CN115572539A - Durable super-hydrophobic anti-weathering material for masonry cultural relics, preparation method and coating preparation method - Google Patents
Durable super-hydrophobic anti-weathering material for masonry cultural relics, preparation method and coating preparation method Download PDFInfo
- Publication number
- CN115572539A CN115572539A CN202211155542.7A CN202211155542A CN115572539A CN 115572539 A CN115572539 A CN 115572539A CN 202211155542 A CN202211155542 A CN 202211155542A CN 115572539 A CN115572539 A CN 115572539A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- masonry
- super
- cultural relics
- weathering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 72
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 25
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 206010037844 rash Diseases 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims description 19
- 238000006253 efflorescence Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000001680 brushing effect Effects 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- JLAHXQDOYAFIGZ-UHFFFAOYSA-N 2-fluoro-3-methyloxirane Chemical compound CC1OC1F JLAHXQDOYAFIGZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 8
- 230000002265 prevention Effects 0.000 abstract description 6
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 13
- 230000008859 change Effects 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 8
- KGYUZRBIQCDOCN-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 KGYUZRBIQCDOCN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- -1 polydimethylsiloxane Polymers 0.000 description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241001489698 Gerridae Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 241000607720 Serratia Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N serine Chemical compound OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention relates to a durable super-hydrophobic efflorescence-proof material for a masonry cultural relic, a preparation method and a coating preparation method. Wherein the partially fluorinated siloxane is prepared by one-step reaction of an amino alkyl silane coupling agent and fluorinated propylene oxide. The partially fluorinated siloxane is amino alkyl silane coupling agent and fluorinated propylene oxide with the molar ratio of 1:1-1:2, and also comprises alcohol solvent; the super-hydrophobic coating material based on the partially fluorinated siloxane is used for preventing the surfaces of the masonry cultural relics from being weathered, endows the masonry cultural relics with excellent hydrophobic and antifouling properties, and has good durability so as to keep the weathered effect for a long time. The method provided by the invention solves the problems that the existing brick-stone cultural relic super-hydrophobic weathering prevention material is complex in preparation process, various in required raw material types, high in cost, poor in material durability and the like, and is not suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the field of cultural relic protection materials and technologies, and relates to a durable super-hydrophobic weatherproof material for a brick and stone cultural relic, a preparation method of the durable super-hydrophobic weatherproof material and a preparation method of a coating.
Background
In an open environment, the masonry cultural relics are subjected to various weathering effects caused by environmental factors and the like for a long time, and the preservation condition is not optimistic. Research has shown that gaseous/liquid water and soluble salts in open air environment are the main causes of efflorescence on the surface of masonry cultural relics. The water-salt-rock interaction directly initiates physical and chemical weathering such as mechanical scouring, freeze-thaw cycle, soluble salt dissolution and loss, clay mineral hydration-dehydration cycle and the like, and also indirectly induces biological weathering such as microbial growth and the like. Therefore, the development of a durable weathering material having good compatibility and excellent hydrophobicity is very urgent for the protection of masonry cultural relics.
In recent years, inspired by the special infiltration phenomenon of many biological surfaces in nature (such as lotus leaf surface, water strider leg, and the like), the bionic super-hydrophobic material with super-hydrophobic and self-cleaning properties is also researched and used for preventing the surfaces of the opencast masonry cultural relics from weathering. Mosquera, karapanagenius and the like prepare nano particle-based (SiO) for stone ancient buildings, stone carvings and the like 2 、TiO 2 ) And organic polymer coatings (acrylics, silicones) (build. Environ.,2022, 211 108743; liu Shaojun and the like develop SiO-based grotto imaging for sandstone 2 /TiO 2 And fluorinated silicone (mater.res.soc.symp.proc., 2011, 1319; and bell et al prepared superhydrophobic copolymers (prog.org.coat., 2021, 151 (9): 106097) using fluorinated polyhedral oligomeric silsesquioxane macromers for use in bluff imagery weathering. The material has outstanding hydrophobicity, but has not been applied and popularized in a large scale, and the problems of complex preparation process, poor environmental weather resistance and the like need to be solved.
