CN109437780B - Super-hydrophobic self-cleaning recycled cement and preparation method thereof - Google Patents
Super-hydrophobic self-cleaning recycled cement and preparation method thereof Download PDFInfo
- Publication number
- CN109437780B CN109437780B CN201811390892.5A CN201811390892A CN109437780B CN 109437780 B CN109437780 B CN 109437780B CN 201811390892 A CN201811390892 A CN 201811390892A CN 109437780 B CN109437780 B CN 109437780B
- Authority
- CN
- China
- Prior art keywords
- polytetrafluoroethylene
- hydrophobic
- hours
- super
- polymer
- 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.)
- Expired - Fee Related
Links
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 75
- 239000004568 cement Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000004140 cleaning Methods 0.000 title claims abstract description 30
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 88
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 57
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 57
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 85
- 239000000463 material Substances 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 33
- 239000000945 filler Substances 0.000 claims description 32
- 229920001296 polysiloxane Polymers 0.000 claims description 31
- 229920000858 Cyclodextrin Polymers 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 230000002209 hydrophobic effect Effects 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 20
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims description 10
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001116 FEMA 4028 Substances 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 10
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 10
- 229960004853 betadex Drugs 0.000 claims description 10
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003490 calendering Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000009998 heat setting Methods 0.000 claims description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 10
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 10
- 229960004063 propylene glycol Drugs 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims description 9
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 9
- LVWSZGCVEZRFBT-UHFFFAOYSA-N 1,7-dibromoheptane Chemical compound BrCCCCCCCBr LVWSZGCVEZRFBT-UHFFFAOYSA-N 0.000 claims description 8
- MSYHGYDAVLDKCE-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluoro-1-imidazol-1-ylbutan-1-one Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)N1C=CN=C1 MSYHGYDAVLDKCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 238000006277 sulfonation reaction Methods 0.000 description 18
- 239000001341 hydroxy propyl starch Substances 0.000 description 11
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003350 kerosene Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004567 concrete Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- BVIXLMYIFZGRBH-UHFFFAOYSA-M sodium;2-chloroethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCl BVIXLMYIFZGRBH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1048—Polysaccharides, e.g. cellulose, or derivatives thereof
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to super-hydrophobic self-cleaning recycled cement which comprises the following preparation raw materials in parts by weight: 100 parts of high-alumina cement and 10-30 parts of polytetrafluoroethylene-based super-hydrophobic polymer. The invention also relates to a preparation method of the super-hydrophobic self-cleaning recycled cement. The super-hydrophobic self-cleaning recycled cement disclosed by the invention is good in self-cleaning performance, strong in hydrophobicity, high in strength and good in market prospect.
Description
Technical Field
The invention relates to the technical field of hydrophobic membranes, in particular to super-hydrophobic self-cleaning recycled cement and a preparation method thereof.
Background
Cement-based exterior walls, cross-sea bridges, harbor wharfs, ships and the like need to use a large amount of cement, and particularly when the cement is applied to special fields such as sewage pools, acid-base liquid storage pools and the like, the cement is required to have better durability. Generally, it is believed that the water gradually corrodes the cement, thereby reducing the strength thereof, and if the hydrophobicity of the cement can be improved, the service life of the cement can be greatly improved.
The polytetrafluoroethylene membrane has the advantages of good chemical stability and corrosion resistance, and can be widely applied to different fields, particularly as a membrane material with strong hydrophobicity (super-hydrophobic material). The surface of the super-hydrophobic polytetrafluoroethylene film generally refers to a surface with a contact angle with water larger than 150 degrees, and when a water drop contacts with the super-hydrophobic surface and rolls, the water drop can carry away pollutants attached to the solid surface, so that the self-cleaning capability is realized.
If the polytetrafluoroethylene film can be combined with cement, it is possible to obtain a novel cement which is excellent in self-cleaning property and highly hydrophobic.
