CN111363445B - High-fluorine-content water-based concrete protective coating - Google Patents

High-fluorine-content water-based concrete protective coating Download PDF

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CN111363445B
CN111363445B CN202010297135.4A CN202010297135A CN111363445B CN 111363445 B CN111363445 B CN 111363445B CN 202010297135 A CN202010297135 A CN 202010297135A CN 111363445 B CN111363445 B CN 111363445B
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fluorine
emulsion
polymer emulsion
content
water
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CN111363445A (en
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万艳贞
霍丽
黄正强
赵磊
杜祥建
杨长聚
张晨曦
白俊敬
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Henan Zhongyuan Transportation Technology Research Institute Co Ltd
Zhongyuan Research Institute Of Zhejiang University
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Zhongyuan Research Institute Of Zhejiang University
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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
    • C09D151/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
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    • C09D127/00—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C09D127/12—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
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    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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Abstract

The invention relates to the technical field of concrete protective coatings, in particular to a high-fluorine-content water-based concrete protective coating. The high-fluorine-content water-based concrete protective coating is prepared from the following raw materials in parts by weight: 30-80 parts of high-fluorine-content polymer emulsion, 0-50 parts of filler, 10-30 parts of water, 2-10 parts of film-forming assistant, 0-0.5 part of pH regulator, 0-0.3 part of bactericide and 0.2-4 parts of necessary assistant; wherein the high fluorine content polymer emulsion is prepared by compounding 10-80% of fluorine-containing alkyl silane emulsion and 20-90% of fluorocarbon emulsion. The coating has high fluorine content, excellent weather resistance, corrosion resistance and self-cleaning capability, and is suitable for coating the surface of porous substrates (such as concrete, tiles and other substrates).

Description

High-fluorine-content water-based concrete protective coating
Technical Field
The invention relates to the technical field of concrete protective coatings, in particular to a high-fluorine-content water-based concrete protective coating.
Background
The fluorine element has high electronegativity and smaller atomic radius, and the introduction of the fluorine element can improve the weather resistance and the chemical corrosion resistance of the coating. The main component of the existing water-based fluorocarbon coating is fluorine-containing acrylate emulsion, the fluorine content is generally not more than 10% due to the limitation of a technical route, and compared with oil-based fluorocarbon coatings, polymer materials with high fluorine content such as anti-fouling, aging-resistant and anti-corrosion performances such as PTFE, FVDF, PCTFE and FEP have larger differences, and the main reason of the performance difference is the fluorine content difference.
The method is influenced by factors such as cost and construction process, the solid content of the coating is generally 45-70%, filling and functional substances such as fillers and auxiliaries are removed, the content of film forming substances generally accounts for 15-40% of the coating system, and the fluorine content of the coating system is further limited, so that a novel fluorine-containing compound is added into the coating system and skillfully participates in the process of curing and film forming of the coating, and the method is an effective method for improving the fluorine content of the coating system.
The alkyl silane can be hydrolyzed to form the silanetriol under certain conditions, and the silanetriol is crosslinked to form a film and can be used as a film forming substance of the coating. The fluorine-containing alkyl silane refers to a compound in which hydrogen elements of alkyl parts of alkyl silane are substituted by fluorine elements, and the hydrolysis crosslinking film-forming property of the fluorine-containing alkyl silane is not changed after fluorine substitution, so that the fluorine-containing alkyl silane can be used as a compound with high fluorine content for preparing the coating. The mechanism of hydrolytic crosslinking of the fluoroalkyl silanes is as follows:
Figure BDA0002452613660000011
the macromolecular chain formed after the crosslinking of the fluorine-containing alkyl silane and the fluorine-containing acrylic acid macromolecule are mutually wound, and a stable coating system is formed through the interaction of hydrogen bonds, Van der Waals force and the like.
Disclosure of Invention
The invention aims at providing a high-fluorine-content polymer emulsion, and the invention aims at providing a high-fluorine-content water-based concrete protective coating.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention firstly provides a high fluorine content polymer emulsion which is prepared by compounding 10-80% of fluorine-containing alkyl silane emulsion and 20-90% of fluorocarbon emulsion by mass percentage.
According to the high fluorine content polymer emulsion, the fluorine-containing polymer emulsion is preferably prepared by compounding 30-70% of fluorine-containing alkyl silane emulsion and 30-70% of fluorocarbon emulsion by mass percentage. More preferably, the high fluorine content polymer emulsion is compounded by 50 percent of fluorine-containing alkyl silane emulsion and 50 percent of fluorocarbon emulsion by mass percentage.
