CN116426184A - Polymer cement anti-corrosion paint based on two-dimensional inorganic material and preparation method thereof - Google Patents
Polymer cement anti-corrosion paint based on two-dimensional inorganic material and preparation method thereof Download PDFInfo
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- CN116426184A CN116426184A CN202310473708.8A CN202310473708A CN116426184A CN 116426184 A CN116426184 A CN 116426184A CN 202310473708 A CN202310473708 A CN 202310473708A CN 116426184 A CN116426184 A CN 116426184A
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- anticorrosive paint
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- 239000011414 polymer cement Substances 0.000 title claims abstract description 44
- 239000003973 paint Substances 0.000 title claims abstract description 39
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 30
- 239000011147 inorganic material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005260 corrosion Methods 0.000 title abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 79
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001238 wet grinding Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 25
- 238000000227 grinding Methods 0.000 claims description 17
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004567 concrete Substances 0.000 description 8
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- 239000008367 deionised water Substances 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 6
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical group CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 5
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- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 239000011435 rock Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 235000017454 sodium diacetate Nutrition 0.000 description 1
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Images
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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a polymer cement anticorrosive paint based on a two-dimensional inorganic material, which comprises the following steps: firstly, adding vinyl trimethoxy silane in the polymerization process of acrylic emulsion to obtain modified acrylic emulsion; secondly, wet grinding the modified emulsion and basalt sheets to obtain mixed slurry; and finally, mechanically stirring the mixed slurry with cement and other raw materials uniformly to obtain the polymer cement anticorrosive paint. According to the invention, vinyl trimethoxy silane is added in the emulsion polymerization process, so that the polymer cross-linked network structure of the emulsion is enlarged, and the water resistance and corrosion resistance of the coating are improved; the emulsion and the basalt flakes are pretreated by utilizing a wet grinding process, so that the compatibility of the basalt flakes and the emulsion is improved, sedimentation of the basalt flakes in the paint is prevented, and the physical barrier effect is effectively exerted. The invention realizes the comprehensive improvement of the water resistance, corrosion resistance and mechanical strength of the polymer cement anticorrosive paint through the double effects of chemical combination and physical barrier.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a polymer cement anti-corrosion coating based on a two-dimensional inorganic material and a preparation method thereof.
Background
With the rapid development of urban construction, the population number of cities is continuously increased, and the sewage discharge amount of China is also increased. Therefore, the construction of sewage treatment plants and sewage pipe networks, which are important components of municipal engineering, is continuously increased in all places, and the durability and operation safety of the facilities play an important role in maintaining the normal operation of cities. Generally, the service life of the urban sewage concrete treatment facilities is designed to be 60-70 years, but the urban sewage concrete treatment facilities are subjected to various corrosion effects such as acid etching, erosion, microorganisms, freeze thawing circulation, carbonization and the like in the long-term operation, and phenomena such as loose concrete surface, mortar falling, bone material exposure, cracking, steel bar corrosion and the like can occur in 5-10 years, so that the service life cannot be reached, and the service function and the structural safety of a structure are seriously influenced.
In urban sewage treatment engineering, design and constructors often neglect the problems of corrosion and protection of concrete sewage tanks (including sedimentation tanks, MSBR tanks, contact tanks, anaerobic tanks, concentration tanks, grit chambers and the like) due to habits. The problem of corrosion of the concrete in the urban sewage pool has become an important factor affecting the quality and the service life of the coating engineering, and effective protective measures are adopted to greatly improve the service life of the concrete sewage pool. At present, urban sewage concrete treatment facilities in China are in a large-scale construction and standard improvement stage, and the performance requirements and application technologies of various anti-corrosion materials are also in a positive searching process. The anti-corrosion coating is a common treatment measure for urban sewage concrete at the present stage, but due to lack of related design, evaluation and construction standards, the coating is often shelled and failed due to unreasonable material selection or design.