At present, china also has some patents related to the super-hydrophobic weathering prevention material and method for masonry cultural relics, for example, chinese patent No. CN201010618653.8 discloses an inorganic-organic super-hydrophobic composite material for the masonry cultural relics and a preparation method thereof. Nano ZnO/SiO with the mass fraction of 0.2-4% and the grain diameter of 20-200nm 2 The particles are dispersed into the hydrophobic organic silicon liquid phase and then coated on the surface of the stone to prepare the super-hydrophobic windproof layer. The method has complex preparation process, and needs to prepare SiO firstly 2 Nanoparticles, subsequently on SiO 2 Coating ZnO on the surface, and dispersing the nano particles in an organic solution by ball milling and ultrasonic dispersion. In addition, in the open air environment due to ZnO/SiO 2 High light catalysisThe use of the material can cause the organic components such as organosilicon, organic fluorine and the like to be subjected to oxidative degradation so as to lose the super-hydrophobic property, so that the durability of the material system is poor.
Chinese patent No. CN201410031729.5 discloses a fluorine-containing organosilicon stone antifouling agent and a preparation method thereof, wherein the antifouling agent comprises petroleum ether, fluorosilicone resin, fluorosilicone oil, a dispersing and wetting agent, a defoaming agent, a preservative, a silane coupling agent, a film-forming auxiliary agent, a pigment, a filler and a thickening agent. The prepared antifouling agent has the advantages of water resistance, oil resistance and good permeability, and the pollution resistance of the stone is improved. However, the method has the disadvantages of various raw materials, high cost and complicated preparation process.
Chinese patent No. CN202011039777.0 discloses a preparation method of a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating. Firstly, preparing nano TiO modified by fluorosilane in isopropanol solution 2 And then adding the mixed solution into a prepared mixed solution of polydimethylsiloxane and a curing agent, finally spraying the mixed solution on the surface of the stone cultural relic, and curing the mixture at room temperature in a vacuum environment to obtain the anti-weathering coating. The curing of the sealing coating in the method needs to be carried out in a vacuum environment, and is not suitable for protecting the opencast stone cultural relics.
The technical solutions provided by the above documents and patents solve some problems of anti-weathering protection of the surface of the masonry cultural relic, but the factors of multiple raw material types, high cost, complex preparation process, poor durability of the material system and the like make the masonry cultural relic not suitable for large-scale application and popularization.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a durable super-hydrophobic anti-weathering material for masonry cultural relics, a preparation method and a coating preparation method, which endow the masonry cultural relics with excellent hydrophobic and antifouling properties and have good durability so as to keep long-term anti-weathering effect. The method provided by the invention solves the problems that the existing brick-stone cultural relic super-hydrophobic weathering prevention material is complex in preparation process, various in required raw material types, high in cost, poor in material durability and the like, and is not suitable for large-scale production and application.
Technical scheme
A durable superhydrophobic efflorescence resistant material for masonry cultural relics, which is characterized by comprising a partially fluorinated siloxane and a solvent; the partially fluorinated siloxane is amino alkyl silane coupling agent and fluorinated propylene oxide with the molar ratio of 1:1-1:2, and also comprises alcohol solvent; the sum of the mass percentages of the raw materials is 100 percent.
The mass percentage of the alcohol solvent is 90-99.95%.
The amino alkyl silane coupling agent is selected from one or more of the following structural formulas:
wherein R is 1 、R 2 、R 3 And R 4 Represents a linear or branched alkyl group having 1 to 30 carbon atoms, and is preferably selected from those having 1 to 18 carbon atoms in view of cost, synthesis difficulty and the like.
The R is 1 、R 3 Selecting the same methyl group (-CH) 3 ) Or ethyl (-C) 2 H 5 ) Or both may be different.
