate buffer solution, boric acid buffer solution and phosphate buffer solution.
7. The waterproof coating according to claim 6, wherein: the buffer solution is dipotassium hydrogen phosphate buffer solution.
8. The waterproof coating according to claim 1, wherein: the surfactant comprises one or more of sodium dodecyl benzene sulfonate, ethoxylated alkyl sodium sulfate and ammonium dodecyl sulfate.
9. The waterproof coating according to claim 8, wherein: the surfactant is ammonium dodecyl sulfate.
10. The waterproof coating according to claim 1, wherein: the weight ratio of divinylbenzene to acrylic-cage polysilsesquioxane is 1:1.
11. The waterproof coating according to claim 1, wherein: the auxiliary agent comprises the following components: one or more of defoamer, preservative, dispersant, buffer, titanium pigment and thickener.
12. The waterproof coating according to claim 1, wherein: the powder comprises one or more of heavy calcium carbonate, barium sulfate and quartz powder.
13. A method of preparing a water-resistant coating according to any one of claims 1 to 12, wherein: the method comprises the following steps: (1) kernel synthesis: mixing n-butyl acrylate, methacrylic acid, divinylbenzene and acrylic acid group-cage polysilsesquioxane to obtain a comonomer mixture, adding the comonomer mixture into water containing a surfactant, a buffer solution and an initiator, and stirring to obtain seed dispersion;
(2) And (3) shell synthesis: mixing ethyl acrylate, methyl methacrylate, styrene, acrylic acid and 1, 4-butanediol diacrylate, adding the mixture into the seed dispersion liquid obtained in the step (1), and dialyzing to remove redundant monomers to obtain an acrylic emulsion;
(3) Mixing the acrylic emulsion, the auxiliary agent and the powder, and uniformly stirring to obtain the acrylic emulsion.
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