Disclosure of Invention
The invention discloses super-hydrophobic self-cleaning recycled cement which comprises the following preparation raw materials in parts by weight:
100 portions of high-alumina cement
10-30 parts of a polytetrafluoroethylene-based super-hydrophobic polymer;
wherein the preparation raw materials of the polytetrafluoroethylene-based super-hydrophobic polymer comprise the following components in parts by weight:
polytetrafluoroethylene 100
Polysiloxane 20-50
10-20 parts of polymer modified nano filler
5-15 parts of lubricant
Hydroxypropyl starch ether 5-10
KH-550 1-5
60-80 parts of solvent.
Preferably, the raw materials for preparing the polytetrafluoroethylene-based superhydrophobic polymer comprise:
polytetrafluoroethylene 100
Polysiloxane 30-40
15-20 parts of polymer modified nano filler
10-15 parts of lubricant
Hydroxypropyl starch ether 6-9
KH-550 2-4
70-80 parts of solvent.
More preferably, the raw materials for preparing the polytetrafluoroethylene-based superhydrophobic polymer include:
polytetrafluoroethylene 100
Polysiloxane 36
Polymer modified nanofiller 17
Lubricant 12
Hydroxypropyl starch ether 7
KH-550 3
And (5) a solvent 75.
Preferably, the polysiloxane is prepared by the following method:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low-sulfonation-degree graphene oxide and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain the polysiloxane.
Preferably, the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Preferably, the lubricant is jet fuel.
Preferably, the solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, ethanol, isopropanol; preferably a mixture of N, N-dimethylformamide and isopropanol; more preferably a 1:3 by weight mixture of N, N-dimethylformamide and isopropanol.
Preferably, the raw materials for preparing the polytetrafluoroethylene-based superhydrophobic polymer further include:
n-heptafluorobutyrylimidazole 1-10
1, 7-dibromoheptane 1-10.
In one embodiment, a method for preparing a polytetrafluoroethylene-based superhydrophobic polymer includes the steps of:
(1) stirring and fully mixing raw materials for preparing the polytetrafluoroethylene-based super-hydrophobic polymer in a stirrer to form a mixed material, and then standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) and grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer.
The invention also provides a method for regenerating cement by super-hydrophobic self-cleaning, which comprises the following steps:
the super-hydrophobic polymer is obtained by fully mixing the high-alumina cement with the super-hydrophobic polymer based on the polytetrafluoroethylene.
The beneficial technical effects of the invention are as follows:
1. the polymer is used for coating the filler, so that a better dispersion effect is obtained, and the crosslinking degree is improved so as to obtain better adhesion and a hydrophobic effect;
2. through the matching of fillers with different particle sizes, a better microstructure is obtained so as to improve the hydrophobicity;
3. the strength of the system can be improved by adding the low-sulfonation-degree graphene oxide;
4. better system dispersibility and hydrophobic effect improvement can be achieved by adjusting the solvent;
5. n-heptafluorobutyrylimidazole and 1, 7-dibromoheptane can increase the degree of crosslinking of the membrane, thereby increasing strength.
Detailed Description
Raw materials:
the preparation method of the sulfonated graphene oxide comprises the following steps:
adding 1 part of graphene oxide, 10 parts of sodium chloroethyl sulfonate, 6 parts of potassium hydroxide and 300 parts of deionized water into a reactor according to parts by weight, then adding 3 parts of concentrated nitric acid, heating to 50 ℃ for reaction for 1-5 hours, pouring the reaction solution into ice water, washing the obtained solid with ice water for 3 times, and fully drying the solid to obtain sulfonated graphene oxide with different sulfonation degrees;
specifically, the reaction time was 1 hour to obtain graphene oxide having a sulfonation degree of about 10%, and the reaction time was 5 hours to obtain graphene oxide having a sulfonation degree of about 30%.
Other materials are commercially available.