In some researches, basalt sheets are applied to a coating system, particularly a resin system, the basalt sheets can divide the resin into a plurality of small spaces, the phenomenon of stress concentration in the resin is effectively improved, a staggered structure is formed among rock sheets, and medium infiltration can be changed into roundabout, so that the path of corrosive medium to matrix resin and the time of penetrating into the matrix are increased, and the corrosion resistance of the coating is improved. However, since basalt flakes have a higher density than resin, and their surface inertness also deteriorates dispersibility and stability in resin, sedimentation is liable to occur, and interface action between them and resin is deteriorated, and at the same time, it is difficult to control arrangement of basalt flakes in resin, so that coating performance cannot be effectively improved. Likewise, it is more difficult to avoid the above problems if it is directly used in a polymer cement organic-inorganic composite system. Therefore, the improvement of the dispersibility and the interface effect of the basalt flakes in a polymer emulsion system is a key for improving the performance of the basalt flakes and emulsion composite material, and is one of research hotspots of basalt flakes anticorrosive paint.
Based on the above, the preparation method of the polymer cement anticorrosive paint containing basalt sheets is researched and developed, the basalt sheets are ensured to be uniformly dispersed in a polymer cement paint system and keep stability, the basalt sheets are fully used as a barrier function of a physical barrier, and are combined with the chemical function of polymer emulsion, so that the water resistance, corrosion resistance and mechanical strength of the polymer cement anticorrosive paint are improved through synergistic effect, the preparation method has important significance on further widening the application field of the polymer cement anticorrosive paint, and the preparation method is a technical problem which needs to be solved by researchers.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a polymer cement anticorrosive paint which can remarkably improve the stability of polymer emulsion and ensure the uniform dispersion of the Xuanwu tablets in a polymer cement system.
The second purpose of the invention is to provide a polymer cement anticorrosive paint based on a two-dimensional inorganic material, which has good water resistance and corrosion resistance and high mechanical strength.
One of the achievement purposes of the invention adopts the technical proposal that: the preparation method of the polymer cement anticorrosive paint based on the two-dimensional inorganic material comprises the following steps:
s1, preparing a pre-emulsion containing a mixed acrylic monomer, a cross-linking agent and vinyl trimethoxy silane; preparing a seed emulsion from the mixed acrylic monomer, a part of initiator and a cross-linking agent; at a certain temperature, synchronously dripping the residual initiator and the pre-emulsion into the seed emulsion, preserving heat for reaction, and cooling, regulating pH and filtering after the reaction is finished to obtain modified acrylic emulsion;
s2, taking the modified acrylic emulsion as a grinding environment, performing wet grinding treatment on the modified acrylic emulsion and basalt sheets under the action of a grinding medium, and sieving to obtain mixed slurry;
and S3, adding cement, a film forming additive, a dispersing agent, a defoaming agent and water into the mixed slurry, and uniformly mixing to obtain the polymer cement anticorrosive paint based on the two-dimensional inorganic material.
The general idea of the invention is as follows: in order to make basalt sheets more effectively play a role in a polymer cement paint system and further improve the water resistance and corrosion resistance of a coating, the preparation method of the invention is mainly improved in the following two aspects:
on the one hand, in order to further improve the water resistance and corrosion resistance of the coating, unlike the traditional method, the method does not directly use the commercial polymer emulsion, but self-prepares the acrylic emulsion by adopting a seed emulsion polymerization method, when a pre-emulsification process is adopted, monomer beads formed in the stirring process of the monomer can not adsorb emulsifying agents from the periphery, so that the system of the emulsion is more stable in the polymerization process, gel is reduced, and the synthesized emulsion has better stability; and adding a vinyl trimethoxy silane modifier in the synthesis stage of the polymer emulsion to combine the molecular chain segment in the modifier with the functional group of the acrylic monomer, so that the polymer cross-linked network structure of the acrylic emulsion is enlarged, and the waterproof and corrosion-resistant performances of the coating are improved.
On the other hand, in order to improve the dispersibility and interface compatibility of basalt sheets in the modified polymer emulsion, the preparation process is optimized, the modified acrylic emulsion is taken as a grinding environment, and the liquid-phase grinding process is adopted to perform wet grinding treatment on the basalt sheets. In the wet milling treatment process, the activity of the basalt flakes is gradually improved along with the increase of the wet milling time, so that the basalt flakes can be effectively prevented from settling in the emulsion, can be uniformly dispersed and arranged in the emulsion, and can effectively exhibit the effect of physical barrier in the coating in the later period, thereby improving the anti-corrosion and anti-fouling properties of the coating.
Further, in step S1, the preparation method of the pre-emulsion includes: mixing water, a mixed emulsifier and a pH buffer and preheating to obtain a mixed solution A; and (3) synchronously dripping 80-90% of mixed solution of the mixed acrylic acid monomer and the cross-linking agent and vinyl trimethoxy silane into the mixed solution A, and uniformly stirring to obtain a pre-emulsion.
Preferably, the vinyl trimethoxy silane is used in an amount of 3 to 5% by weight based on the total weight of the mixed acrylic monomers for preparing the modified acrylic emulsion.
Further, in step S1, the preparation method of the seed emulsion includes: mixing water, a mixed emulsifier and a pH buffer, and heating in a water bath to obtain a mixed solution B; and (3) synchronously dripping 10-20% of initiator and the rest mixed solution of the mixed acrylic monomer and the cross-linking agent into the mixed solution B, and uniformly stirring to obtain seed emulsion.
In step S1, the temperature of the heating reaction is 85-90 ℃, and the heating reaction time is 2-3 h. After the heating reaction is finished, the temperature is kept for 40 to 50 minutes, and after natural cooling, the pH value is adjusted to 7 to 8.
Further, the mixed emulsifier consists of an anionic emulsifier and a nonionic emulsifier; the mass ratio is (10-15): (15-25).
Preferably, the anionic emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Preferably, the nonionic emulsifier is dodecylphenol polyoxyethylene ether.
Preferably, the pH buffer is sodium bicarbonate or sodium hydrogen acetate.
Preferably, the mixed acrylic monomer is prepared from a soft monomer, a hard monomer and a functional monomer according to (5-8): (0.2-0.5): (3-6) mass ratio; in some preferred embodiments, the soft monomer is butyl acrylate, the hard monomer is methyl methacrylate, and the functional monomer is acrylic acid or methacrylic acid.
Preferably, the crosslinking agent is acrylamide.
Preferably, the initiator solution is an aqueous ammonium persulfate solution.
In step S2, the grinding medium is zirconia balls, and the diameter of the zirconia balls is 1.2-1.4 mm.
Further, in step S2, the mass ratio of the modified acrylic emulsion, basalt flakes and zirconia balls is (35 to 45): (20-40): (10-20).
Further, in the step S2, the rotational speed of the wet grinding treatment is 450-500 rpm/min, and the time of the wet grinding treatment is 20-60 min. Under the condition of the wet grinding rotating speed, the lifted height of the zirconia balls is higher, the zirconia balls are separated from the tank body after being lifted to a certain height, fall along a parabolic track, have a larger impact effect at a throwing point, and have higher grinding efficiency. If the rotation speed is lower than the rotation speed, the lifted height of the ball in the grinding tank is too small, the ball vertically descends under the gravity action of the ball, the impact force of the ball is small, and the grinding effect is not obvious; if the rotational speed is higher than the rotational speed, the balls can not fall along with the rotation of the tank body in a centrifugal operation state, and the balls have no impact force and cannot play an effective grinding role. Preferably, the rotational speed of the wet milling treatment is 450rpm/min and the time of the wet milling treatment is 60min.
Further, in step S2, the thickness of the basalt flakes (i.e., basalt flakes) is 2-4 μm, and the flake diameter is 25-3 mm; in the mixed slurry, the average particle size of basalt sheets after wet grinding is 2-3 mu m.
In step S3, the mixing is performed by mechanical stirring, the rotation speed of the mechanical stirring is 600-800 rpm/min, and the continuous stirring time is 3-5 min.