The R2 is selected from propyl (-C) 3 H 7 ) Or butyl (-C) 4 H 9 )。
The R is 4 Selecting ethyl (-C) 2 H 5 )。
The fluorinated propylene oxide has the following structural formula:
R f ＝(CF 2 ) 5 CF 3 ；(CF 2 ) 7 CF 3 ；(CF 2 ) 9 CF 3
or (CF) 2 ) 4 CF(CF 3 ) 2 ；(CF 2 ) 6 CF(CF 3 ) 2 ；(CF 2 ) 8 CF(CF 3 ) 2 。
A preparation method of the durable super-hydrophobic efflorescence preventing material for the masonry cultural relics is characterized by comprising the following steps:
step 2: respectively weighing 0.05-10% of partially fluorinated siloxane and 90-99.95% of solvent according to the mass percent, and fully stirring and uniformly mixing, wherein the solvent is an alcohol solvent;
the sum of the mass percentages of the raw materials is 100 percent.
A method for preparing a super-hydrophobic weatherproof layer by adopting the durable super-hydrophobic weatherproof material for the masonry cultural relics is characterized by comprising the following steps of: coating the anti-weathering material on the surface of the masonry cultural relic by spraying or brushing equipment for hydrophobic treatment; and after the solvent is completely volatilized, the super-hydrophobic self-cleaning anti-weathering layer is prepared.
The concentration of the anti-weathering material is 0.01-30%, more preferably 0.05-10%, and the percentage is mass percent.
Advantageous effects
The invention provides a durable super-hydrophobic anti-efflorescence material for a masonry cultural relic, a preparation method and a coating preparation method. Wherein the partially fluorinated siloxane is prepared by one-step reaction of an amino alkyl silane coupling agent and fluorinated propylene oxide. The partially fluorinated siloxane is amino alkyl silane coupling agent and fluorinated propylene oxide with the molar ratio of 1:1-1:2, and also comprises alcohol solvent; the super-hydrophobic coating material based on the partially fluorinated siloxane is used for preventing the surfaces of the masonry cultural relics from being weathered, endows the masonry cultural relics with excellent hydrophobic and antifouling properties, and has good durability so as to keep the weathered effect for a long time. The method provided by the invention solves the problems that the existing brick-stone cultural relic super-hydrophobic anti-weathering material is complex in preparation process, various in required raw materials, high in cost, poor in material durability and the like, and is not suitable for large-scale production and application.
The advantages and the beneficial effects of the invention are as follows:
1. the super-hydrophobic anti-weathering material disclosed by the invention is few in raw material variety, very simple and convenient in preparation method, and low in time consumption and energy consumption. At room temperature, the super-hydrophobic efflorescence-proof material can be prepared by dispersing the super-hydrophobic efflorescence-proof material into a solvent which is harmless to human beings and does not pollute the environment by adopting magnetic stirring. The material is coated on the surface of the masonry cultural relic by a spraying or brushing method, and the super-hydrophobic self-cleaning anti-weathering layer can be obtained after the solvent is quickly volatilized, so that the whole process does not need extreme conditions such as high temperature, high pressure or vacuum and the like, and has application prospects in daily life and industrial production.
2. The super-hydrophobic material forms an anti-weathering layer on the surface of a masonry cultural relic, the water contact angle of the anti-weathering layer is 152-165 degrees, the water drop contact angle hysteresis value is 3.5-9.5 degrees, and meanwhile, the anti-weathering layer shows stable super anti-wettability to complex water dispersion systems such as tea, coffee, milk and the like, shows stable anti-wettability to liquid drops with different volumes, and strictly meets the technical requirements of super-hydrophobic and self-cleaning coatings.
3. The super-hydrophobic material has high performance, and can endow the masonry cultural relics with super-hydrophobic performance by using a small amount. For the masonry cultural relics with different porosities, the effective dosage of the material is not higher than 25g/m 2 。
4. The anti-weathering layer formed by the super-hydrophobic material has high-efficiency capillary hydrophobic performance, and the capillary hydrophobic efficiency of different masonry substrates with the porosity of 2% -45% is higher than 90% after the different masonry substrates are treated by the material.
5. The weathering layer formed by the super-hydrophobic material does not change the original appearance, patterns, colors and other characteristics of the masonry cultural relics. The color change of the surface of the substrate after the weathering treatment is lower than the degree of discernable by the unaided human eye (Delta E) * Less than 3) and strictly meets the cultural relic protection requirement.
6. The anti-weathering layer formed by the super-hydrophobic material can effectively protect the original air permeability of the brick-stone substrate, the water vapor diffusivity loss in the substrate after the treatment of the material is less than 10%, and the cultural relic protection requirement is strictly met.
7. The anti-weathering layer formed on the surface of the masonry cultural relic by the super-hydrophobic material disclosed by the invention is resistant to chemical corrosion and shows stable super-wetting resistance to solutions with the pH value within the range of 3-14; the weatherproof layer has mechanical wear resistance, and the super-hydrophobic performance is still kept after the sand paper is polished for 50 cycles; the weathering layer has environmental weatherability, and the weathering effect is not obviously weakened after accelerated environmental aging, thereby meeting the requirements of use in the open air environment.
8. The raw materials used in the invention have moderate cost, are harmless to human and environment, and are green and environment-friendly.
Drawings
Fig. 1 is a contact angle test chart of the super-hydrophobic, self-cleaning and windproof layer prepared in example 1 and water.
Fig. 2 is a graph showing the change of the capillary water absorption amount of the stone substrate before and after the weathering treatment and the change of the capillary hydrophobic efficiency of the weathering layer in example 1.
FIG. 3 is a graph showing the change in hydrophobicity of the weatherproof layer obtained in example 4 before and after the accelerated aging test.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
unless otherwise specified, various starting materials in the present invention are commercially available products or can be obtained according to a preparation method generally used in the art. The terminology used herein is the same as that conventional in the art.
Example 1
Respectively measuring 0.175ml of 3-aminopropyltrimethoxysilane and 0.376g of 3- (perfluoro-n-hexyl) propylene oxide; firstly, adding the measured 3-aminopropyl trimethoxy silane into a reaction flask at room temperature in a nitrogen environment; slowly dropping the measured 3- (perfluoro-n-hexyl) propylene oxide into the flask under magnetic stirring; 10ml of isopropanol is added into the flask to be fully mixed, the reactants are heated to 50 ℃, and the reaction is continued for 8 hours to obtain the fluorinated siloxane.
0.05g of the product obtained in the step 1 is measured and dispersed into 6.3ml of isopropanol under magnetic stirring to prepare the anti-weathering material with the concentration of 1%. The percentage is mass ratio.
Step 3, preparing a super-hydrophobic self-cleaning weatherproof layer by using a weatherproof material
And (3) coating the anti-weathering material prepared in the step (2) on the surface of Italian Leike stone (biocalcalium limestone with the porosity of 35-47%) with the surface area of 5 multiplied by 5 square centimeters, and obtaining the super-hydrophobic self-cleaning anti-weathering layer after the solvent is completely volatilized.
The hydrophobic property of the weatherproof layer is tested, the water contact angle is 158 degrees +/-2.6 degrees, the water contact angle hysteresis value is 6.5 degrees, and the coating has super-hydrophobic and self-cleaning properties (figure 1). The hydrophobicity of the weathering layer was tested using, for example, coffee, tea, milk, etc., and the results showed that the weathering layer also has superior resistance to wetting by complex aqueous dispersions. The capillary hydrophobic performance of the weatherproof layer is tested according to European Union standards, and the result shows that the weatherproof layer can effectively reduce the capillary water absorption of the porous material, and the capillary hydrophobic efficiency is higher than 90% within 24 hours (figure 2). And (3) representing the micro morphology of the surface of the weathered layer by using a scanning electron microscope, and finding that the weathered layer has a multi-level coarse structure on a micro-nano scale and the surface has high F element content. In addition, the water vapor diffusivity of the stone substrate is only lost by 5% after the weathering treatment, and the surface color change value of the substrate is less than the human naked eye identification degree (delta E is less than 3), so that the basic requirement of cultural relic protection is completely met.
Example 2
Respectively measuring 0.175ml of 3-aminopropyltrimethoxysilane and 0.752g of 3- (perfluoro-n-hexyl) propylene oxide; firstly, adding the measured 3-aminopropyl trimethoxy silane into a reaction flask at room temperature in a nitrogen environment; slowly dropping the measured 3- (perfluoro-n-hexyl) propylene oxide into the flask under magnetic stirring; 10ml of isopropanol is added into the flask, the mixture is uniformly stirred, reactants are heated to 50 ℃, and the reaction is continuously carried out for 12 hours, so that the fluorinated siloxane is prepared.
0.05g of the product obtained in the step 1 is measured and dispersed into 6.3ml of isopropanol under magnetic stirring to prepare the anti-weathering material with the concentration of 1%. The percentage is mass ratio.
Step 3, preparing a super-hydrophobic self-cleaning weatherproof layer by using a weatherproof material
And (3) coating the anti-weathering material prepared in the step (2) on the surface of Italian Leike stone (biocalcalium limestone with the porosity of 35-47%) with the surface area of 5 multiplied by 5 square centimeters, and obtaining the super-hydrophobic self-cleaning anti-weathering layer after the solvent is completely volatilized.
The hydrophobicity test shows that the water contact angle of the anti-weathering layer is 160 degrees +/-2.3 degrees, the water contact angle hysteresis value is 5.6 degrees, and the anti-weathering layer has super-hydrophobic and self-cleaning functions. After the anti-weathering layer is added, the surface color change value of the stone substrate is smaller than the identification degree (delta E is less than 3) of human eyes, and the original characteristics of the stone sample such as appearance, color, patterns and the like are not changed. In addition, the weathering layer was tested for chemical resistance using corrosive liquids (pH =3 acetic acid solution, pH =14 sodium hydroxide solution, etc.), and the results showed that the weathering layer was excellent in corrosion resistance and was able to stably maintain its superhydrophobic property.
Example 3
0.025g of the product obtained in step 1 was weighed and dispersed in 3.2ml of isopropanol under magnetic stirring to prepare an anti-efflorescence material with a concentration of 1%. The percentage is mass ratio.
And (3) brushing the weathering prevention material prepared in the step (2) on the surface of Italian seralanite (sandstone with the porosity of 3-6%) with the surface area of 5 multiplied by 5 square centimeters, and obtaining the super-hydrophobic self-cleaning weathering prevention layer after the solvent is completely volatilized.
The water contact angle of the prepared weatherproof layer is 162 degrees +/-3.0 degrees, and the water contact angle hysteresis value is 4.5 degrees. The data show that, although the weathering material is present in an effective amount (10 g/m) 2 ) Less than the embodiment1(20g/m 2 ) But its self-cleaning performance is better. After the surface is weathered, the water vapor diffusivity of the stone substrate is reduced by about 7%, and the color change value of the surface of the substrate is less than the identification degree of naked human eyes (delta E < 3).
Example 4
Respectively measuring 0.209ml of 3-aminopropylmethyldiethoxysilane and 0.376g of 3- (perfluoro-n-hexyl) propylene oxide; at room temperature and in a nitrogen environment, firstly adding the measured 3-aminopropyl methyl diethoxy silane into a reaction flask; slowly dropping the measured 3- (perfluoro-n-hexyl) propylene oxide into the flask under magnetic stirring; the fluorinated siloxane was prepared by adding 10ml of isopropanol to the flask and heating the reaction to 50 ℃ for 8 hours.
Respectively measuring 0.05g, 0.025g and 0.025g of the product obtained in the step 1, and dispersing the product into a proper amount of isopropanol under magnetic stirring to prepare three parts of anti-weathering material with the concentration of 1%. The percentage is mass ratio.
Step 3, preparing a super-hydrophobic self-cleaning weatherproof layer by using a weatherproof material
And (3) respectively brushing the three parts of the anti-weathering material prepared in the step (2) on the surfaces of Italian Leiti stone, serratia stone and the red brick for construction with the surface area of 5 multiplied by 5 square centimeters, and obtaining the super-hydrophobic self-cleaning anti-weathering layer after the solvent is completely volatilized.