Example 1
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 20 g of polysiloxane, 10 g of polymer modified nano filler, 5 g of aviation kerosene, 5 g of hydroxypropyl starch ether, KH-5501 g and 60 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3) in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Example 2
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 30 g of polysiloxane, 15 g of polymer modified nano filler, 10 g of aviation kerosene, 6 g of hydroxypropyl starch ether, KH-5502 g and 70 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3) in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Example 3
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 36 g of polysiloxane, 17 g of polymer modified nano filler, 12 g of aviation kerosene, 7 g of hydroxypropyl starch ether, KH-5503 g and 75 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3) in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Example 4
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 36 g of polysiloxane, 17 g of polymer modified nano filler, 12 g of aviation kerosene, 7 g of hydroxypropyl starch ether, KH-5503 g, 75 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Comparative example 1
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 36 g of polysiloxane, 17 g of polymer modified nano filler, 12 g of aviation kerosene, 7 g of hydroxypropyl starch ether, KH-5503 g, 75 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of sulfonated graphene oxide (with the sulfonation degree of 30%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Comparative example 2
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 36 g of polysiloxane, 17 g of polymer modified nano filler, 12 g of aviation kerosene, 7 g of hydroxypropyl starch ether, KH-5503 g, 75 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 2mol of 1, 2-propylene glycol, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and the temperature is raised to 90 ℃, then raising the temperature to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, then cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, then raising the temperature to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Comparative example 3
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 36 g of polysiloxane, 17 g of polymer modified nano filler, 12 g of aviation kerosene, 7 g of hydroxypropyl starch ether, KH-5503 g, 75 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 85 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of graphene oxide with low sulfonation degree (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
Comparative example 4
Fully mixing 100 parts by weight of high-alumina cement and 20 parts by weight of super-hydrophobic polymer based on polytetrafluoroethylene in a stirrer to obtain super-hydrophobic self-cleaning regenerated cement;
the preparation method of the polytetrafluoroethylene-based super-hydrophobic polymer comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 36 g of polysiloxane, 17 g of polymer modified nano filler, 12 g of aviation kerosene, 7 g of hydroxypropyl starch ether, KH-5503 g, 75 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 5 g of nano yttrium oxide (average particle size of 300 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is stirred for 2 hours at room temperature, and then the mixture is filtered by suction, and the obtained solid is fully dried to obtain the polymer modified nano filler.
Testing
The regenerated cement, the fine sand and the water obtained in any one of the above examples 1 to 4 and comparative examples 1 to 4 are mixed according to a mass ratio of 1: 1.5: 3 mixing and stirring to form cement paste; then pouring the cement paste into a mould, and naturally drying to obtain the super-hydrophobic concrete.
The properties of the above concrete were tested and the results are shown in Table 1 below.
TABLE 1
| Examples of the present invention | Water contact angle ° | Angle of roll ° |
| Example 1 | 144 | 4 |
| Example 2 | 146 | 4 |
| Example 3 | 157 | 3 |
| Example 4 | 155 | 3 |
| Comparative example 1 | 130 | 6 |
| Comparative example 2 | 132 | 6 |
| Comparative example 3 | 136 | 5 |
| Comparative example 4 | 135 | 5 |
| Pure high-alumina cement | 125 | 13 |
Claims (11)
1. The super-hydrophobic self-cleaning recycled cement is characterized by comprising the following preparation raw materials in parts by weight:
100 portions of high-alumina cement
10-30 parts of a polytetrafluoroethylene-based super-hydrophobic polymer;
the preparation method comprises the following steps of (1) preparing a polytetrafluoroethylene-based super-hydrophobic polymer by weight:
2. the superhydrophobic self-cleaning recycled cement of claim 1, wherein the preparation raw materials of the polytetrafluoroethylene-based superhydrophobic polymer are as follows by weight:
3. the super-hydrophobic self-cleaning recycled cement as claimed in claim 2, wherein the polytetrafluoroethylene-based super-hydrophobic polymer is prepared from the following raw materials in parts by weight:
4. the superhydrophobic self-cleaning recycled cement of claim 1, wherein the polysiloxane is prepared by the following method:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low-sulfonation-degree graphene oxide and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain the polysiloxane.
