CN115304403A - Hydrophobic composite material for protecting stone cultural relics and preparation method thereof - Google Patents
Hydrophobic composite material for protecting stone cultural relics and preparation method thereof Download PDFInfo
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- CN115304403A CN115304403A CN202211148454.4A CN202211148454A CN115304403A CN 115304403 A CN115304403 A CN 115304403A CN 202211148454 A CN202211148454 A CN 202211148454A CN 115304403 A CN115304403 A CN 115304403A
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- 239000004575 stone Substances 0.000 title claims abstract description 45
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 12
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VUQBDNXYMFPPFM-UHFFFAOYSA-N 2,3,5,6-tetrahydroxyterephthalic acid Chemical compound OC1=C(C(=O)O)C(=C(C(=C1O)C(=O)O)O)O VUQBDNXYMFPPFM-UHFFFAOYSA-N 0.000 claims description 6
- PVQMWZDAOPIATO-UHFFFAOYSA-N 2,3,5-trihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C(O)=C1O PVQMWZDAOPIATO-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 4
- LBTSNEJGMVFUEW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,8,8,8-dodecafluorooctoxy-dimethoxy-propylsilane Chemical compound FC(C(C(C(C(F)(F)CO[Si](OC)(OC)CCC)(F)F)(F)F)(F)F)CC(F)(F)F LBTSNEJGMVFUEW-UHFFFAOYSA-N 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 13
- 230000004913 activation Effects 0.000 description 10
- 239000011435 rock Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000003075 superhydrophobic effect Effects 0.000 description 5
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- 238000007906 compression Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000012669 compression test Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000915 pathological change Toxicity 0.000 description 2
- 230000036285 pathological change Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- COGJUEPPUXTFJM-UHFFFAOYSA-N CO[SiH](OC)OC.FC(CC)(F)F Chemical compound CO[SiH](OC)OC.FC(CC)(F)F COGJUEPPUXTFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
Abstract
The invention relates to a hydrophobic composite material for protecting stone cultural relics and a preparation method thereof, wherein a mixed solution of absolute ethyl alcohol and deionized water is prepared, the pH is adjusted to be 4-5, a fluorosilane coupling agent is added into the mixed solution, the mixture is fully stirred and reacts to obtain a solution B, and UIO-66- (OH) n And (2) putting the powder into a three-neck flask, dropwise adding the solution B into the three-neck flask at a low speed, carrying out ultrasonic treatment and electric stirring on the mixed system, drying, solidifying and grinding the mixed system to obtain UIO-O-FS powder, adding the powder into a dispersant solution, and carrying out ultrasonic treatment to obtain UIO-O-FS sol, namely the hydrophobic composite material for protecting the stone cultural relics. The stone cultural relic protection material prepared by the invention is a novel nano composite material with a microporous molecular structure, has the characteristics of hydrophobicity, breathability and the like, can effectively prevent the attachment and permeation of liquid water and the condensation of water vapor, and has important significance for the protection of stone cultural relics.
Description
Technical Field
The invention belongs to the technical field of preparation of cultural relic protection materials, and particularly relates to a hydrophobic composite material for protecting stone cultural relics and a preparation method thereof.
Background
The Chinese has a very rich cultural heritage, wherein the stone cultural relics are the treasure for human beings and the historical memory of the Chinese, and the Chinese can better know and deeply understand the history. The stone cultural relic material has the greatest advantage of being capable of being stored for a longer time compared with other materials.
However, with the continuous improvement of modern industrialization level and the increase of economy, natural disasters such as acid rain, acid mist and the like are frequent due to harmful gases and the like discharged from industrial chimneys, and the weathering and erosion degree of the stone cultural relics is increased. And most of the stone cultural relics are exposed in the natural environment, the surfaces of the stone cultural relics are eroded by the nature to become fuzzy and damaged, some of the stone cultural relics are even disappeared, the stone cultural relics also bear the influence of physical, chemical, biological and other weathering effects, even the harm caused by human factors to the stone cultural relics, the damage to the interiors of the stone cultural relics is unavoidable, and the research value and the appreciation value of the stone cultural relics are seriously influenced. Therefore, protection of stone cultural relics from damage has become a major issue.
The existing protective materials have a plurality of defects, such as waxes, which have high viscosity and can not permeate into rocks, and generally outdoor cultural relics are not protected by the waxes; inorganic materials are difficult to permeate into deep layers of rocks, are high in brittleness, and the weathering of the rocks is aggravated due to poor adhesion and the like. Therefore, the invention aims to provide a novel stone cultural relic protection material to make up for the defects of the existing material.
Disclosure of Invention
In order to solve the problems, the invention provides a hydrophobic composite material for protecting stone cultural relics and a preparation method thereof, wherein a hydrolyzed fluorosilane coupling agent and UIO-66- (OH) n (n = 1-4) carrying out grafting reaction, adding a dispersant solution, and constructing the microporous surface of the super-hydrophobic metal organic framework by a method of modifying and bridging ligand nodes, wherein the prepared material has a pore molecular structure, so that the material has the characteristics of hydrophobicity, breathability and the like, can effectively prevent the attachment and permeation of liquid water and the condensation of water vapor, avoids a series of pathological changes caused by water on the surface of the stone cultural relic and in the stone cultural relic, and has important significance for the protection of the stone cultural relic.
The invention is realized by the following technical scheme, and the preparation method of the hydrophobic composite material for protecting the stone cultural relics, which is provided by the invention, comprises the following steps:
(1) Firstly, preparing a mixed solution of absolute ethyl alcohol and deionized water, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 1: (3-5) adjusting the pH value of the mixed solution to 4-5 by using glacial acetic acid to obtain a solution A, adding a fluorosilane coupling agent into the solution A, and stirring for sufficient reaction, wherein the stirring time is 5-8min, and the rotating speed is 1500r/min to obtain a solution B;
(2) UIO-66- (OH) n Putting the powder into a three-neck flask, dropwise adding the solution B obtained in the step (1) into the three-neck flask at a low speed of 20-45 drops/min by using a separating funnel, carrying out ultrasonic and stirring treatment on a mixed system at the temperature of 30-50 ℃, wherein the treatment time is 10-30min, and the stirring speed is 60-150r/min; then, drying and curing the UIO-O-FS powder in an oven to obtain UIO-O-FS particles, and grinding the UIO-O-FS particles by a mortar to obtain light yellow UIO-O-FS powder;
(3) Preparing 3-10 wt% of deionized water solution of a dispersant, uniformly stirring, adding the light yellow UIO-O-FS powder obtained in the step (2), and performing ultrasonic treatment to obtain sol, namely the hydrophobic composite material for protecting the stone cultural relics.
Further, the dosage of the deionized water in the step (1) is 3-8mL.
Further, the addition amount of the fluorosilane coupling agent is 1-5mL.
Preferably, the fluorosilane coupling agent is one or more selected from dodecafluoroheptylpropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, nonafluorohexyltrimethoxysilane, trifluoropropyltrimethoxysilane and tridecafluorooctyltrimethoxysilane.
Preferably, in step (2), UIO-66- (OH) n The volume ratio of the powder to the solution B is 1: (0.8-1.5), UIO-66- (OH) n The powder is UIO-66-OH, UIO-66- (OH) 2 、UIO-66-(OH) 3 、UIO-66-(OH) 4 One or more of (a).