The second technical scheme adopted for realizing the purpose of the invention is as follows: providing a polymer cement anticorrosive paint based on a two-dimensional inorganic material, which is prepared by the preparation method according to one of the purposes of the invention, and consists of a solid phase material and a liquid phase material; according to the mass portion of the components,
the solid phase material comprises: 10-30 parts of cement and 20-40 parts of basalt sheets;
the liquid phase material comprises: 35-45 parts of modified acrylic emulsion, 1-2 parts of film forming additive, 0.5-1 part of dispersing agent, 0.5-1 part of defoamer and 1-5 parts of deionized water.
Preferably, the cement is Portland cement having a strength grade of 42.5 or 52.5.
Preferably, the film forming aid is selected from one or more of ethylene glycol butyl ether, ethylene glycol butyl ether acetate or propylene glycol butyl ether.
Preferably, the dispersant is polyoxyethylene sorbitan monooleate.
Preferably, the defoamer is selected from silicone-type defoamers or polyether-type defoamers.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the polymer cement anti-corrosion coating based on the two-dimensional inorganic material, when the acrylic emulsion is synthesized by using a seed emulsion polymerization mode, the waterproof and anti-corrosion performance of the polymer emulsion is improved by using a chemical modification method, and the stability of the polymer emulsion is improved; in the process of preparing the coating, a physical treatment mode of wet grinding is used for carrying out wet grinding pretreatment on the modified polymer emulsion and the basalt flakes of the inorganic material, so that the physical barrier effect can be effectively exerted in the coating after the modified polymer emulsion and the basalt flakes of the inorganic material. The invention improves the stability of polymer emulsion and ensures the uniform dispersion of the Xuanwu tablets in the polymer cement system by combining the functions of two aspects of physical barriers, thereby realizing the comprehensive improvement of the water resistance, corrosion resistance and mechanical strength of the polymer cement anticorrosive paint.
(2) According to the polymer cement anti-corrosion coating based on the two-dimensional inorganic material and the preparation method thereof, basalt sheets are added into the modified acrylic emulsion, so that the emulsion can be divided into a plurality of small spaces, the phenomenon of stress concentration in the emulsion is effectively improved, staggered layers are formed among the basalt sheets, and medium permeation can be changed into tortuous, so that the path of corrosive medium diffusing into the coating and the time of penetrating into a substrate are increased, and the anti-corrosion performance of the coating is improved. Furthermore, the basalt chips and the modified acrylic emulsion are pretreated by the wet grinding process, so that the basalt chips are effectively prevented from settling in the emulsion, and the basalt chips can effectively play a role in the coating.
(3) The polymer cement anticorrosive paint based on the two-dimensional inorganic material provided by the invention adopts basalt flakes as the two-dimensional inorganic material to replace part of cement, and compared with cement products with high energy consumption and high carbon emission, the polymer cement anticorrosive paint based on the two-dimensional inorganic material has lower energy consumption in production, and has important significance for structural adjustment, energy conservation and emission reduction of building materials in China.
Drawings
Fig. 1 is a schematic flow chart of a polymer cement anticorrosive paint based on a two-dimensional inorganic material.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further illustrated, but is not limited, by the following examples.
The main raw materials and parts by weight involved in the preparation of the polymer cement paint in examples 1 to 9 of the present invention are shown in the following table 1.
TABLE 1
In the table above, the cement is ordinary Portland cement, and the strength grade is 42.5; the film forming auxiliary agent is selected from one of ethylene glycol butyl ether, ethylene glycol butyl ether acetate or propylene glycol butyl ether; the dispersing agent is polyoxyethylene sorbitan monooleate; the defoamer is selected from organosilicon defoamer or polyether defoamer. The basalt sheets are of a dark green sheet-shaped structure, the thickness of the basalt sheets is 2-4 mu m, and the sheet diameter is 25-3 mm; after the wet grinding treatment in the step 2, the average grain diameter of basalt sheets in the wet grinding slurry is 2-3 mu m.
Example 1
The preparation method of the polymer cement anticorrosive paint based on the two-dimensional inorganic material comprises the following steps:
step 1:
a) 56g of deionized water, 1.2g of sodium dodecyl sulfate, 2g of dodecylphenol polyoxyethylene ether and 0.4g of sodium bicarbonate are mixed and preheated to 40 ℃, a mixed solution containing 56.7g of butyl acrylate, 3.6g of methyl methacrylate, 29.7g of methacrylic acid and 1.35g of acrylamide and 5g of vinyltrimethoxysilane are synchronously added dropwise to the preheated mixed solution within 45min, and magnetic stirring is carried out uniformly, so that a stable pre-emulsion is obtained.
b) 14g of deionized water, 0.3g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether and 0.1g of sodium bicarbonate are added into a four-necked flask to be mixed, the mixture is heated to 75 ℃ in a water bath, a mixed solution containing 6.3g of butyl acrylate, 0.4g of methyl methacrylate, 3.3g of methacrylic acid and 0.15g of acrylamide and a 0.06g of ammonium persulfate aqueous solution are synchronously added into the heated mixed solution in a dropwise manner within 10min, and the mixture is magnetically stirred uniformly to obtain seed emulsion.
c) Raising the water bath temperature to 85 ℃, synchronously dripping 0.54g of ammonium persulfate aqueous solution and the stable pre-emulsion into the seed emulsion within 2-3 h to perform subsequent reaction, performing heat preservation and development for 45min, naturally cooling for 20min, adjusting the pH of the product to 7-8, and filtering and collecting filtrate to obtain the modified acrylic emulsion.
Step 2: 45g of modified acrylic emulsion, 40g of basalt sheets and 20g of zirconia balls (1.2 mm) are taken and added into a grinding tank, the modified acrylic emulsion is taken as a grinding environment, the zirconia balls are taken as a grinding medium, and the grinding tank is placed into a wet mill to be ground for 60min at the rotating speed of 450rpm/min, and then the mixed slurry is obtained through sieving.
Step 3: and (3) respectively adding cement, a film-forming auxiliary agent, a dispersing agent, a defoaming agent and deionized water into the mixed slurry under the mechanical stirring condition of 700rpm/min, and continuing stirring for 4min until the components are uniformly dispersed, so as to obtain the polymer cement anticorrosive paint prepared from the two-dimensional inorganic material.
Example 2
This embodiment differs from embodiment 1 in that: when the acrylic emulsion is synthesized in the step 1, 4g (accounting for 4 percent of the total mass of the mixed monomers) of vinyl trimethoxy silane is added, and other steps and parameters are unchanged, so that the two-dimensional inorganic material modified polymer cement anticorrosive paint is obtained.
Example 3
This embodiment differs from embodiment 1 in that: 3g (3% of the total mass of the mixed monomers) of vinyl trimethoxy silane is added during the synthesis of the acrylic emulsion in the step 1, and other steps and parameters are unchanged, so that the two-dimensional inorganic material modified polymer cement anticorrosive paint is obtained.
Example 4
This embodiment differs from embodiment 1 in that: and (3) adjusting the raw material consumption, adding 30g of basalt sheets during wet grinding pretreatment in the step (2), adding 20g of cement in the step (3), and obtaining the two-dimensional inorganic material modified polymer cement anticorrosive paint without changing other steps and parameters.
Example 5
This embodiment differs from embodiment 1 in that: and (3) adjusting the raw material consumption, adding 20g of basalt sheets during wet grinding pretreatment in the step (2), adding 30g of cement in the step (3), and obtaining the two-dimensional inorganic material modified polymer cement anticorrosive paint without changing other steps and parameters.
Example 6
This embodiment differs from embodiment 1 in that: and (3) adjusting the wet grinding pretreatment time in the step (2) to 40min, and keeping other steps and parameters unchanged to obtain the two-dimensional inorganic material modified polymer cement anticorrosive paint.
Example 7
This embodiment differs from embodiment 1 in that: and (3) adjusting the wet grinding pretreatment time in the step (2) to 20min, and keeping other steps and parameters unchanged to obtain the two-dimensional inorganic material modified polymer cement anticorrosive paint.
Examples 8 and 9
The difference from example 1 is that: according to the formula shown in Table 1, the dosage of each raw material is adjusted, and other steps and operation methods are unchanged, so that the two-dimensional inorganic material modified polymer cement anticorrosive paint is prepared respectively.
Comparative example 1
An acrylic emulsion was prepared without modification with vinyltrimethoxysilane.
The difference between this comparative example and example 1 is that: when the step 1 is used for synthesizing the acrylic emulsion by using a seed emulsion polymerization process, a vinyl trimethoxy silane modifier is not added, and other steps and parameters are unchanged, so that the two-dimensional inorganic material modified polymer cement anticorrosive paint is obtained.
Comparative example 2
And preparing the polymer cement anticorrosive paint which is not pretreated by a wet grinding process.
The difference between this comparative example and example 1 is that: omitting the wet grinding pretreatment step of the step 2, uniformly mixing basalt sheets and modified acrylic emulsion in the step 3 by using a mechanical stirring mode, and obtaining the two-dimensional inorganic material modified polymer cement anti-corrosive paint without changing other steps and parameters.
Comparative example 3
Directly preparing the conventional polymer cement anticorrosive paint.
Step 1: a) 56g of deionized water, 1.2g of sodium dodecyl sulfate, 2g of dodecylphenol polyoxyethylene ether and 0.4g of sodium bicarbonate are mixed and preheated to 40 ℃, and a mixed solution containing 56.7g of butyl acrylate, 3.6g of methyl methacrylate, 29.7g of methacrylic acid and 1.35g of acrylamide is synchronously added dropwise to the preheated mixed solution within 45min, and the mixture is magnetically stirred uniformly to obtain a stable pre-emulsion.
b) 14g of deionized water, 0.3g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether and 0.1g of sodium bicarbonate are added into a four-necked flask to be mixed, the mixture is heated to 75 ℃ in a water bath, a mixed solution containing 6.3g of butyl acrylate, 0.4g of methyl methacrylate, 3.3g of methacrylic acid and 0.15g of acrylamide and a 0.06g of ammonium persulfate aqueous solution are synchronously added into the heated mixed solution in a dropwise manner within 10min, and the mixture is magnetically stirred uniformly to obtain seed emulsion.
c) Raising the temperature of the water bath to 85 ℃, synchronously dripping 0.54g of ammonium persulfate aqueous solution and the stable pre-emulsion into the seed emulsion for 2-3 h by weight to carry out subsequent reaction, and carrying out heat preservation and development for 45min, naturally cooling for 20min, adjusting the pH of the product to 7-8, and filtering and collecting the filtrate to obtain the modified acrylic emulsion.
Step 2: and uniformly stirring the cement and the basalt sheets in a stirrer to obtain powder components. Adding deionized water, a film forming additive, a dispersing agent and a defoaming agent into the prepared modified acrylic emulsion, and uniformly stirring to obtain a liquid component. And finally, adding the uniformly mixed powder into the liquid material, and mechanically stirring at the rotating speed of 700rpm/min for 4min until the powder is uniformly mixed to obtain the polymer cement anticorrosive paint.
Performance testing
The polymer cement anticorrosive coatings prepared in examples 1-9 and comparative examples 1-3 were subjected to performance tests, and according to the GB/T16777-2008 standard, the tensile strength, elongation at break and bonding strength of the coatings under the conditions of no treatment, acid treatment, alkali treatment and ultraviolet aging treatment are tested; the coating was tested for its barrier properties according to the GB/T23445-2009 standard. The resulting performance test data are shown in tables 2 and 3.
Table 2:
TABLE 3 Table 3
As can be seen from tables 2 and 3,
according to the test results of comparative examples 1-3, it is known that the mechanical strength, the anti-aging corrosion resistance and the anti-permeability of the coating can be enhanced to a certain extent by adding the vinyl trimethoxy silane modifier in the emulsion synthesis stage or adding the basalt sheet in the preparation of the coating, but the effect is limited.
Further, as can be seen from comparison of the experimental results of example 1 and comparative example 2, the coating performance obtained by pretreatment of the modified acrylic emulsion and basalt flakes by the wet milling process of the present invention is better than the coating application performance obtained by the conventional stirring method. Furthermore, as can be seen from a comparison of the test results of example 1 with examples 6 and 7, the application properties of the coating are also related to the time of the wet milling pretreatment: on the premise of fixed wet milling rotation speed, the longer the wet milling time is, the higher the activity of basalt flakes is, the stronger the interface compatibility with emulsion is, the less sedimentation is easy to occur, and the more uniform the staggered structure is in the emulsion, so that the coating has better performance.
Further, in the present invention, the coating properties are also related to the amount of modifier incorporated in the preparation of the emulsion and the amount of basalt flakes used in the wet milling process. The data of comparative examples 1, 2 and 3 show that the higher the amount of vinyltrimethoxysilane, the more fully it reacts with the acrylic monomer mixture, and the more complex the crosslinked network structure of the emulsion, thereby improving the properties of the coating in all respects. As can be seen from the data of comparative examples 1, 4 and 5, the more basalt flakes are added during the wet milling process, the denser and more complex the "maze effect" will be created in the coating thereafter, thereby further improving the performance of the coating in all respects.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the polymer cement anticorrosive paint based on the two-dimensional inorganic material is characterized by comprising the following steps of:
s1, preparing a pre-emulsion containing a mixed acrylic monomer, a cross-linking agent and vinyl trimethoxy silane; preparing a seed emulsion from the mixed acrylic monomer, a part of initiator and a cross-linking agent; at a certain temperature, synchronously dripping the residual initiator and the pre-emulsion into the seed emulsion, preserving heat for reaction, and cooling, regulating pH and filtering after the reaction is finished to obtain modified acrylic emulsion;
s2, taking the modified acrylic emulsion as a grinding environment, performing wet grinding treatment on the modified acrylic emulsion and basalt sheets under the action of a grinding medium, and sieving to obtain mixed slurry;
and S3, adding cement, a film forming additive, a dispersing agent, a defoaming agent and water into the mixed slurry, and uniformly mixing to obtain the polymer cement anticorrosive paint based on the two-dimensional inorganic material.
2. The method according to claim 1, wherein the vinyl trimethoxysilane is added in an amount of 3 to 5% by weight based on the total weight of the mixed acrylic monomers used to prepare the modified acrylic emulsion in step S1.
3. The method according to claim 1, wherein in step S1, the mixed acrylic monomer is prepared from a soft monomer, a hard monomer and a functional monomer according to (5 to 8): (0.2-0.5): (3-6) by mass ratio.
4. The method according to claim 1, wherein in the step S1, the reaction temperature is 85-90℃and the reaction time is 2-3 hours.
5. The method according to claim 1, wherein in step S2, the grinding medium is zirconia balls having a diameter of 1.2 to 1.4mm.
6. The method according to claim 1, wherein in step S2, the mass ratio of the modified acrylic emulsion, basalt flakes, and grinding medium is (35 to 45): (20-40): (10-20).
7. The method according to claim 1, wherein in step S2, the rotational speed of the wet milling treatment is 450 to 500rpm/min, and the time of the wet milling treatment is 20 to 60min.
8. The method according to claim 1, wherein in the step S2, the basalt sheet has a thickness of 2 to 4 μm and a sheet diameter of 25 to 3mm; in the mixed slurry, the average particle size of basalt sheets after wet grinding is 2-3 mu m.
9. The method according to claim 1, wherein in step S3, the mixing is performed by mechanical stirring at 600 to 800rpm/min for 3 to 5min.
10. A polymer cement anticorrosive paint based on a two-dimensional inorganic material prepared by the preparation method according to any one of claims 1 to 9, characterized by comprising the following raw materials in parts by mass:
solid phase material: 10-30 parts of cement and 20-40 parts of basalt sheets;
liquid phase material: 35-45 parts of modified acrylic emulsion, 1-2 parts of film forming additive, 0.5-1 part of dispersing agent, 0.5-1 part of defoamer and 1-5 parts of water.
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