The anti-weathering layers prepared on the surfaces of the lei-cut stone, the serina stone and the architectural red brick have super-hydrophobic and self-cleaning performances, and the water contact angles are all higher than 150 degrees and the hysteresis value of the water contact angle is lower than 9 degrees. Meanwhile, the addition of the weatherproof layer does not change the surface color characteristics of the three substrates (delta E < 3), and the water vapor diffusivity losses of the substrates are all lower than 10%. In addition, conditions such as temperature, humidity and ultraviolet radiation in an open-air environment are simulated by using the artificial climate box in an accelerated mode, and the performance change conditions of the weathering layer on the surfaces of the Leiche stone, the Serrana stone and the building red brick sample are tested after aging for 30 days and 60 days so as to research the environmental durability of the weathering layer. As shown in fig. 3, the weathering resistance of the weathering layer was excellent, the superhydrophobic property and the high capillary hydrophobic efficiency were maintained after aging for 60 days, and the surface color was not changed visibly.
Example 5
In this example, step 1 partially fluorinated siloxane preparation was not carried out and 0.05g (0.049 ml) of 3-aminopropyltrimethoxysilane was used directly as an antisoiling material by brushing to a surface area of 5X 5cm 2 The surface of the Italian lai-chi rock is subjected to complete volatilization of the solvent to obtain the weatherproof layer.
The hydrophobicity test shows that the weatherproof layer has no super-hydrophobic property, the water contact angle is 106 degrees +/-2.4 degrees, and a water drop can not roll on the surface of the weatherproof layer. Capillary hydrophobic tests showed that the capillary hydrophobic efficiency of the weathered layer was below 80% in 24 hours. And analyzing the surface micro-morphology of the weatherproof layer by using a scanning electron microscope, and displaying that the surface of the weatherproof layer is not provided with a multi-scale micro-nano rough structure. The application effect of the embodiment shows that the micro-nano multilevel coarse structure formed after the fluoroalkyl long-chain and partially fluorinated siloxane of the fluorinated epoxide are cured is two necessary conditions for constructing the super-hydrophobic self-cleaning windproof layer.
The above 5 embodiments do not represent a limited scope of application of the patent. Aiming at the masonry cultural relics with different materials, areas and degradation degrees, the use concentration, the volume, the use amount and the like of the weathering prevention material can be flexibly adjusted to achieve the optimal super-hydrophobic and self-cleaning effects.
Claims (10)
1. A durable superhydrophobic efflorescence resistant material for masonry cultural relics, which is characterized by comprising a partially fluorinated siloxane and a solvent; the partially fluorinated siloxane is amino alkyl silane coupling agent and fluorinated propylene oxide with the molar ratio of 1:1-1:2, and also comprises alcohol solvent; the sum of the mass percentages of the raw materials is 100 percent.
2. The durable superhydrophobic efflorescence resistant material of masonry cultural relics of claim 1, wherein: the mass percentage of the alcohol solvent is 90-99.95%.
3. The durable superhydrophobic weather-proofing material of masonry cultural relics of claim 1, wherein: the amino alkyl silane coupling agent is selected from one or more of the following structural formulas:
wherein R is 1 、R 2 、R 3 And R 4 Represents a linear or branched alkyl group having 1 to 30 carbon atoms, and is preferably selected from those having 1 to 18 carbon atoms in view of cost, synthesis difficulty and the like.
4. The durable superhydrophobic efflorescence resistant material of masonry cultural relics of claim 3, characterized in that: the R is 1 、R 3 Selecting the same methyl group (-CH) 3 ) Or ethyl (-C) 2 H 5 ) Or both may be different.
5. The durable superhydrophobic efflorescence resistant material of masonry cultural relics of claim 3, characterized in that: the R2 is selected from propyl (-C) 3 H 7 ) Or butyl (-C) 4 H 9 )。
6. The durable superhydrophobic weather-proofing material of masonry cultural relics of claim 3, wherein: the R is 4 Selecting ethyl (-C) 2 H 5 )。
7. The durable superhydrophobic efflorescence resistant material of masonry cultural relics of claim 1, wherein: the fluorinated propylene oxide has the following structural formula:
8. a preparation method of the durable superhydrophobic weather-proofing material for masonry cultural relics, which is characterized by comprising the following steps:
step 1, preparation of partially fluorinated siloxane: under inert atmosphere, measuring aminoalkyl silane coupling agent and fluoro-propylene oxide according to the molar ratio of 1:1 or 1:2, adding alcohol solvent, fully stirring and mixing, heating to 50-60 ℃ for reaction, and preparing partially fluorinated siloxane after the reaction is finished;
step 2: respectively weighing 0.05-10% of partially fluorinated siloxane and 90-99.95% of solvent according to the mass percent, and fully stirring and uniformly mixing, wherein the solvent is an alcohol solvent;
the sum of the mass percentages of the raw materials is 100 percent.
9. A method for preparing a super-hydrophobic weatherproof layer by using the durable super-hydrophobic weatherproof masonry object material as claimed in any one of claims 1 to 7, wherein the method comprises the following steps: coating the anti-weathering material on the surface of the masonry cultural relic by spraying or brushing equipment for hydrophobic treatment; and after the solvent is completely volatilized, the super-hydrophobic self-cleaning anti-weathering layer is prepared.
10. The method of claim 9, further comprising: the concentration of the anti-weathering material is 0.01-30%, more preferably 0.05-10%, and the percentage is mass percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211155542.7A CN115572539B (en) | 2022-09-22 | 2022-09-22 | Durable superhydrophobic weather-proof material for masonry cultural relics, preparation method and coating preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211155542.7A CN115572539B (en) | 2022-09-22 | 2022-09-22 | Durable superhydrophobic weather-proof material for masonry cultural relics, preparation method and coating preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115572539A true CN115572539A (en) | 2023-01-06 |
| CN115572539B CN115572539B (en) | 2024-01-16 |
Family
ID=84580910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211155542.7A Active CN115572539B (en) | 2022-09-22 | 2022-09-22 | Durable superhydrophobic weather-proof material for masonry cultural relics, preparation method and coating preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115572539B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1795546A1 (en) * | 2005-12-12 | 2007-06-13 | Rohm and Haas Company | Aqueous polymer dispersions with high unsaturated flow promoter content |
| CN101157824A (en) * | 2007-11-15 | 2008-04-09 | 宁君 | Organosilicon water-proof emulsion for building surface and preparation thereof |
| CN101707907A (en) * | 2007-05-15 | 2010-05-12 | 大金工业株式会社 | Water-repellent oil-repellent antifouling agent having good solubility in solvent |
| US20150344652A1 (en) * | 2014-06-03 | 2015-12-03 | Karlsruher Institut für Technologie | Reactive Superhydrophobic Surfaces, Patterned Superhydrophobic Surfaces, Methods For Producing The Same And Use Of The Patterned Superhydrophobic Surfaces |
| CN205069247U (en) * | 2015-10-20 | 2016-03-02 | 昆明理工大电力工程技术有限公司 | Antifouling flashover insulator |
| CN106675395A (en) * | 2016-12-26 | 2017-05-17 | 苏州市建筑科学研究院集团股份有限公司 | Permeation type organosilicone protecting agent for surface of building and preparation method of permeation type organosilicone protecting agent |
| CN107059409A (en) * | 2017-02-06 | 2017-08-18 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN108659600A (en) * | 2018-05-29 | 2018-10-16 | 曹颐戬 | A kind of super-amphiphobic, automatically cleaning fluorine silicon coating material and preparation method thereof |
| CN112225581A (en) * | 2020-09-28 | 2021-01-15 | 太原理工大学 | Preparation method of durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating |
-
2022
- 2022-09-22 CN CN202211155542.7A patent/CN115572539B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1795546A1 (en) * | 2005-12-12 | 2007-06-13 | Rohm and Haas Company | Aqueous polymer dispersions with high unsaturated flow promoter content |
| CN101707907A (en) * | 2007-05-15 | 2010-05-12 | 大金工业株式会社 | Water-repellent oil-repellent antifouling agent having good solubility in solvent |
| CN101157824A (en) * | 2007-11-15 | 2008-04-09 | 宁君 | Organosilicon water-proof emulsion for building surface and preparation thereof |
| US20150344652A1 (en) * | 2014-06-03 | 2015-12-03 | Karlsruher Institut für Technologie | Reactive Superhydrophobic Surfaces, Patterned Superhydrophobic Surfaces, Methods For Producing The Same And Use Of The Patterned Superhydrophobic Surfaces |
| CN205069247U (en) * | 2015-10-20 | 2016-03-02 | 昆明理工大电力工程技术有限公司 | Antifouling flashover insulator |
| CN106675395A (en) * | 2016-12-26 | 2017-05-17 | 苏州市建筑科学研究院集团股份有限公司 | Permeation type organosilicone protecting agent for surface of building and preparation method of permeation type organosilicone protecting agent |
| CN107059409A (en) * | 2017-02-06 | 2017-08-18 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN108659600A (en) * | 2018-05-29 | 2018-10-16 | 曹颐戬 | A kind of super-amphiphobic, automatically cleaning fluorine silicon coating material and preparation method thereof |
| CN112225581A (en) * | 2020-09-28 | 2021-01-15 | 太原理工大学 | Preparation method of durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating |
Non-Patent Citations (3)
| Title |
|---|
| 上海树脂厂: "《环氧树脂》", 上海人民出版社, pages: 22 - 24 * |
| 张兵峰;: "石窟造像防风化加固材料探讨", no. 04 * |
| 杨隽永;徐飞;: "有机-无机复合疏水型二氧化硅涂层制备及性能", 文物保护与考古科学, no. 02, pages 22 - 25 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115572539B (en) | 2024-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100548658B1 (en) | Fluoroalkyl-functional organosiloxane-containing compositions based on alcohols and preparation methods thereof | |
| US4754012A (en) | Multi-component sol-gel protective coating composition | |
| US4731264A (en) | Sol-gel compositions containing silane and alumina | |
| CN107353677B (en) | A kind of aqueous transparent super hydrophobic coating and preparation method thereof | |
| US8298679B2 (en) | Aqueous silane systems based on bis(trialkoxysilylalkyl)amines | |
| EP2294152B1 (en) | A superhydrophobic aerogel that does not require per-fluoro compounds or contain any fluorine | |
| KR101228691B1 (en) | Block condensates of organofunctional siloxanes, their preparation and use, and their properties | |
| CN108659600B (en) | Super-amphiphobic self-cleaning fluorine-silicon coating material and preparation method thereof | |
| CN101193992A (en) | Solution or dispersion for treating surface of base material, containing titanium oxide doped with metal element, method for treating surface of base material by using the liquid, and surface-treated | |
| CN101560078A (en) | External wall heat-insulating coating | |
| CN101555385B (en) | Water-reducible silicone coating and preparation method thereof | |
| Ershad-Langroudi et al. | Application of polymer coatings and nanoparticles in consolidation and hydrophobic treatment of stone monuments | |
| CN110183965A (en) | A kind of preparation method of novel aqueous organic silicon stone protective agent | |
| CN1171958C (en) | Process for preparing self-cleaning bionic organic paint with lotus leaf function of external wall of building | |
| CN107629627B (en) | Permeable hydrophobic multifunctional waterproof coating and preparation method and application thereof | |
| US7993707B2 (en) | Production of coated substrates | |
| CN113881323A (en) | Preparation method and application of super-hydrophobic coating | |
| CN102585232B (en) | Fluorine-containing organic silicon stone anti-fouling agent | |
| Wang et al. | Sandstone protection by using nanocomposite coating of silica | |
| CN112280339A (en) | Preparation method and application of super-hydrophobic composite material | |
| CN108070258B (en) | High-permeability water-in-oil long-acting alkyl siloxane oligomer composition and preparation method thereof | |
| CN115572539B (en) | Durable superhydrophobic weather-proof material for masonry cultural relics, preparation method and coating preparation method | |
| KR20030043535A (en) | Multi Functional Silicon-polymer Composite for Coating | |
| CN108410218A (en) | A kind of coupling agent modified organo-mineral complexing concrete protection coating and its preparation method and application | |
| CN115991942B (en) | Weather-proof material for surface of open-air masonry cultural relics and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |