CN116042181A - Inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent and preparation method thereof - Google Patents
Inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent and preparation method thereof Download PDFInfo
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- 239000004566 building material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 41
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 91
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011258 core-shell material Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 238000003541 multi-stage reaction Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 231100000252 nontoxic Toxicity 0.000 claims description 7
- 230000003000 nontoxic effect Effects 0.000 claims description 7
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- XTIIITNXEHRMQL-UHFFFAOYSA-N tripotassium methoxy(trioxido)silane Chemical compound [K+].[K+].[K+].CO[Si]([O-])([O-])[O-] XTIIITNXEHRMQL-UHFFFAOYSA-N 0.000 claims description 6
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 230000002045 lasting effect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 11
- 239000005871 repellent Substances 0.000 description 11
- 239000004575 stone Substances 0.000 description 11
- 238000004078 waterproofing Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000011449 brick Substances 0.000 description 7
- 239000004567 concrete Substances 0.000 description 7
- -1 tiles Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000002519 antifouling agent Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- AIPVRBGBHQDAPX-UHFFFAOYSA-N hydroxy(methyl)silane Chemical compound C[SiH2]O AIPVRBGBHQDAPX-UHFFFAOYSA-N 0.000 description 4
- 239000003223 protective agent Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000007903 penetration ability Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- BHGADZKHWXCHKX-UHFFFAOYSA-N methane;potassium Chemical compound C.[K] BHGADZKHWXCHKX-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- FXSGDOZPBLGOIN-UHFFFAOYSA-N trihydroxy(methoxy)silane Chemical compound CO[Si](O)(O)O FXSGDOZPBLGOIN-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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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
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Abstract
The invention relates to an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent and a preparation method thereof, belonging to the technical field of building material surface treatment. The treating agent is prepared by dispersing methyl silicate particles serving as a core and a core-shell structure coating serving as a shell and a fluorosilane film serving as a main component in ethanol, water or an ethanol-water mixed solvent. The treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted by water and then sprayed on the surface of a building material, and has simple and convenient use method; the treated building material has lasting waterproof, oil-proof and antifouling effects. The preparation method takes fluorosilane and methyl silicate as main raw materials, ethanol and water as solvents and dispersants, and is obtained by the composite reaction of fluorosilane and methyl silicate, and is cheap and good; the method has the advantages of easily obtained raw materials, no toxicity or harm, simple preparation process, mild conditions, strict and controllable technological parameters, high product yield, high yield, low cost, safe and environment-friendly production process and suitability for large-scale production.
Description
Technical Field
The invention relates to an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent and a preparation method thereof, belonging to the technical field of building material surface treatment.
Background
Inorganic nonmetallic building materials such as cement, stone, bricks, tiles, concrete and the like are basic structural materials of modern buildings. In practical application, the building materials are easily corroded by water, acidic or alkaline substances, salt, dust, plants or microorganisms and the like due to exposure, so that the strength of the building materials is reduced, the safety of the building is endangered, the surface pollution of the building is caused, the attractiveness of the building is influenced, and even the leakage of the building is possibly caused, and the service life of the building is reduced.
The organosilicon waterproofing agent has excellent waterproof, weather-proof and chemical corrosion resistance because of the good permeability of inorganic groups with similar properties with inorganic nonmetallic building materials on the surface of the building materials, and the organic groups have hydrophobic properties, so the organosilicon waterproofing agent is widely used as a first-generation building waterproofing material for protecting inorganic nonmetallic building materials such as cement, stone, bricks, tiles, concrete and the like. At present, silicone waterproofing agents are of the following types: methyl silanol, silicone resins, silicone emulsion and alkylalkoxysilanes. Methyl silanol has the characteristics of low volatile matter (VOC) release, low cost and convenient use. However, methyl silanol reacts with carbon monoxide (CO) and its water solubility is enhanced after a long time of action, which results in easy peeling of the coating and deterioration of waterproof durability. In addition, methyl silanol can cause wall yellowing and the like when being eroded by high alkalinity substances, and the quality and the appearance of the wall are affected. The organic silicon resin is a neutral resin, and must be dissolved in alcohol solvent when in use; however, alcohol solvents are flammable, have safety hazards, and are volatile and pollute the environment. Compared with the organic silicon resin, the organic silicon emulsion is more friendly to the environment, but the poor stability of the organic silicon emulsion limits the popularization and the application of the organic silicon emulsion. The alkylalkoxysilane has good durability and acid and alkali resistance, and is widely used for protecting the surfaces of various silicate-based building materials; however, when the alkyl group is too large, the penetration ability of the waterproofing agent on the surface of the building material is poor, and under the acid-base condition, the alkoxy group stability is poor, self-crosslinking is easy, and the penetration ability is also affected. Moreover, none of these materials possess oil repellency.