According to the above-mentioned high fluorine content polymer emulsion, preferably, the fluorine-containing alkyl silane emulsion is a product obtained by emulsifying fluorine-containing alkyl silane, and the structural formula of the fluorine-containing alkyl silane is CnF2n+1(CH2)2Si(OR)3Wherein n is 3 to 16 and R represents-CH3or-CH2CH3(ii) a More preferably, n is 3 or 6 or 8.
Preferably, the fluorine-containing alkyl silane is perfluorooctyl triethoxysilane [ C ] according to the above-mentioned high fluorine content polymer emulsion6F13(CH2)2Si(OCH2CH3)3]Perfluoropentyltriethoxysilane [ C ]3F7(CH2)2Si(OCH2CH3)3]Perfluorodecyl triethoxysilane [ C ]8F17(CH2)2Si(OCH2CH3)3]Perfluorooctyltrimethoxysilane [ C ]6F13(CH2)2Si(OCH3)3]Perfluoropentyltrimethoxysilane [ C ] 3F7(CH2)2Si(OCH3)3]Any one of them. More preferably, the fluoroalkyl silane is perfluorooctyl triethoxysilane [ C ]6F13(CH2)2Si(OCH2CH3)3]。
According to the high fluorine content polymer emulsion, preferably, the preparation method of the fluorine-containing alkyl silane emulsion comprises the following steps:
(1) adding an emulsifier A into the fluorine-containing alkyl silane, and stirring until the emulsifier A is uniformly dispersed to obtain a mixed solution A for later use;
(2) adding an emulsifier B into water, and stirring until the emulsifier B is uniformly dispersed to obtain a mixed solution B;
(3) and adding the mixed solution A into the mixed solution B while stirring, and continuously stirring until the mixed solution A and the mixed solution B are completely emulsified after the addition is finished to obtain the fluorine-containing alkyl silane emulsion.
According to the above high fluorine content polymer emulsion, preferably, the emulsifier A is milk T-80 or S-80; the emulsifier B is any one of S-40, OP-20 and OP-15.
According to the high fluorine content polymer emulsion, the stirring speed in the step (3) is preferably 800-1500 rpm.
According to the high fluorine content polymer emulsion, preferably, the fluorocarbon emulsion is one or more of a fluorine-containing acrylate emulsion, a PVDF type fluorocarbon emulsion and a FEVE type fluorocarbon emulsion.
According to the above-mentioned high fluorine content polymer emulsion, preferably, the fluorine-containing alkyl silane content in the fluorine-containing alkyl silane emulsion is 10% to 90% by mass. More preferably, the fluorine-containing alkyl silane emulsion contains 30-80% of fluorine-containing alkyl silane by mass percent.
The invention also provides a preparation method of the high fluorine content polymer emulsion, which comprises the following steps: adding fluorocarbon emulsion into the fluorine-containing alkyl silane emulsion, and stirring until the fluorocarbon emulsion is uniformly dispersed to obtain the high-fluorine-content polymer emulsion.
According to the preparation method of the high-fluorine-content polymer emulsion, preferably, the stirring speed is 600-1000 rpm, and the stirring time is 5-20 min.
The invention also provides an application of the high-fluorine-content polymer emulsion in a water-based paint. Further, the high fluorine content polymer emulsion can be used as a film forming material of a coating for preparing a water-based coating.
The invention also provides a high-fluorine-content water-based concrete protective coating which is prepared from the following raw materials in parts by weight: 30-80 parts of high-fluorine-content polymer emulsion, 0-50 parts of filler, 10-30 parts of water, 2-10 parts of film-forming assistant, 0-0.5 part of pH regulator, 0-0.3 part of bactericide and 0.2-4 parts of necessary assistant, wherein the high-fluorine-content polymer emulsion is the high-fluorine-content polymer emulsion.
According to the high fluorine content water-based concrete protective coating, the film forming auxiliary agent is preferably dodecyl alcohol ester.
According to the above-mentioned high fluorine content water-based concrete protective coating, preferably, the filler is one or more of titanium dioxide, barium sulfate and wollastonite.
According to the above-mentioned high fluorine content water-based concrete protective coating, preferably, the necessary auxiliary agent is one or more of a dispersant, a defoamer and a thickener.
According to the water-based concrete protective coating with high fluorine content, the water-based concrete protective coating is preferably prepared from the following raw materials in parts by weight: 50 parts of high-fluorine polymer emulsion, 35 parts of filler, 11.7 parts of water, 2 parts of film-forming assistant, 0.2 part of pH regulator, 0.1 part of bactericide, 0.6 part of dispersant, 0.2 part of defoamer and 0.2 part of thickener, wherein the high-fluorine polymer emulsion is the high-fluorine polymer emulsion.
According to the high fluorine content water-based concrete protective coating, preferably, the pH regulator is DMAE (N, N-dimethylethanolamine); the bactericide is MC.
The invention also provides a preparation method of the high-fluorine-content water-based concrete protective coating, which comprises the following steps:
a. adding a dispersing agent into water, stirring until the dispersing agent is uniformly dispersed, adding a defoaming agent, eliminating bubbles, adding a pH regulator, and adjusting the pH of the system to 8-10 to obtain slurry;
b. adding a filler into the slurry prepared in the step a, and stirring until the filler is uniformly dispersed;
c. b, grinding the slurry treated in the step b until the fineness is less than 10 mu m, and discharging;
d. And c, adding the high-fluorine-content polymer emulsion into the slurry treated in the step c, stirring until the dispersion is uniform, then adding the film-forming aid, stirring and dispersing uniformly, then adding the thickening agent and the bactericide, and stirring and dispersing uniformly to obtain the high-fluorine-content water-based concrete protective coating.
According to the preparation method of the high-fluorine-content water-based concrete protective coating, preferably, the stirring speed in the step b is 1200-1500 rpm, and the stirring time is 10-20 min.
According to the preparation method of the high-fluorine-content water-based concrete protective coating, preferably, the stirring speed in the step d is 800-1000 rpm, and the stirring time is 5-10 min.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention takes the fluorine-containing alkyl silane as a raw material, adopts two emulsifiers to emulsify the fluorine-containing alkyl silane in three steps, emulsifies the fluorine-containing alkyl silane into water-based emulsion, and has good compatibility with water-based paint.
(2) The alkyl silane can be hydrolyzed to form the silicon triol under certain conditions, the silicon triol is crosslinked to form a film, can be used as a film forming substance of paint, the fluorine-containing alkyl silane is a compound of which the hydrogen element of the alkyl part of the alkyl silane is replaced by fluorine element, the hydrolysis crosslinking film forming property of the fluorine-containing alkyl silane after fluorine replacement is not changed, can be used as a compound with high fluorine content for preparing coating, therefore, the invention uses the fluorine-containing alkyl silane emulsion to modify fluorocarbon emulsion to prepare polymer emulsion with high fluorine content, the polymer emulsion can be used as a film forming substance for preparing water-based paint, improves the fluorine content of the water-based paint by more than 15 percent, so that the fluorine content of the coating system can reach 17.5 percent to the maximum, and the weather resistance, the chemical corrosion resistance and the self-cleaning capability (namely the stain resistance) of the coating are greatly improved.
(3) The fluorine-containing alkyl silane is hydrolyzed into the silanetriol with the side chain containing the fluorine-containing alkyl in the film forming process of the paint and is continuously crosslinked into a main chain-Si-O-macromolecular chain, so that the water-based paint is prepared by taking the high-fluorine-content polymer emulsion as a film forming substance, the primer fluorine element is added into the water-based paint, and the primer is added into the film forming substance with the main chain of-Si-O-bond, thereby further improving the air permeability and the strength of the paint coating.
(4) The high-fluorine-content water-based concrete protective coating prepared by the invention has excellent weather resistance, corrosion resistance and self-cleaning capability, is suitable for coating the surface of a porous substrate (such as concrete, brick and tile and other substrates), is particularly suitable for coating the concrete in heavy-duty anti-corrosion areas such as coastal wharfs, seaside power plants and the like, can prolong the service life of the concrete in the heavy-duty anti-corrosion areas, reduces the maintenance and reconstruction cost, and has great economic benefit.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
(one) preparing high fluorine content polymer emulsion
Example 1:
the high fluorine content polymer emulsion consists of perfluoro amyl trimethoxy silane in 50 wt% 3F7(CH2)2Si(OCH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion. Wherein the mass percentage of the perfluoropentyltrimethoxysilane in the perfluoropentyltrimethoxysilane emulsion is 30%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 30g of perfluoropentyltrimethoxysilane, adding 0.5g of emulsifier A, and stirring at 300rpm for 15min to obtain a mixed solution A for later use; wherein the emulsifier A is T-80;
(2) weighing 69g of water, adding 0.5g of emulsifier B, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B; wherein the emulsifier B is S-40;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluoropentyl trimethoxy silane emulsion, and defoaming stably;
(4) and (3) adding 100g of fluorocarbon emulsion into the perfluoropentyl trimethoxy silane emulsion, and dispersing for 10min at 800rpm to obtain the high fluorine content polymer emulsion.
Example 2:
the high fluorine content polymer emulsion consists of perfluoro octyl trimethoxyl silane in 50 wt%6F13(CH2)2Si(OCH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl trimethoxy silane in the perfluorooctyl trimethoxy silane emulsion is 30 percent; the fluorocarbon emulsion was the same as in example 1.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the fluorine-containing alkyl silane is perfluorooctyl trimethoxy silane; the emulsifier A is T-80, and the using amount is 0.2 g; the emulsifier B is OP-20, and the dosage is 0.8 g.
Example 3:
the high fluorine content polymer emulsion consists of perfluoro amyl triethoxy silane in 50 wt%3F7(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluoropentyltriethoxysilane in the perfluoropentyltriethoxysilane emulsion is 30%; the fluorocarbon emulsion was the same as in example 1.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the fluorine-containing alkyl silane is perfluoropentyl triethoxysilane; the emulsifier A is S-80, and the using amount is 0.2 g; the emulsifier B is OP-15, and the dosage is 0.8 g.
Example 4:
high fluorine content polymer emulsion containing in mass percentCalculated by 50% of perfluorooctyltriethoxysilane [ C ]6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 30%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the fluorine-containing alkyl silane is perfluorooctyl triethoxysilane.
Example 5:
the high fluorine content polymer emulsion consists of perfluoro decyl triethoxy silane in 50 wt%8F17(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorodecyl triethoxysilane in the perfluorodecyl triethoxysilane emulsion is 30%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
Method for preparing the high fluorine content polymer emulsion the method for preparing the high fluorine content polymer emulsion is substantially the same as in example 1 except that: the fluorine-containing alkyl silane is perfluorodecyl triethoxysilane.
Example 6:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane in 50 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 50%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%The solid content is about 50 percent, the product number is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 50g of perfluorooctyl triethoxysilane, adding 0.5g of emulsifier T-80, and stirring at 300rpm for 15min to obtain a mixed solution A for later use;
(2) weighing 49g of water, adding 0.5g of emulsifier S-40, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluorooctyl triethoxysilane emulsion, and defoaming is stable;
(4) And (3) adding 100g of fluorocarbon emulsion into the perfluorooctyl triethoxysilane emulsion, and dispersing for 10min at 800rpm to obtain the high fluorine content polymer emulsion.
Example 7:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane in 50 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 80%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 80g of perfluorooctyl triethoxysilane, adding 0.2g of emulsifier S-80, and stirring at 300rpm for 15min to obtain a mixed solution A for later use;
(2) weighing 19g of water, adding 0.8g of emulsifier OP-15, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluorooctyl triethoxysilane emulsion with stable defoaming;
(4) And (3) adding 100g of fluorocarbon emulsion into the perfluorooctyl triethoxysilane emulsion, and dispersing for 10min at 800rpm to obtain the high-fluorine-content polymer emulsion.
Example 8:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane C in 66.7 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion and 33.3 percent of fluorocarbon emulsion are compounded; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 50%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 50g of perfluorooctyl triethoxysilane, adding 0.5g of emulsifier T-80, and stirring at 300rpm for 15min to obtain a mixed solution A for later use;
(2) weighing 49g of water, adding 0.5g of emulsifier S-40, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluorooctyl triethoxysilane emulsion, and defoaming is stable;
(4) And (3) adding 50g of fluorocarbon emulsion into the perfluorooctyl triethoxysilane emulsion, and dispersing for 10min at 800rpm to obtain the high-fluorine-content polymer emulsion.
Example 9:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane [ C ] in 10 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 90 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 90%; the fluorocarbon emulsion is PVDF fluorocarbon emulsion.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the usage amounts of the perfluorooctyl triethoxysilane, the water and the PVDF fluorocarbon emulsion in the preparation method are different.
Example 10:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane C in 90 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 10 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 10%; the fluorocarbon emulsion is FEVE type fluorocarbon emulsion.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the dosages of the perfluorooctyl triethoxysilane, the water and the FEVE type fluorocarbon emulsion in the preparation method are different.
Example 11:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane [ C ] in 30 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 70 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 40%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the dosage of the perfluorooctyl triethoxysilane, the water and the fluorocarbon emulsion in the preparation method is different.
(II) preparation of Water-based paint
Example 12:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 50g of high-fluorine-content polymer emulsion, 10g of titanium dioxide, 15g of barium sulfate, 10g of wollastonite, 11.7g of water, 2g of dodecyl alcohol ester (film-forming aid), 50400.6 g of dispersing agent, BYK-0280.2 g of defoaming agent, 0.2g of pH regulator, 0.1g of bactericide MC and RM-20200.2 g of thickening agent; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 1.
The preparation method of the high-fluorine-content water-based concrete protective coating comprises the following steps:
a. adding deionized water into a high-speed dispersion machine, adding a dispersing agent 5040, stirring at 500rpm until the deionized water is uniformly dispersed, adding a defoaming agent BYK-028, eliminating bubbles, adding a pH regulator DMAE, and adjusting the pH to 8-10 to obtain slurry;
b. b, sequentially adding titanium dioxide, barium sulfate and wollastonite into the slurry prepared in the step a, and stirring at 1400rpm until the titanium dioxide, the barium sulfate and the wollastonite are uniformly dispersed;
c. transferring the slurry treated in the step b to a grinder, grinding the slurry until the fineness of the slurry is less than 10 mu m, and discharging the slurry;
d. and c, adding the high-fluorine-content polymer emulsion into the slurry treated in the step c, stirring at 800rpm for 5min, then adding the dodecyl alcohol ester, continuing stirring for 5min, then adding the thickening agent and the bactericide, and stirring at 800rpm for 10min to obtain the high-fluorine-content water-based concrete protective coating, which is recorded as sample 1.
Example 13:
example 13 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 2.
The high fluorine content aqueous concrete protective coating prepared in example 13 is designated as sample 2.
Example 14:
example 14 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 3.
The high fluorine content aqueous concrete protective coating prepared in example 14 is designated as sample 3.
Example 15:
example 15 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 4.
The high fluorine content aqueous concrete protective coating prepared in example 15 is designated as sample 4.
Example 16:
example 16 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 5.
The high fluorine content aqueous concrete protective coating prepared in example 16 is designated as sample 5.
Example 17:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 80g of high-fluorine-content polymer emulsion, 15.1g of water, 4g of dodecyl alcohol ester (film-forming aid), 0.5g of pH regulator DMAE, 0.1g of bactericide MC and 0.3g of thickener U5050; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 4.
The preparation method of the high-fluorine-content water-based concrete protective coating comprises the following steps:
a. adding the high-fluorine-content polymer emulsion and water into a high-speed dispersion machine at the same time, and stirring at 600rpm until the polymer emulsion and the water are uniformly dispersed to obtain slurry;
b. Adding dodecyl alcohol ester, a pH regulator DMAE and a bactericide MC into the slurry prepared in the step a in sequence, and stirring at 600rpm until the mixture is uniformly dispersed;
c. and c, adding a thickening agent U505 into the slurry treated in the step b, stirring and dispersing at 1000rpm for 15min to obtain the high-fluorine-content water-based concrete protective coating. This coating was an aqueous varnish and was denoted as sample 6.
Example 18:
the contents of example 18 are substantially the same as those of example 12, except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 6.
The high fluorine content waterborne concrete protective coating prepared in example 18 was designated as sample 7.
Example 19:
example 19 is substantially the same as example 17 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 6.
The high fluorine content aqueous concrete protective coating prepared in example 19 was designated as sample 8.
Example 20:
the contents of example 20 are substantially the same as those of example 12, except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 7.
The high fluorine content aqueous concrete protective coating prepared in example 20 is designated as sample 9.
Example 21:
the contents of example 21 are substantially the same as those of example 17, except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 7.
The high fluorine content aqueous concrete protective coating prepared in example 21 was designated as sample 10.
Example 22:
the contents of example 22 are substantially the same as those of example 12, except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 8.
The high fluorine content aqueous concrete protective coating prepared in example 22 is designated as sample 11.
Example 23:
example 23 is substantially the same as example 17 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 8.
The high fluorine content waterborne concrete protective coating prepared in example 23 is designated as sample 12.
Example 24:
the high-fluorine-content water-based concrete protective coating is prepared from the following raw materials: 30g of high-fluorine-content polymer emulsion, 20g of titanium dioxide, 20g of barium sulfate, 10g of wollastonite, 14.7g of water, 2g of dodecyl alcohol ester (film-forming aid), 50402 g of dispersing agent, 0.1g of defoaming agent BYK-0281 g of pH regulator, 0.1g of bactericide MC and 0.78 g of thickening agent RM-20200.1 g; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 7.
The preparation method of the high fluorine content water-based concrete protective coating is the same as that of the example 12.
Example 25:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 40g of high-fluorine-content polymer emulsion, 8g of titanium dioxide, 15g of barium sulfate, 5g of wollastonite, 27g of water, 3g of dodecyl alcohol ester (film-forming aid), 50400.5 g of dispersing agent, BYK-0280.2 g of defoaming agent, 0.5g of pH regulator, 0.3g of bactericide MC and RM-20200.5 g of thickening agent; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 7.
The preparation method of the high fluorine content water-based concrete protective coating is the same as that of the example 12.
Example 26:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 65g of high-fluorine polymer emulsion, 27.3g of water, 6g of dodecyl alcohol ester (film-forming aid), 0.5g of pH regulator DMAE, 0.2g of bactericide MC, and thickener U5051 g; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 7.
The preparation method of the high fluorine content water-based concrete protective coating is the same as that of the example 17.
And (III) detecting the fluorine content and the performance index of the water-based concrete protective coating prepared by the invention:
1. And (3) detecting fluorine content and performance indexes of samples 1 to 5:
the coating samples (sample 1 to sample 5) prepared in examples 12 to 16 were subjected to fluorine content measurement and performance index measurement, and the measurement results are shown in table 1. Wherein, the performance index detection comprises stability (the state of the coating after being placed for 7 days at room temperature), hardness, acid resistance, weather resistance and scrawling resistance (namely the cleanable grade); the hardness test refers to the standard GB/T6739 Pencil determination method for coating hardness; the acid resistance test refers to standard HG/T3792-; weather resistance test and evaluation reference standard GB/T1865-1997 Artificial weathering and Artificial radiation Exposure (filtered xenon arc radiation) for paints and varnishes; anti-graffiti reference standard JG/T304 & 2011 anti-graffiti paint for building (cleanable grade assessment is shown in Table 2).
TABLE 1 results of measuring fluorine content and performance index of coating samples prepared in examples 9 to 13
Figure BDA0002452613660000121
TABLE 2 cleanability grade of human engineering method
Grade Graffiti removal situation
Level 1 Can be removed by dry lint-free cotton cloth
Stage 2 Can be removed by 1% neutral water-based weak cleaning agent
Grade 3 Can be removed with orange-based detergent
4 stage Can be removed by anhydrous alcohol
Grade 5 The 4 cleaning materials can not be removed, or the coating after cleaning has obvious light loss, color change or other damages
The aqueous coating formulations described in examples 12 to 16 were identical in all the components and amounts except for the fluoroalkyl silane-containing component in the fluoroalkyl silane-containing emulsion. As can be seen from Table 1, the water-based paint compositions prepared in examples 12 to 16 have significant differences in fluorine content and properties, and among them, the water-based paint composition prepared in example 12 (sample 4) has a high fluorine content, excellent acid resistance and weather resistance, and good anti-graffiti properties of grade 3, with the best overall properties. Therefore, the water paint prepared by taking the perfluorooctyl triethoxysilane emulsion as the raw material has good comprehensive performance.
2. And (3) detecting fluorine content and performance indexes of samples 6 to 12:
the coating samples (sample 6 to sample 12) prepared in examples 17 to 23 were subjected to fluorine content measurement and performance index measurement, and the measurement results are shown in table 3.
Table 3 results of measuring fluorine content and performance index of coating samples prepared in examples 17 to 23
Figure BDA0002452613660000131
As can be seen from table 3, in the preparation of the colored paint coating (see example 15, example 18, and example 20), as the content of the fluoroalkyl silane, which is an active ingredient in the fluoroalkyl silane emulsion, increases, the fluorine content of the aqueous coating system gradually increases, and the weather resistance and the anti-graffiti property of the coating are gradually improved, with the anti-graffiti property level being at most 2; when the varnish coating (see example 17, example 19 and example 21) is prepared, along with the increase of the content of the fluorine-containing alkyl silane which is an active ingredient in the fluorine-containing alkyl silane emulsion, the fluorine content of a water-based coating system is gradually increased, the fluorine content reaches 17.5 percent at most, the weather resistance and the anti-graffiti property of the coating are also gradually improved, and the anti-graffiti property grade reaches 1 grade at most, which shows that the water-based coating prepared by the invention has strong stain resistance and better self-cleaning capability. Furthermore, it can be seen from the data in Table 3 that the graffiti resistance of the clear coat coating systems is superior to that of the pigmented coat coatings.
3. Comparison of the Performance of the aqueous concrete protective coating of the invention
To further verify the effect of the high fluorine content polymer emulsion of the present invention on the performance of the aqueous concrete protective coating, the aqueous concrete protective coating prepared in example 23 of the present invention was taken as an example for performance verification. Meanwhile, for comparison, the invention also provides the following comparative experiments, namely comparative experiment 1, comparative experiment 2 and comparative experiment 3.
Comparative experiment 1:
the content of comparative experiment 1 is substantially the same as in example 23, except that: the high fluorine content polymer emulsion in the water paint formula is replaced by fluorocarbon emulsion, and the dosage of the fluorocarbon emulsion is the same as that of the high fluorine content polymer emulsion in the embodiment 23; wherein the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
Comparative experiment 2:
the content of comparative experiment 2 is substantially the same as in example 23, except that: the high fluorine polymer emulsion in the water paint formulation was replaced with octyl triethoxysilane modified fluorocarbon emulsion, which was designated as polymer emulsion, and the amount of polymer emulsion used was the same as the high fluorine polymer emulsion in example 23.
The polymer emulsion is prepared by compounding 33.3 percent of octyl triethoxysilane, 33.3 percent of fluorocarbon emulsion and 33.4 percent of water according to mass percentage. Wherein the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the polymer emulsion comprises the following steps: 33.3g of fluorocarbon emulsion is weighed in a high-speed disperser, 33.3g of octyl triethoxysilane is added under the rotation speed of 600rpm for dispersing for 10min, and 33.4g of water is added for dispersing for 5 min. Thus obtaining the octyl triethoxy silane modified polymer emulsion.
Comparative experiment 3:
the content of comparative experiment 3 is substantially the same as in example 23, except that: the high fluorine content polymer emulsion in the water paint formula is replaced by hydrolyzed silane modified fluorocarbon emulsion, which is recorded as hydrolyzed silane modified polymer emulsion. The hydrolyzed silane-modified polymer emulsion was used in the same amount as the high fluorine content polymer emulsion of example 23.
The hydrolyzed silane modified polymer emulsion is prepared from 33.3 percent of hydrolyzed octyl triethoxysilane, 33.3 percent of fluorocarbon emulsion and 33.4 percent of deionized water in percentage by mass. Wherein the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The specific preparation method of the hydrolyzed silane modified polymer emulsion comprises the following steps:
(1) 152g of octyl triethoxysilane and 50g of ethanol are weighed and placed in a 500mL three-neck flask, the three-neck flask is heated to 75 ℃ under the stirring state, 24g of deionized water is dripped, the dripping is completed within 1 hour, the heat preservation reaction is carried out for 0.5 hour after the dripping is completed, the vacuum pumping is carried out, the ethanol generated in the reaction and added in the early stage is removed, and the hydrolyzed triethoxysilane can be obtained.
(2) 33.3g of fluorocarbon emulsion is taken to be placed in a high-speed dispersion machine, 33.3g of the hydrolyzed octyl triethoxysilane prepared in the step (1) is added under the rotation speed of 600rpm, the dispersion is carried out for 10min, 33.4g of deionized water is added, and the dispersion is carried out for 5 min. Thus obtaining the hydrolyzed silane modified polymer emulsion.
The fluorine content and the performance of the aqueous coating materials prepared in example 23 of the present invention, comparative experiment 1, comparative experiment 2 and comparative experiment 3 were measured, and the measurement results are shown in table 4.
TABLE 4 results of fluorine content and performance measurements of waterborne coatings prepared in example 23, comparative experiment 1-comparative experiment 3
Figure BDA0002452613660000151
As shown in Table 4, in comparative experiment 1, when the water-based paint is prepared by using the conventional water-based fluorocarbon emulsion without modification, the water-based paint has poor hardness, acid resistance, weather resistance and anti-graffiti property, the anti-graffiti property of the paint is tested by using an oil-based marking pen, and yellow traces remain after the paint is wiped by using alcohol. In a comparison experiment 2, the polymer emulsion is prepared by modifying fluorocarbon emulsion without special treatment by using common silane, the stability of the water-based paint prepared by the polymer emulsion is poor, and when the silane content is excessively large, a paint system is very easy to layer; in addition, the acid resistance, weather resistance and graffiti resistance of the water-based paint are poor. Comparative experiment 3 adopts modified fluorocarbon emulsion after silane hydrolysis to prepare polymer emulsion, and the compatibility of the water-based paint prepared from the polymer emulsion is improved to some extent, but hydrolyzed silane is extremely unstable, and gel is easily generated when the addition amount is too large, so that the use of the paint is influenced. Compared with a comparative experiment 1, a comparative experiment 2 and a comparative experiment 3, the water-based paint prepared by the polymer emulsion modified by the fluoroalkyl silane has the advantages that the hardness, the acid resistance, the weather resistance and the anti-graffiti property are greatly improved, the anti-graffiti property can reach level 1, and the performance is optimal. Therefore, the high-fluorine-content polymer emulsion prepared by modifying fluorocarbon emulsion with the fluoroalkyl silane-containing emulsion can be used as a film forming substance for preparing water-based paint, improves the fluorine content of the water-based paint, and greatly improves the weather resistance, chemical corrosion resistance and self-cleaning capability (stain resistance) of the paint.
The above description is only a few preferred embodiments of the present invention, and is not intended to limit the scope of the embodiments of the present invention. Various changes can be made within the scope of the concept of the technical scheme of the invention, and the changes are all within the protection scope of the invention.

Claims (7)

1. The high fluorine content polymer emulsion is characterized by being prepared by compounding 10-80 percent of fluorine-containing alkyl silane emulsion and 20-90 percent of fluorocarbon emulsion by mass percentage; the fluorine-containing alkyl silane emulsion is emulsified by fluorine-containing alkyl silaneThe product of (1), the fluorine-containing alkyl silane is perfluorooctyl triethoxysilane [ C ]6F13(CH2)2Si(OCH2CH3)3]；
The preparation method of the fluorine-containing alkyl silane emulsion comprises the following steps:
(1) adding an emulsifier A into the fluorine-containing alkyl silane, and stirring until the emulsifier A is uniformly dispersed to obtain a mixed solution A for later use;
(2) adding an emulsifier B into water, and stirring until the emulsifier B is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, and continuously stirring until the mixed solution A and the mixed solution B are completely emulsified after the addition is finished to obtain a fluorine-containing alkyl silane emulsion;
the emulsifier A is T-80 or S-80; the emulsifier B is any one of S-40, OP-20 and OP-15.
2. The high fluorine content polymer emulsion according to claim 1, wherein the rotation speed of the stirring in the step (3) is 800 to 1500 rpm.
3. The high fluorine content polymer emulsion of claim 1, wherein said fluorocarbon emulsion is one or more of a fluoroacrylate emulsion, a PVDF-based fluorocarbon emulsion, and a FEVE-based fluorocarbon emulsion.
4. The emulsion of claim 1, wherein the fluoroalkyl silane is present in an amount of 10 to 90% by weight of the emulsion.
5. Use of the high fluorine content polymer emulsion according to any one of claims 1 to 4 in an aqueous coating.
6. The high-fluorine-content water-based concrete protective coating is characterized by being prepared from the following raw materials in parts by weight: 30-80 parts of high-fluorine-content polymer emulsion, 0-50 parts of filler, 10-30 parts of water, 2-10 parts of film forming auxiliary agent, 0-0.5 part of pH regulator, 0-0.3 part of bactericide and 0.2-4 parts of auxiliary agent, wherein the high-fluorine-content polymer emulsion is the high-fluorine-content polymer emulsion disclosed by any one of claims 1-4; the auxiliary agent is one or more of a dispersing agent, a defoaming agent and a thickening agent.
7. The high fluorine content aqueous concrete protective coating according to claim 6, wherein the film forming aid is a dodecanol ester; the filler is one or more of titanium dioxide, barium sulfate and wollastonite.
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