Further, the UIO-66- (OH) n The powder is prepared by the following method: zirconium tetrachloride and polyhydroxy terephthalic acid are mixed according to the molar ratio of1:1 is dissolved in DMF, a magnetic stirrer is used for stirring the mixed solution, the mixed solution is stirred at a uniform speed of 1500r/min for 30min, then the mixture is transferred to a stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene, and the mixture is heated and reacted for 12h at 120 ℃; cooling the product to room temperature, centrifuging at 10000r/min for 10min to obtain powder, washing the powder with DMF and anhydrous ethanol for 3 times, and drying in oven at 120 deg.C for 12h to obtain UIO-66- (OH) n ；
The polyhydroxy terephthalic acid is one or more of 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2,3, 5-trihydroxy terephthalic acid and 2,3,5, 6-tetrahydroxy terephthalic acid; preparing 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2,3, 5-trihydroxy terephthalic acid and 2,3,5, 6-tetrahydroxy terephthalic acid according to the method to obtain UIO-66-OH and UIO-66- (OH) respectively 2 、UIO-66-(OH) 3 、UIO-66-(OH) 4 。
Further, the temperature of the oven drying in the step (2) is 80 ℃.
Preferably, the mass ratio of the UIO-O-FS powder to the dispersing agent in the step (3) is 1: (1-1.5).
Preferably, the dispersant is one or more selected from sodium polyacrylate, sodium carboxymethylcellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyethylene glycol 400, polyethylene glycol 2000 and polyethylene glycol 4000.
Compared with the prior art, the invention has obvious advantages and beneficial effects. It has at least the following advantages:
(1) The stone cultural relic protection material prepared by the invention is a novel nano composite material with a microporous molecular structure, has the characteristics of hydrophobicity, breathability and the like, can effectively prevent the attachment and permeation of liquid water and the condensation of water vapor, further avoids a series of pathological changes caused by water on the surface of the stone cultural relic and in the stone cultural relic, avoids the erosion of acid rain on the stone cultural relic, and has a self-cleaning function, so that the stone cultural relic can be better protected. In addition, the hydrophobic material can form an air-permeable channel, so that air and moisture inside and outside the stone cultural relic can circulate, the erosion probability of the stone cultural relic is greatly reduced, and the ornamental value, the mechanical property and the like of the stone cultural relic are not reduced.
(2) The preparation process of the invention is simple and convenient, the method of ultrasonic treatment and electric stirring is adopted, the operation condition is easy to control, the product quality is stable, and UIO-66- (OH) can be ensured by controlling the dropping speed of the modifier and adding a proper amount of dispersant solution n The grafting effect of the powder and the hydrophobic group is better.
(3) The material prepared by the synthesis method provided by the invention avoids the defects of the traditional stone cultural relic protection material, such as wax which has high viscosity and can not permeate into the interior of rock and is not generally used for protecting outdoor cultural relics by using wax; inorganic materials are difficult to permeate into deep layers of rocks, are high in brittleness, and the weathering of the rocks is aggravated due to poor adhesion and the like. The material prepared by the invention is a novel nano composite material with a microporous molecular structure, and the hydrolyzed fluorosilane coupling agent and UIO-66- (OH) n (n = 1-4) carrying out grafting reaction, adding the grafting reaction into a dispersant solution, and constructing the micropore surface of the super-hydrophobic metal organic framework by a method of modifying bridging ligand nodes, wherein the prepared material has a pore molecular structure, so that the material has a good hydrophobic function and has important significance for protecting stone cultural relics.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is the chemical reaction principle of UIO-O-FS prepared in example 1;
FIG. 2 is the water contact angle of UIO-O-FS powder prepared in example 1;
FIG. 3 is an infrared spectrum of UIO-O-FS powder prepared in example 1;
FIG. 4 is a transmission electron micrograph of UIO-O-FS powder prepared in example 1;
FIG. 5 is an XRD pattern of UIO-O-FS powder prepared in example 1.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments and with reference to the accompanying drawings. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The hydrophobic composite material for protecting the stone cultural relics is prepared by the following method:
(1) Firstly, preparing a mixed solution of absolute ethyl alcohol and deionized water, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 1: (3-5), adjusting the pH of the mixed solution to 4-5 with glacial acetic acid to obtain a solution A, adding 1-5mL of fluorosilane coupling agent into the solution A, and stirring by a magnetic stirrer for sufficient reaction, wherein the stirring time is 5-8min and the rotating speed is 1500r/min to obtain a solution B. The fluorosilane coupling agent comprises one or more of dodecafluoroheptyl propyl trimethoxy silane, heptadecafluorodecyl trimethoxy silane, nonafluorohexyl trimethoxy silane, trifluoropropane trimethoxy silane and tridecafluorooctyl trimethoxy silane.
(2) UIO-66- (OH) n Placing the powder into a three-neck flask, dropwise adding the solution B obtained in the step (1) into the three-neck flask by using a separating funnel at a low speed, and UIO-66- (OH) n The volume ratio of the powder to the solution B is 1: (0.8-1.5), the dropping speed is 20-45 drops/min, the mixed system is subjected to ultrasonic treatment and stirring treatment at the temperature of 30-50 ℃, the treatment time is 10-30min, and the stirring speed is 60-150r/min. Then, it was put in an oven at 80 ℃ for drying and curing treatment to obtain UIO-O-FS particles, which were ground by a mortar to obtain pale yellow UIO-O-FS powder.
(3) Preparing 3-10 wt% of deionized water solution of a dispersant, uniformly stirring, adding the light yellow UIO-O-FS powder obtained in the step (2), and performing ultrasonic treatment to obtain sol, namely the hydrophobic composite material for protecting the stone cultural relics. Wherein the dispersant can be one or more of sodium polyacrylate, sodium carboxymethylcellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyethylene glycol 400, polyethylene glycol 2000 and polyethylene glycol 4000, and the mass ratio of the UIO-O-FS powder to the dispersant is 1: (1-1.5).
Further, UIO-66- (OH) in step (2) n UIO-66-OH, UIO-66- (OH) may be selected 2 、UIO-66-(OH) 3 、UIO-66-(OH) 4 One or more of (a).
The UIO-66- (OH) n Is prepared by the following method: zirconium tetrachloride (ZrCl) 4 ) And polyhydroxyterephthalic acid in a molar ratio of 1:1 was dissolved in N, N-Dimethylformamide (DMF). Stirring the mixed solution by using a magnetic stirrer, and uniformly stirring at 1500r/min for 30min. Then, the mixture was transferred to a stainless steel autoclave 50mL lined with Teflon and heated at 120 ℃ for 12 hours. And cooling the product to room temperature, and centrifuging at the rotating speed of 10000r/min for 10min to obtain powder. Washing the obtained powder with DMF and anhydrous ethanol repeatedly for 3 times, and drying in oven at 120 deg.C for 12 hr to obtain activated UIO-66- (OH) n 。
In UIO-66- (OH) n In the preparation, the polyhydroxy terephthalic acid is selected from one or more of 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2,3, 5-trihydroxy terephthalic acid and 2,3,5, 6-tetrahydroxy terephthalic acid. 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2,3, 5-trihydroxy terephthalic acid and 2,3,5, 6-tetrahydroxy terephthalic acid are independently selected and prepared according to the method to respectively obtain UIO-66-OH and UIO-66- (OH) 2 、UIO-66-(OH) 3 、UIO-66-(OH) 4 。
The following is a detailed description of specific examples:
example 1
(1) Preparing a mixed solution of absolute ethyl alcohol and deionized water, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 1: and 4, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid to obtain a solution A, adding 2mL of dodecafluoroheptyl propyl trimethoxy silane into the solution A, and stirring by using a magnetic stirrer for fully reacting for 5min at the rotating speed of 1500r/min to obtain a solution B.
(2) Putting UIO-66-OH powder into a three-neck flask, dropwise adding the solution B obtained in the step (1) into the three-neck flask at a low speed by using a separating funnel, wherein the volume ratio of the UIO-66-OH powder to the solution B is 1:0.8. the dropping speed was 20 drops/min. Meanwhile, ultrasonic stirring treatment is carried out at the temperature of 30 ℃, the treatment time is 10min, and the stirring speed is 60r/min. Then, the UIO-O-FS powder is put in an oven for drying and curing treatment to obtain UIO-O-FS particles, and the UIO-O-FS particles are ground by a mortar to obtain light yellow UIO-O-FS powder.
(3) And (3) preparing 3wt% of sodium polyacrylate deionized water solution, uniformly stirring, adding the light yellow UIO-O-FS powder obtained in the step (2), and performing ultrasonic treatment to obtain sol, namely the hydrophobic composite material for protecting the stone cultural relics. The mass ratio of UIO-O-FS powder to the dispersing agent is 1:1.
and (3) performance testing:
and (3) performing a water contact angle test on the UIO-O-FS powder obtained in the step (2), wherein the measured water contact angle is 133.78 degrees, and the formation of the super-hydrophobic MOF is shown as a figure 2.
FIG. 3 is an infrared spectrum of the UIO-O-FS powder prepared in this example, in the UIO-O-FS curve, 1000-1400cm -1 Is the infrared absorption peak of C-F at 1313cm -1 A deformation vibration peak is found, which indicates that C-F has been successfully linked; 690-890cm -1 Is the infrared absorption peak of C-Si at 867cm -1 And a deformation vibration peak is found, and C-Si can be considered to be successfully linked.
FIG. 4 is a transmission electron micrograph of the UIO-O-FS powder prepared in this example, from which it can be seen that the particle size of the powder is in the range of 9-46nm, and the organic hydrophobic group (i.e., R group in FIG. 1) is successfully grafted on the surface of UIO-66-OH, indicating that the obtained UIO-O-FS has a hydrophobic effect.
FIG. 5 is an XRD pattern of the UIO-O-FS powder prepared in this example, from which it can be seen that UIO-O-FS has a certain crystalline form.
According to the formula of the activation index,
the activation index of the sample can be calculated, and the higher the activation index is, the better the activation effect is and the better the hydrophobic property is. The activation index test calculation is carried out on UIO-O-FS, the measured activation index is 77.48%, and the obtained material is proved to have good hydrophobic property.
Uniformly coating the UIO-O-FS sol prepared in the step (3) on the surface of a limestone cylinder with the diameter of 50mm and the height of 100mm, marking the limestone cylinder as a sample II, marking the limestone cylinder without a protective material and with the diameter of 50mm and the height of 100mm as a sample I, soaking the sample I and the sample II in NaCl solution with the pH =4 for 30 days, then carrying out uniaxial compression test on the limestone-O-FS sol by using an RMT-301 rock and concrete compression testing machine, wherein the displacement control rate is adopted in the test, and the size is 0.002mm/s. As a result, the decrease in peak strength before and after the corrosion of sample II was reduced by 5.23% as compared with the uniaxial compressive strength of sample I (Table 1), indicating that the UIO-O-FS sol thus prepared has a good protective effect on the stone sample and can effectively reduce the corrosion of the acidic solution.
Example 2
(1) Preparing a mixed solution of absolute ethyl alcohol and deionized water, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 1: and 3, adjusting the pH value of the mixed solution to 5 by using glacial acetic acid to obtain a solution A, adding 5mL of heptadecafluorodecyltrimethoxysilane into the solution A, and stirring by using a magnetic stirrer for fully reacting for 8min at the rotating speed of 1500r/min to obtain a solution B.
(2) Mixing UIO-66- (OH) 2 Placing the powder into a three-neck flask, dropwise adding the solution B obtained in the step (1) into the three-neck flask by using a separating funnel at a low speed, and UIO-66- (OH) 2 The volume ratio of the powder to the solution B is 1:1, the dropping speed is 30 drops/min. Meanwhile, ultrasonic stirring treatment is carried out at 40 ℃, the treatment time is 20min, and the stirring speed is 100r/min. Then, it was put in an oven to be dried and cured to obtain UIO-O-FS particles, which were ground in a mortar to obtain light yellowColor UIO-O-FS powder.
(3) Preparing 10wt% of sodium carboxymethylcellulose solution, uniformly stirring, adding the light yellow UIO-O-FS powder obtained in the step (2), and performing ultrasonic treatment to obtain sol, namely the hydrophobic composite material for protecting the stone cultural relics. The mass ratio of UIO-O-FS powder to the dispersing agent is 1:1.5.
and (4) performance testing:
and (3) carrying out a water contact angle test on the UIO-O-FS powder obtained in the step (2), wherein the measured water contact angle is 154.23 degrees, which shows that the super-hydrophobic MOF is formed. The particle size range of the UIO-O-FS powder obtained in this example was 20-62nm.
The activation index of the UIO-O-FS is tested and calculated, and the measured activation index is 81.02%, which shows that the obtained UIO-O-FS material has good hydrophobic property.
Uniformly coating the UIO-O-FS sol prepared in the step (3) on the surface of a limestone cylinder with the diameter of 50mm and the height of 100mm, marking as a sample III, soaking the sample III in a NaCl solution with the pH =4 for 30 days, and then carrying out a uniaxial compression test on the sample III by using an RMT-301 rock and concrete compression testing machine, wherein the displacement control rate is adopted in the test, and the size is 0.002mm/s. As a result, the decrease in peak strength before and after the attack of sample III was reduced by 3.54% as compared with the uniaxial compressive strength of sample I (Table 1), indicating that the prepared UIO-O-FS sol has a good protective effect on the stone sample and can effectively reduce the attack of the acidic solution.
Example 3
(1) Preparing a mixed solution of absolute ethyl alcohol and deionized water, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 1: and 5, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid to obtain a solution A, adding 1mL of tridecafluorooctyltrimethoxysilane into the solution A, and stirring by using a magnetic stirrer for fully reacting for 6min at the rotating speed of 1500r/min to obtain a solution B.
(2) UIO-66- (OH) 4 Placing the powder into a three-neck flask, dropwise adding the solution B obtained in the step (1) into the three-neck flask by using a separating funnel at a low speed, and UIO-66- (OH) 4 The volume ratio of the powder to the solution B is 1:1, droppingThe acceleration was 30 drops/min. Meanwhile, ultrasonic stirring treatment is carried out at 50 ℃, the treatment time is 30min, and the stirring speed is 150r/min. Then, it was put in an oven for drying and curing treatment to obtain UIO-O-FS particles, which were ground by a mortar to obtain pale yellow UIO-O-FS powder.
(3) And (3) preparing 6wt% of polyvinylpyrrolidone solution, uniformly stirring, adding the light yellow UIO-O-FS powder obtained in the step (2), and performing ultrasonic treatment to obtain sol, namely the hydrophobic composite material for protecting the stone cultural relics. The mass ratio of UIO-O-FS powder to the dispersing agent is 1:1.2.
and (3) performance testing:
and (3) carrying out a water contact angle test on the UIO-O-FS powder obtained in the step (2), wherein the measured water contact angle is 168.89 degrees, which indicates that the super-hydrophobic MOF is formed. The particle size range of the UIO-O-FS powder obtained in this example was 40-85nm.
The activation index of UIO-O-FS is tested and calculated, and the measured activation index is 86.65%, which indicates that the obtained material has good hydrophobic property.
Uniformly coating the UIO-O-FS sol prepared in the step (3) on the surface of a limestone cylinder with the diameter of 50mm and the height of 100mm, marking the sample as a sample IV, soaking the sample IV in a NaCl solution with the pH =4 for 30 days, and then carrying out a uniaxial compression test on the sample IV by using an RMT-301 rock and concrete compression tester, wherein the displacement control rate is adopted in the test, and the size of the displacement control rate is 0.002mm/s, so that the reduction amount of the peak strength of the sample IV before and after erosion is reduced by 1.15% (shown in the table 1) compared with the uniaxial compression strength of the sample I, and the prepared UIO-O-FS sol has a good protection effect on a stone sample and can effectively reduce the erosion of an acidic solution.
TABLE 1 Peak Strength Change before and after erosion of three examples and test pieces without protective Material
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (9)
1. A preparation method of a hydrophobic composite material for protecting stone cultural relics is characterized by comprising the following steps:
(1) Firstly, preparing a mixed solution of absolute ethyl alcohol and deionized water, wherein the mass ratio of the deionized water to the absolute ethyl alcohol is 1: (3-5), regulating the pH of the mixed solution to 4-5 by using glacial acetic acid to obtain a solution A, adding a fluorosilane coupling agent into the solution A, stirring to enable the fluorosilane coupling agent to react fully to obtain a solution B, wherein the stirring time is 5-8min, and the rotating speed is 1500r/min;
(2) Mixing UIO-66- (OH) n Putting the powder into a three-neck flask, dropwise adding the solution B obtained in the step (1) into the three-neck flask at a low speed, wherein the dropwise adding speed is 20-45 drops/min, performing ultrasonic and stirring treatment on a mixed system at the temperature of 30-50 ℃, the treatment time is 10-30min, and the stirring speed is 60-150r/min; then, drying and curing the UIO-O-FS powder in an oven to obtain UIO-O-FS particles, and grinding the UIO-O-FS particles by a mortar to obtain light yellow UIO-O-FS powder;
(3) Preparing 3-10 wt% of deionized water solution of a dispersant, uniformly stirring, adding the light yellow UIO-O-FS powder obtained in the step (2), and performing ultrasonic treatment to obtain sol, namely the hydrophobic composite material for protecting the stone cultural relics.
2. The method of claim 1, wherein the amount of deionized water used in step (1) is 3-8mL.
3. The method according to claim 2, wherein the amount of the fluorosilane coupling agent added is 1-5mL.
4. The method of claim 1 or 3, wherein the fluorosilane coupling agent is one or more of dodecafluoroheptylpropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, nonafluorohexyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.
5. The method of claim 1, wherein in step (2) UIO-66- (OH) n The volume ratio of the powder to the solution B is 1: (0.8-1.5), UIO-66- (OH) n The powder is UIO-66-OH, UIO-66- (OH) 2 、UIO-66-(OH) 3 、UIO-66-(OH) 4 One or more of (a).
6. The method of claim 1 or 5, wherein the UIO-66- (OH) is a hydrophobic composite n The powder is prepared by the following method: zirconium tetrachloride and polyhydroxy terephthalic acid are mixed according to a molar ratio of 1:1 is dissolved in DMF, a magnetic stirrer is used for stirring the mixed solution, the mixed solution is stirred at a uniform speed of 1500r/min for 30min, then the mixture is transferred to a stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene, and the mixture is heated and reacted for 12h at 120 ℃; cooling the product to room temperature, centrifuging at 10000r/min for 10min to obtain powder, washing the powder with DMF and anhydrous ethanol for 3 times, and drying in oven at 120 deg.C for 12h to obtain UIO-66- (OH) n ；
The polyhydroxy terephthalic acid is one or more of 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2,3, 5-trihydroxy terephthalic acid and 2,3,5, 6-tetrahydroxy terephthalic acid; 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2,3, 5-trihydroxy terephthalic acid and 2,3,5, 6-tetrahydroxy terephthalic acid are independently selected and prepared according to the method to respectively obtain UIO-66-OH and UIO-66- (OH) 2 、UIO-66-(OH) 3 、UIO-66-(OH) 4 。
7. The method of claim 1, wherein the oven drying of step (2) is carried out at a temperature of 80 ℃.
8. The method for preparing the hydrophobic composite material for protecting the stony cultural relics, according to the claim 1, wherein the mass ratio of the UIO-O-FS powder to the dispersing agent in the step (3) is 1: (1-1.5).
9. The method for preparing the hydrophobic composite material for protecting the stony relics, according to the claim 1 or 8, characterized in that the dispersant is selected from one or more of sodium polyacrylate, sodium carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyethylene glycol 400, polyethylene glycol 2000 and polyethylene glycol 4000.
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