On the other hand, the methyl silicate is an inorganic nonmetallic building material waterproofing agent mainly used in China at present because of low price and ideal short-term protection effect. The silane coupling agent is adopted as the building waterproofing agent, has the advantages of simple operation, long waterproof time, safety, environmental protection, no influence on the next construction of the building and the like, is a high-end green product with excellent waterproof performance, and is generally adopted abroad at present in spite of higher price; and the silane coupling agent is used for building waterproofing in China, so that the research on the silane coupling agent for building waterproofing is started later, and the silane coupling agent-based waterproofing product produced and sold in China is not too much, so that the silane coupling agent has huge market potential in China as a novel waterproofing product.
In a word, at present, many reports and products exist on the waterproof treatment of inorganic nonmetallic building materials such as cement, stone, bricks, tiles, concrete and the like, but the problems that the waterproof effect of the treated products is not durable, oil is not prevented at all or the oil resistance is poor exist generally, and the problem that the buildings adopting the building materials are polluted easily for a long time exist.
The fluorosilane has the characteristics of hydrophobicity and oleophobicity because of low surface energy of fluorine-containing groups, is coated on the surface of inorganic nonmetallic building materials, has good waterproof, oil-proof and antifouling properties, and has the characteristics of long duration of waterproof effect and easy cleaning of oil-proof and antifouling surfaces. However, fluorosilane is expensive and is difficult to be used on a large scale as a water-repellent, oil-repellent and stain-repellent treatment agent for building materials alone. On the other hand, methyl silicate is inexpensive and has an ideal short-term water-repellent effect, but does not have an oil-repellent effect. If the special features of the water-proof oil-proof antifouling agent can be combined, the water-proof oil-proof antifouling agent can be designed, the cost is low, and the building material water-proof oil-proof antifouling agent can be used in a large scale, so that the building material water-proof oil-proof antifouling agent has a wide market application prospect. However, methylsilicate is readily soluble in water but insoluble in ethanol, and is usually used directly after dilution with water, while fluorosilane is insoluble in water and readily hydrolyzed, and is usually used after dilution with ethanol; therefore, both methyl silicate and fluorosilane cannot generally be used in combination.
In order to solve the problems, the invention provides an inorganic nonmetallic building material waterproof oil-proof antifouling treatment agent based on a methylsilicate@fluorosilane core-shell structure coating and a preparation method thereof. In the technology provided by the invention, fluorosilane and methylsilicate are used as main raw materials, ethanol and water are used as solvents and dispersants, and a special reaction process is adopted to obtain the methylsilicate core-shell cladding structural material subjected to surface modification by fluorosilane, namely the methylsilicate@fluorosilane core-shell cladding. The treating agent prepared by adopting the technical scheme of the invention has stable physical and chemical properties, can be mutually dissolved with water, can be used after being diluted with water directly, has simple and convenient use method, has excellent waterproof, oil-proof and antifouling effects, and is cheap and good. In addition, when the treating agent provided by the invention is prepared, raw materials are easy to obtain, nontoxic and harmless, the preparation process is simple, the conditions are mild, the process parameters are strictly controllable, the product yield is high, the cost is low, and the production and use processes are safe and environment-friendly, so that the treating agent is suitable for large-scale production.
Disclosure of Invention
The invention aims at providing an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on a methylsilicate@fluorosilane core-shell structure coating. The main component of the treating agent is a methylsilicate core-shell coating structure material subjected to surface modification by fluorosilane, wherein methylsilicate particles are taken as cores, fluorosilane films are taken as shells, so that a methylsilicate@fluorosilane core-shell structure coating with the diameter of 20-300nm is formed, and the treating agent is obtained by dispersing by ethanol, water or an ethanol-water mixed solvent. The treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted by water, and is used for the surface treatment of inorganic nonmetallic building materials such as cement, stone, bricks, tiles, concrete and the like, and the using method is simple and convenient; the treating agent has the advantages of fluorosilane and methyl silicate, and has high permeation capacity on inorganic non-metal building material, such as cement, stone, brick, tile, concrete, etc. and excellent waterproof, oil-proof and antifouling effects, and the problems of waterproof, oil-proof and antifouling performance when the methyl silicate is used alone are solved. In addition, the treating agent also effectively solves the problems of incompatibility, non-uniformity and unstable performance of the methyl silicate and the fluorosilane in the independent use process; in addition, the treating agent disclosed by the invention uses methyl silicate as a main protective agent and fluorosilane as a secondary protective agent, so that the problem of high cost when the fluorosilane is singly used as the treating agent is solved.
The second purpose of the invention is to provide a preparation method of the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating. When the treating agent is prepared by the technical scheme of the invention, raw materials are easy to obtain, nontoxic and harmless, the preparation process is simple, the conditions are mild, the process parameters are strictly controllable, the product yield is high, the cost is low, the production process is safe and environment-friendly, and the treating agent is suitable for large-scale production.
In order to achieve the aim, the inorganic nonmetallic building material waterproof, oil-proof and anti-fouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating is characterized in that the main component of the treatment agent is a methylsilicate core-shell structure coating material subjected to surface modification by fluorosilane, wherein methylsilicate particles are taken as cores, fluorosilane films are taken as shells, the methylsilicate@fluorosilane core-shell structure coating is formed, and the inorganic nonmetallic building material waterproof, oil-proof and anti-fouling treatment agent is obtained by dispersing the methylsilicate@fluorosilane core-shell structure coating with the diameter of 20-300nm in ethanol, water or an alcohol-water mixed solvent. The treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted with water for use, and has excellent waterproof, oil-proof and antifouling effects; and the raw materials for preparing the treating agent are easy to obtain, nontoxic and harmless, the preparation process is simple, the use method is simple, safe and environment-friendly, and the product has excellent performance and low price.
The invention provides a preparation method of an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on a methylsilicate@fluorosilane core-shell structure coating, which is characterized in that the method is prepared by taking fluorosilane and methylsilicate as main raw materials, ethanol and water as solvents and dispersing agents, and carrying out a composite reaction on the fluorosilane and the methylsilicate.
The invention provides a preparation method of an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on a methylsilicate@fluorosilane core-shell structure coating, which comprises the following steps:
the preparation method comprises the following steps:
(1) Firstly, in a three-necked bottle equipped with a reflux condensing device, fluorosilane is dissolved in ethanol and stirred and dispersed uniformly;
(2) Then adding methyl silicate powder, stirring and dispersing uniformly;
(3) Reflux heating the mixture obtained in the step (2), and preserving heat for a period of time;
(4) And (3) dropwise adding deionized water into the sample obtained in the step (3) under the condition of continuous reflux heating, and stirring until the solid disappears, thus obtaining the inorganic nonmetallic building material waterproof oil-proof antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
In the above-mentioned method of preparation, the fluorosilane in the step (1) is 1H, 2H-perfluoro decyl triethoxysilane 1H, 2H-perfluorooctyl trimethoxysilane, 1H, 2H-perfluorodecyl trimethoxysilane 1H, 2H-perfluorooctyl trimethoxysilane 1H, 2H-perfluorodecyl trimethoxysilane.
In the above preparation method, in the step (1), the ethanol is reagent grade absolute ethanol.
In the preparation method, the mass ratio of the fluorosilane to the ethanol in the step (1) is 1:100-1:20.
In the above preparation method, the methyl silicate in the step (2) is mainly one or two of potassium methyl silicate and sodium methyl silicate.
In the preparation method, the mass ratio of the methyl silicate in the step (2) to the fluorosilane in the step (1) is 1:20-1:5.
In the preparation method, the heating temperature in the step (3) is 60-80 ℃, and the heat preservation time is 6-12h.
In the preparation method, the heating temperature in the step (4) is 40-80 ℃.
In the preparation method, the mass ratio of the deionized water added in the step (4) to the methyl silicate added in the step (2) is 8:1-10:1.
The preparation method comprises the following steps:
(1) Firstly, adding ethanol and deionized water into a three-necked bottle provided with a reflux condensing device, and stirring and dispersing uniformly;
(2) Then adding methyl silicate, stirring and dispersing until the methyl silicate is completely dissolved;
(3) Then adding fluorosilane into the solution obtained in the step (2), and stirring and dispersing uniformly;
(4) Reflux heating the mixture obtained in the step (3), and preserving heat for a period of time;
(5) And (3) adding deionized water into the sample obtained in the step (4) for dilution to obtain the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
In the preparation method, the dosage ratio of the ethanol to the deionized water in the step (1) is 1:3-1:5, and the ethanol is industrial ethanol.
In the above preparation method, the methyl silicate in the step (2) is mainly one or two of potassium methyl silicate and sodium methyl silicate.
In the preparation method, the mass ratio of the methyl silicate in the step (2) to the deionized water in the step (1) is 1:6-1:3.
In the above-mentioned method of preparation, the fluorosilane in the step (3) is 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro octyl trimethoxysilane one or more of 1H, 2H-perfluorodecyl trimethoxysilane, 1H, 2H-perfluorooctyl triethoxysilane.
In the preparation method, the mass ratio of the fluorosilane in the step (3) to the methyl silicate in the step (2) is 1:20-1:5.
In the preparation method, the heating temperature in the step (4) is 50-80 ℃, and the heat preservation time is 6-12h.
In the preparation method, the ratio of the amount of deionized water added in the step (5) to the total amount of the solution obtained in the step (4) is 1:1-3:1.
The invention is characterized in that:
(1) The invention provides a treating agent which is an inorganic nonmetallic building material waterproof, oil-proof and antifouling treating agent based on a methylsilicate@fluorosilane core-shell structure coating. The main component of the treating agent is a methylsilicate core-shell coating structure material subjected to surface modification by fluorosilane, wherein methylsilicate particles are taken as cores, fluorosilane films are taken as shells, so that a methylsilicate@fluorosilane core-shell structure coating with the diameter of 20-300nm is formed, and the treating agent is obtained by dispersing by ethanol, water or an ethanol-water mixed solvent.
(2) The preparation method of the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating provided by the invention is characterized in that fluorosilane and methylsilicate are used as main raw materials, ethanol and water are used as solvents and dispersants, and the treatment agent is obtained through the composite reaction of fluorosilane and methylsilicate.
The invention has the advantages that:
(1) The treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted by water, and is then used for the surface treatment of inorganic nonmetallic building materials such as cement, stone, bricks, tiles, concrete and the like, and the use method is simple and convenient, has stable performance and long duration.
(2) The treating agent has the advantages of fluorosilane and methyl silicate, has strong penetrating power on the surfaces of inorganic nonmetallic building materials such as cement, stone, bricks, tiles, concrete and the like, has excellent waterproof, oil-proof and antifouling effects, and solves the problems of water resistance, no durability, no oil-proof and no antifouling when the methyl silicate is singly used as the treating agent.
(3) The treating agent also effectively solves the problems of incompatibility, non-uniformity and unstable performance of the methyl silicate and the fluorosilane in the independent use process; in addition, the treating agent disclosed by the invention adopts methyl silicic acid as a main protective agent and fluorosilane as a secondary protective agent, so that the problem of high cost when the fluorosilane is singly used as the treating agent is solved.
(4) When the treating agent is prepared by the technical scheme of the invention, raw materials are easy to obtain, nontoxic and harmless, the preparation process is simple, the conditions are mild, the process parameters are strictly controllable, the product yield is high, the cost is low, the production process is safe and environment-friendly, and the treating agent is suitable for large-scale production.
(5) The treating agent can be mutually dissolved with water, and when the treating agent is used, the condition that the fluorosilane treating agent is singly used as an organic solvent is avoided, the using amount of the organic solvent is reduced, and the construction and use processes are more convenient, safer and more environment-friendly.
(6) By adopting the technical scheme of the invention, the raw materials for preparing the treating agent are easy to obtain, the cost is low, the preparation process is simple, the use method is simple and convenient, and the product has excellent performance and low price.
Drawings
FIG. 1 is a scanning electron micrograph of a dried sample of the treating agent prepared in example 1 of the present invention
FIG. 2 is a photograph showing the water-repellent, oil-repellent and stain-repellent effects of the product of example 1 of the present invention after construction with the prepared treating agent
FIG. 3 is a scanning electron micrograph of a dried sample of the treating agent prepared in example 2 of the present invention
FIG. 4 is a photograph showing the water-repellent, oil-repellent and stain-repellent effects of the product of example 2 of the present invention after construction with the prepared treating agent
Detailed Description
The technical scheme of the invention is further described below by combining examples.
The invention provides an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on a methylsilicate@fluorosilane core-shell structure coating, which is characterized in that the main component of the treatment agent is a methylsilicate core-shell coating structure material subjected to surface modification by fluorosilane, wherein methylsilicate particles are taken as cores, fluorosilane films are taken as shells to form the methylsilicate@fluorosilane core-shell structure coating, and the coating is 20-300nm in diameter and is obtained by dispersing the methylsilicate@fluorosilane core-shell structure coating by ethanol, water or an ethanol-water mixed solvent; the treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted with water for use, and has excellent waterproof, oil-proof and antifouling effects; and the raw materials for preparing the treating agent are easy to obtain, nontoxic and harmless, the preparation process is simple, the use method is simple, safe and environment-friendly, and the product has excellent performance and low price.
The invention provides a preparation method of an inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on a methylsilicate@fluorosilane core-shell structure coating, which is characterized in that the method is prepared by taking fluorosilane and methylsilicate as main raw materials, ethanol and water as solvents and dispersing agents, and carrying out a composite reaction on the fluorosilane and the methylsilicate.
The preparation method of the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating provided by the invention comprises the following steps:
(1) Firstly, in a three-necked bottle equipped with a reflux condensing device, fluorosilane is dissolved in ethanol and stirred and dispersed uniformly;
(2) Then adding methyl silicate powder, stirring and dispersing uniformly;
(3) Reflux heating the mixture obtained in the step (2), and preserving heat for a period of time;
(4) And (3) dropwise adding deionized water into the sample obtained in the step (3) under the condition of continuous reflux heating, and stirring until the solid disappears, thus obtaining the inorganic nonmetallic building material waterproof oil-proof antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
(5) In the above-mentioned method of preparation, the fluorosilane in the step (1) is 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro octyl trimethoxysilane one or more of 1H, 2H-perfluorodecyl trimethoxysilane, 1H, 2H-perfluorooctyl triethoxysilane, the ethanol is reagent grade absolute ethanol, and the mass ratio of the fluorosilane to the ethanol is 1:100-1:20.
(6) In the preparation method, the methyl silicate in the step (2) is mainly one or two of potassium methyl silicate and sodium methyl silicate; and the mass ratio of the methyl silicate in the step (2) to the fluorosilane in the step (1) is 1:20-1:5.
(7) In the preparation method, the heating temperature in the step (3) is 60-80 ℃, and the heat preservation time is 6-12h; the heating temperature in the step (4) is 40-80 ℃; and the mass ratio of the deionized water added in the step (4) to the methyl silicate added in the step (2) is 8:1-10:1.
The preparation method II of the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating provided by the invention comprises the following steps:
(1) Firstly, adding ethanol and deionized water into a three-necked bottle provided with a reflux condensing device, and stirring and dispersing uniformly;
(2) Then adding methyl silicate, stirring and dispersing until the methyl silicate is completely dissolved;
(3) Then adding fluorosilane into the solution obtained in the step (2), and stirring and dispersing uniformly;
(4) Reflux heating the mixture obtained in the step (3), and preserving heat for a period of time;
(5) And (3) adding deionized water into the sample obtained in the step (4) for dilution to obtain the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
(6) In the preparation method, the dosage ratio of the ethanol to the deionized water in the step (1) is 1:3-1:5, and the ethanol is industrial ethanol; the methyl silicate in the step (2) is mainly one or two of potassium methyl silicate and sodium methyl silicate; the mass ratio of the methyl silicate in the step (2) to the deionized water in the step (1) is 1:6-1:3.
(7) In the above-mentioned method of preparation, the fluorosilane in the step (3) is 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro octyl trimethoxysilane one or more of 1h,2 h-perfluorodecyl trimethoxysilane, 1h,2 h-perfluorooctyl triethoxysilane; the mass ratio of the fluorosilane in the step (3) to the methyl silicate in the step (2) is 1:20-1:5; the ratio of the dosage of the deionized water added in the step (5) to the total amount of the solution obtained in the step (4) is 1:1-3:1.
(8) In the preparation method, the heating temperature in the step (4) is 50-80 ℃, and the heat preservation time is 6-12h.
The obtained inorganic nonmetallic building material waterproof, oil-proof and anti-fouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating is colorless and transparent in appearance, and is observed under a scanning electron microscope to be a methylsilicate core-shell structure coating material subjected to surface modification by fluorosilane after being dried, wherein methylsilicate particles are cores, fluorosilane films are shells to form the methylsilicate@fluorosilane core-shell structure coating, and the diameter of the methylsilicate@fluorosilane core-shell structure coating is 20-300nm. The treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted with water for use, and has excellent waterproof, oil-proof and antifouling effects; and the raw materials for preparing the treating agent are easy to obtain, nontoxic and harmless, the preparation process is simple, the use method is simple, safe and environment-friendly, and the product has excellent performance and low price.
Example 1: firstly, 1000g of ethanol is added into a 5L three-necked flask equipped with a reflux condensing device, 20g of 1H, 2H-perfluoro decyl trimethoxy silane is dissolved in the ethanol, and the mixture is stirred and dispersed uniformly; then adding 200g of sodium methyl silicate powder, and stirring and dispersing uniformly; reflux heating the mixture at 80deg.C, and maintaining the temperature for 8 hr; finally, under the condition of continuously refluxing and heating at 80 ℃, dropwise adding deionized water and stirring until the solid disappears, and dropwise adding 1500g of deionized water to obtain a colorless transparent solution, namely the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
Taking 2mL of the obtained solid obtained by drying the treating agent, observing the solid under an electron microscope, and finding that the solid is a core-shell coating structure material with the diameter of 100-250nm, and analyzing by an energy spectrometer attached to the electron microscope, wherein the methylsilicate particles are cores, and the fluorosilane film is a shell (see figure 1). Taking 100g of the treating agent, diluting with 3kg of water at room temperature to prepare a treating agent solution, and spraying the prepared treating agent solution on a prepared solution of 1m 2 The surface of the stone slab is about 10-50g of the treating agent solution, and after the stone slab is left to be naturally dried for 6 hours, the pollutant solution can not infiltrate at all on the surface of the stone slab, and the stone has excellent waterproof, oil-proof and pollution-proof effects (see figure 2).
Example 2: firstly, 200g of ethanol and 750g of deionized water are added into a 5L three-necked flask equipped with a reflux condensing device, and the mixture is stirred and dispersed uniformly; then 200g of methyl potassium silicate is added, stirred and dispersed until the mixture is completely dissolved; then 10g of 1H, 2H-perfluorooctyl trimethoxy silane is added into the obtained solution, and the mixture is stirred and dispersed uniformly; then, the mixture is heated under reflux at 60 ℃ and is kept for 10 hours, and the mixture is changed into transparent solution from a white turbidity state; finally, adding 1200g of deionized water into the obtained transparent solution for dilution, thus obtaining the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
Taking 2mL of the obtained solid obtained by drying the treating agent, observing the solid under an electron microscope, and finding that the solid is a core-shell coating structure material with the diameter of 20-100nm, and analyzing by an energy spectrometer attached to the electron microscope, wherein the methylsilicate particles are cores, and the fluorosilane film is a shell (see figure 3). Taking 100g of the treating agent, diluting with 3kg of water at room temperature to prepare a treating agent solution, and spraying the prepared treating agent solution on a prepared solution of 1m 2 About 30-80g of the treating agent solution is used for the surface of the cement board, after the cement board is left for 4 hours to be naturally dried, the pollutant solution cannot infiltrate at all on the surface of the cement board, and the cement board has excellent waterproof, oil-proof and pollution-proof effects (see figure 4).
Claims (9)
1. The inorganic nonmetallic building material waterproof, oil-proof and anti-fouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating is characterized in that the main component of the treatment agent is a methylsilicate core-shell structure coating material subjected to surface modification by fluorosilane, wherein methylsilicate particles are taken as cores, fluorosilane films are taken as shells, the methylsilicate@fluorosilane core-shell structure coating with the diameter of 20-300nm is formed, and the treatment agent is obtained by dispersing ethanol, water or an alcohol-water mixed solvent; the treating agent has stable physical and chemical properties, can be mutually dissolved with water, can be directly diluted with water for use, and has excellent waterproof, oil-proof and antifouling effects; and the raw materials for preparing the treating agent are easy to obtain, nontoxic and harmless, the preparation process is simple, the use method is simple, safe and environment-friendly, and the product has excellent performance and low price.
2. The preparation method of the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent for the methylsilicate@fluorosilane core-shell structure coating material according to claim 1, which is characterized in that the method is prepared by taking fluorosilane and methylsilicate as main raw materials, ethanol and water as solvents and dispersing agents, and carrying out a composite reaction on fluorosilane and the methylsilicate; the method comprises the following steps:
(1) Firstly, in a three-necked bottle equipped with a reflux condensing device, fluorosilane is dissolved in ethanol and stirred and dispersed uniformly;
(2) Then adding methyl silicate powder, stirring and dispersing uniformly;
(3) Reflux heating the mixture obtained in the step (2), and preserving heat for a period of time;
(4) And (3) dropwise adding deionized water into the sample obtained in the step (3) under the condition of continuous reflux heating, and stirring until the solid disappears, thus obtaining the inorganic nonmetallic building material waterproof oil-proof antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
3. A process according to claim 2, wherein, the fluorosilane in the step (1) is 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro octyl trimethoxysilane one or more of 1H, 2H-perfluorodecyl trimethoxysilane, 1H, 2H-perfluorooctyl triethoxysilane, the ethanol is reagent grade absolute ethanol, and the mass ratio of the fluorosilane to the ethanol is 1:100-1:20.
4. The method according to claim 2, wherein the methyl silicate in the step (2) is mainly one or two of potassium methyl silicate and sodium methyl silicate; and the mass ratio of the methyl silicate in the step (2) to the fluorosilane in the step (1) is 1:20-1:5.
5. The preparation method according to claim 2, wherein the heating temperature in the step (3) is 60-80 ℃ and the heat preservation time is 6-12h; the heating temperature in the step (4) is 40-80 ℃; and the mass ratio of the deionized water added in the step (4) to the methyl silicate added in the step (2) is 8:1-10:1.
6. The preparation method of the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent for the methylsilicate@fluorosilane core-shell structure coating material according to claim 1, which is characterized in that the method is prepared by taking fluorosilane and methylsilicate as main raw materials, ethanol and water as solvents and dispersing agents, and carrying out a composite reaction on fluorosilane and the methylsilicate; the method comprises the following steps:
(1) Firstly, adding ethanol and deionized water into a three-necked bottle provided with a reflux condensing device, and stirring and dispersing uniformly;
(2) Then adding methyl silicate, stirring and dispersing until the methyl silicate is completely dissolved;
(3) Then adding fluorosilane into the solution obtained in the step (2), and stirring and dispersing uniformly;
(4) Reflux heating the mixture obtained in the step (3), and preserving heat for a period of time;
(5) And (3) adding deionized water into the sample obtained in the step (4) for dilution to obtain the inorganic nonmetallic building material waterproof, oil-proof and antifouling treatment agent based on the methylsilicate@fluorosilane core-shell structure coating.
7. The method according to claim 6, wherein the ratio of ethanol to deionized water in the step (1) is 1:3-1:5, and the ethanol is industrial ethanol; the methyl silicate in the step (2) is mainly one or two of potassium methyl silicate and sodium methyl silicate; the mass ratio of the methyl silicate in the step (2) to the deionized water in the step (1) is 1:6-1:3.
8. A process according to claim 6, wherein, the fluorosilane in the step (3) is 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro octyl trimethoxysilane one or more of 1h,2 h-perfluorodecyl trimethoxysilane, 1h,2 h-perfluorooctyl triethoxysilane; the mass ratio of the fluorosilane in the step (3) to the methyl silicate in the step (2) is 1:20-1:5; the ratio of the dosage of the deionized water added in the step (5) to the total amount of the solution obtained in the step (4) is 1:1-3:1.
9. The process according to claim 6, wherein the heating temperature in the step (4) is 50 to 80℃and the holding time is 6 to 12 hours.
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