5. The super-hydrophobic self-cleaning recycled cement as claimed in claim 1, wherein the polymer modified nano filler is prepared by the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide with the average particle size of 300 nm, 3 g of nano silicon dioxide with the average particle size of 100 nm, 5 g of hydroxyapatite with the average particle size of 1 micron and 5 g of silane coupling agent KH-550 are added, the room temperature is maintained, the mixture is stirred for 2 hours, and then the polymer modified nano filler is obtained after suction filtration and full drying of the obtained solid.
6. The superhydrophobic self-cleaning recycled cement of claim 1, wherein said lubricant is jet fuel.
7. The superhydrophobic self-cleaning recycled cement of claim 1, wherein the solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, ethanol, isopropanol.
8. The superhydrophobic self-cleaning recycled cement of claim 7, wherein the solvent is a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3.
9. The superhydrophobic self-cleaning recycled cement of claim 1, wherein the raw materials for preparing the polytetrafluoroethylene-based superhydrophobic polymer further comprise, by weight:
n-heptafluorobutyrylimidazole 1-10
1, 7-dibromoheptane 1-10.
10. The superhydrophobic self-cleaning recycled cement according to any of claims 1-9, wherein said preparation method of the polytetrafluoroethylene-based superhydrophobic polymer comprises the steps of:
(1) stirring and fully mixing the raw materials of the polytetrafluoroethylene-based super-hydrophobic polymer in a stirrer to form a mixed material, and then standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expander, sintering and heat-setting at 330 ℃ for 2 hours to obtain a hydrophobic composite membrane material;
(4) and grinding the hydrophobic composite membrane material into fine particles to obtain the polytetrafluoroethylene-based super-hydrophobic polymer.
11. The method for preparing the superhydrophobic self-cleaning recycled cement according to any one of claims 1-9, comprising the steps of: and (3) fully mixing the high-alumina cement with the polytetrafluoroethylene-based super-hydrophobic polymer to obtain the high-alumina cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811390892.5A CN109437780B (en) | 2018-11-21 | 2018-11-21 | Super-hydrophobic self-cleaning recycled cement and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811390892.5A CN109437780B (en) | 2018-11-21 | 2018-11-21 | Super-hydrophobic self-cleaning recycled cement and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109437780A CN109437780A (en) | 2019-03-08 |
| CN109437780B true CN109437780B (en) | 2021-04-16 |
Family
ID=65553265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811390892.5A Expired - Fee Related CN109437780B (en) | 2018-11-21 | 2018-11-21 | Super-hydrophobic self-cleaning recycled cement and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109437780B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229013B (en) * | 2019-07-19 | 2020-10-27 | 中国科学技术大学 | Self-cleaning lightweight concrete and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051120A (en) * | 2009-11-03 | 2011-05-11 | 汉高股份有限及两合公司 | Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating |
| CN202430851U (en) * | 2011-11-18 | 2012-09-12 | 东南大学 | Super-hydrophobic self cleaning wall body |
| CN103756460A (en) * | 2014-01-19 | 2014-04-30 | 深圳市九合伟业科技有限公司 | Nanoscale waterproof film and preparation method thereof |
| CN103992701A (en) * | 2014-05-23 | 2014-08-20 | 中国人民武装警察部队杭州士官学校 | Method for preparing super hydrophobic polymer composite coating containing nano particles and product thereof |
| CN104437126A (en) * | 2013-09-23 | 2015-03-25 | 上海碧科清洁能源技术有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene microporous membrane, membrane prepared by preparation method and application of super-hydrophobic polytetrafluoroethylene microporous membrane |
| CN107285715A (en) * | 2017-08-03 | 2017-10-24 | 安徽真信涂料有限公司 | A kind of energy-conserving and environment-protective building coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080221263A1 (en) * | 2006-08-31 | 2008-09-11 | Subbareddy Kanagasabapathy | Coating compositions for producing transparent super-hydrophobic surfaces |
| US8431220B2 (en) * | 2009-06-05 | 2013-04-30 | Xerox Corporation | Hydrophobic coatings and their processes |
-
2018
- 2018-11-21 CN CN201811390892.5A patent/CN109437780B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051120A (en) * | 2009-11-03 | 2011-05-11 | 汉高股份有限及两合公司 | Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating |
| CN202430851U (en) * | 2011-11-18 | 2012-09-12 | 东南大学 | Super-hydrophobic self cleaning wall body |
| CN104437126A (en) * | 2013-09-23 | 2015-03-25 | 上海碧科清洁能源技术有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene microporous membrane, membrane prepared by preparation method and application of super-hydrophobic polytetrafluoroethylene microporous membrane |
| CN103756460A (en) * | 2014-01-19 | 2014-04-30 | 深圳市九合伟业科技有限公司 | Nanoscale waterproof film and preparation method thereof |
| CN103992701A (en) * | 2014-05-23 | 2014-08-20 | 中国人民武装警察部队杭州士官学校 | Method for preparing super hydrophobic polymer composite coating containing nano particles and product thereof |
| CN107285715A (en) * | 2017-08-03 | 2017-10-24 | 安徽真信涂料有限公司 | A kind of energy-conserving and environment-protective building coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109437780A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108690478B (en) | Anticorrosive paint for flue gas desulfurization equipment and preparation method thereof | |
| CN109504006B (en) | Self-cleaning nano modified super-hydrophobic composite membrane and preparation method thereof | |
| CN105602432B (en) | A kind of water nano flame retardant polyurethane floating coating and preparation method thereof | |
| Ekambaram et al. | Fouling resistant PVDF/Carboxymethyl chitosan composite nanofiltration membranes for humic acid removal | |
| CN109437780B (en) | Super-hydrophobic self-cleaning recycled cement and preparation method thereof | |
| CN105131227A (en) | Synthetic-leather-used UV solidifying and flame-retarding polyurethane and preparation method thereof | |
| CN115710823B (en) | Flexible ablation heat protection composite material and preparation method thereof | |
| CN114891409B (en) | Single-coating water-based ceramic heat-insulating anticorrosive paint for metal material and preparation method thereof | |
| CN106010048A (en) | Heat-insulation waterproof building coating and preparation method thereof | |
| CN110746812A (en) | Thixotropic mixtures containing nonionic polyurethane compounds and aqueous leather surface treatment coatings comprising the same | |
| CN114015346A (en) | Water-based paint for refitted vehicle and preparation method thereof | |
| CN109486354B (en) | Conductive super-hydrophobic coating and preparation method thereof | |
| CN112820921B (en) | Nafion/g-C3N4Composite membrane and preparation method and application thereof | |
| CN109535594B (en) | Super-hydrophobic pipe and preparation method thereof | |
| CN115124876B (en) | Functional filler, water-based anti-icing paint for wind power blade and preparation method of anti-icing paint | |
| CN111073496A (en) | Environment-friendly polymer cement waterproof coating and preparation method thereof | |
| CN116410617A (en) | Surface modified glass bead composite filler and preparation method and application thereof | |
| CN104910389A (en) | Anti-soil hyperbranched dispersing agent and preparation method thereof | |
| CN114836084A (en) | Corrosion-resistant polymer cement coating and preparation method thereof | |
| CN109762462B (en) | Anticorrosive paint with barrier property | |
| CN112961570A (en) | Environment-friendly underwater toughening epoxy resin adhesive and preparation method thereof | |
| CN116589907B (en) | Durable concrete surface protective coating | |
| CN111569669A (en) | Modified super-hydrophobic epoxy resin composite membrane and preparation method thereof | |
| CN109535932B (en) | Fluid conveying pipe with super-hydrophobic surface structure and preparation method thereof | |
| CN117883985B (en) | Preparation method of modified polytetrafluoroethylene composite nanofiltration membrane |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210416 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |