CN109504006A - Modified super-hydrophobic composite film of a kind of self-cleaning nona and preparation method thereof - Google Patents
Modified super-hydrophobic composite film of a kind of self-cleaning nona and preparation method thereof Download PDFInfo
- Publication number
- CN109504006A CN109504006A CN201811393848.XA CN201811393848A CN109504006A CN 109504006 A CN109504006 A CN 109504006A CN 201811393848 A CN201811393848 A CN 201811393848A CN 109504006 A CN109504006 A CN 109504006A
- Authority
- CN
- China
- Prior art keywords
- grams
- self
- composite film
- hours
- hydrophobic composite
- 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
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 33
- 238000004140 cleaning Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 56
- 230000004048 modification Effects 0.000 claims abstract description 36
- 238000012986 modification Methods 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 33
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 33
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 58
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- 238000010792 warming Methods 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006277 sulfonation reaction Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 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
- 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 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229920000858 Cyclodextrin Polymers 0.000 claims description 10
- 239000001116 FEMA 4028 Substances 0.000 claims description 10
- GTXWPZRNXZAPGM-UHFFFAOYSA-N NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical class NCCC[SiH](OC(OCC)(OCC)OCC)OC GTXWPZRNXZAPGM-UHFFFAOYSA-N 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- 238000012423 maintenance Methods 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
- 229920000728 polyester Polymers 0.000 claims description 10
- 229960004063 propylene glycol Drugs 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims description 9
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical class CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- TZFKFDQPHRPMKH-UHFFFAOYSA-N 4,4-dibromoheptane Chemical compound CCCC(Br)(Br)CCC TZFKFDQPHRPMKH-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- LVWSZGCVEZRFBT-UHFFFAOYSA-N 1,7-dibromoheptane Chemical compound BrCCCCCCCBr LVWSZGCVEZRFBT-UHFFFAOYSA-N 0.000 description 1
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 1
- UMJJNXFVAMHNIE-UHFFFAOYSA-N ClCC[Na] Chemical compound ClCC[Na] UMJJNXFVAMHNIE-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 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
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a kind of modified super-hydrophobic composite films of self-cleaning nona, and preparing raw material includes: polytetrafluoroethylene (PTFE), polysiloxanes, polymer modification nanofiller, lubricant and solvent.The invention further relates to the preparation methods of the modified super-hydrophobic composite film of the self-cleaning nona.The modified super-hydrophobic composite film self-cleaning performance of self-cleaning nona of the invention is good, hydrophobicity is strong and intensity is high, good market prospect.
Description
Technical field
The present invention relates to hydrophobic technical field of membrane, in particular to a kind of self-cleaning nona is modified super-hydrophobic composite film and its system
Preparation Method.
Background technique
Polytetrafluoroethylene film has the advantages that chemical stability is good and corrosion resistant, can be widely applied to different necks
Domain, especially as the membrane material (super hydrophobic material) of strong-hydrophobicity.The surface of super-hydrophobic polytetrafluoroethylene film typically refer to
The contact angle of water is greater than 150 ° of surface, when water droplet is contacted and rolled with super hydrophobic surface, it will takes away and is attached to admittedly
The pollutant in body surface face, to have self-cleaning ability.
The preparation method of the wider super-hydrophobic polytetrafluoroethylene film of application is pulling method at present, and the film that this method obtains is dredged
Aqueous energy is general, and intensity is low, it is difficult to large-scale use.
For this reason, it may be necessary to carry out process exploitation, it is formulated to improve and obtains that self-cleaning performance is good and that intensity is good is novel from clearly
Clean nano modification super-hydrophobic composite film.
Summary of the invention
The invention discloses a kind of modified super-hydrophobic composite films of self-cleaning nona, and by weight, preparing raw material includes:
Polytetrafluoroethylene (PTFE) 100
Polysiloxanes 20-50
Polymer modification nanofiller 10-20
Lubricant 5-15
Solvent 60-80；
Preferably, preparing raw material includes:
Polytetrafluoroethylene (PTFE) 100
Polysiloxanes 30-40
Polymer modification nanofiller 15-20
Lubricant 10-15
70-80 parts of solvent；
It is highly preferred that it prepares raw material includes:
Polytetrafluoroethylene (PTFE) 100
Polysiloxanes 35
Polymer modification nanofiller 18
Lubricant 12
77 parts of solvent.
In one embodiment, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides and 0.2 gram of tetramethylammonium hydroxide are added in reactor, lead to nitrogen
Protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain polysiloxanes.
In one embodiment, the sulfonation degree of the low sulfonation degree graphene oxide is 10%-30%.
In one embodiment, the polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
In one embodiment, the lubricant is aviation kerosine.
In one embodiment, the solvent is selected from dimethyl sulfoxide, n,N-Dimethylformamide, N, N- dimethyl second
At least one of amide, acetone, ethyl alcohol, isopropanol；The preferably mixture of n,N-Dimethylformamide and isopropanol；It is more excellent
N,N-Dimethylformamide and isopropanol are selected as by weight the mixture of 1:3.
In a preferred embodiment, the modified super-hydrophobic composite film of the self-cleaning nona, by weight, system
Standby raw material further include:
Seven fluorine bytyry imidazoles 1-10 of N-
1,7- dibromo-heptane 1-10.
The present invention also provides the preparation methods of the modified super-hydrophobic composite film of self-cleaning nona, comprising the following steps:
(1) above-mentioned raw materials are stirred and is sufficiently mixed in blender, to form mixed material, then the mixed material is in room temperature
Lower standing cures 5 hours；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona.
Preferably, the stirring rate in the step (1) is 500-5000 revs/min.
The advantageous effects of invention are as follows:
1, by polymer overmold filler, obtain better dispersion effect, and improve the degree of cross linking with obtain better adhesion strength with
And hydrophobic effect；
2, by the cooperation of different-grain diameter filler, better microstructure is obtained, to improve hydrophobicity；
3, the intensity of system can be improved in the addition of low sulfonation degree graphene oxide；
4, better system dispersibility can be obtained by the adjustment of solvent and improves hydrophobic effect；
5, seven fluorine bytyry imidazoles of N- and 1, the degree of cross linking of film can be improved in 7- dibromo-heptane, to improve intensity.
Specific embodiment
Raw material:
Sulfoxidation graphene the preparation method comprises the following steps:
By weight, 1 part of graphene oxide, 10 parts of chloroethyl sodium sulfonate, 6 parts of potassium hydroxide and 300 parts of deionized water are added
Enter in reactor, after 3 parts of concentrated nitric acid is then added and is warming up to 50 DEG C of reactions 1-5 hours, reaction solution is poured into ice water, ice is used
After water washing obtained solid 3 times, by the sulfoxidation graphene of sufficiently dry the different sulfonation degrees of the solid；
Specifically, the reaction time is 1 hour, obtains the graphene oxide that sulfonation degree is about 10% and obtains when the reaction time is 5 hours
Obtain the graphene oxide that sulfonation degree is about 30%.
Other raw materials are commercially available.
Embodiment 1
(1) by 100 grams of polytetrafluoroethylene (PTFE), 20 grams of polysiloxanes, 10 grams of polymer modification nanofiller, 5 grams of aviation kerosine, solvent
60 grams (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3) are stirred and are sufficiently mixed in blender, with
Mixed material is formed, then the mixed material stands curing 5 hours at normal temperature；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Embodiment 2
(1) by 100 grams of polytetrafluoroethylene (PTFE), 30 grams of polysiloxanes, 15 grams of polymer modification nanofiller, 10 grams of aviation kerosine, molten
70 grams of agent (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3) is stirred and is sufficiently mixed in blender,
To form mixed material, then the mixed material stands curing 5 hours at normal temperature；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Embodiment 3
(1) by 100 grams of polytetrafluoroethylene (PTFE), 35 grams of polysiloxanes, 18 grams of polymer modification nanofiller, 12 grams of aviation kerosine, molten
77 grams of agent (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3) is stirred and is sufficiently mixed in blender,
To form mixed material, then the mixed material stands curing 5 hours at normal temperature；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Embodiment 4
(1) by 100 grams of polytetrafluoroethylene (PTFE), 35 grams of polysiloxanes, 18 grams of polymer modification nanofiller, 12 grams of aviation kerosine, molten
77 grams of agent (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3), seven 5 grams of fluorine bytyry imidazoles of N-, 1,7-
5 grams of dibromo-heptane are stirred and are sufficiently mixed in blender, then that the mixed material is quiet at normal temperature to form mixed material
Set curing 5 hours；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Comparative example 1
(1) by 100 grams of polytetrafluoroethylene (PTFE), 35 grams of polysiloxanes, 18 grams of polymer modification nanofiller, 12 grams of aviation kerosine, molten
77 grams of agent (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3), seven 5 grams of fluorine bytyry imidazoles of N-, 1,7-
5 grams of dibromo-heptane are stirred and are sufficiently mixed in blender, and to form mixed material, then the mixed material is stood at normal temperature
Curing 5 hours；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 30%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Comparative example 2
(1) by 100 grams of polytetrafluoroethylene (PTFE), 35 grams of polysiloxanes, 18 grams of polymer modification nanofiller, 12 grams of aviation kerosine, molten
77 grams of agent (mixture of n,N-Dimethylformamide and ethyl alcohol by weight 1:3), seven 5 grams of fluorine bytyry imidazoles of N-, 1,7- bis-
5 grams of heptyl bromide are stirred and are sufficiently mixed in blender, and to form mixed material, then the mixed material is stood ripe at normal temperature
Change 5 hours；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Comparative example 3
(1) by 100 grams of polytetrafluoroethylene (PTFE), 35 grams of polysiloxanes, 18 grams of polymer modification nanofiller, 12 grams of aviation kerosine, molten
77 grams of agent (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3), seven 5 grams of fluorine bytyry imidazoles of N-, 1,7-
5 grams of dibromo-heptane are stirred and are sufficiently mixed in blender, and to form mixed material, then the mixed material is stood at normal temperature
Curing 5 hours；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 85 grams of 1,3,5,7- tetramethyl-ring tetrasiloxanes, 5 grams of low sulfonation degree oxygen
Graphite alkene (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide are added in reactor, lead to nitrogen protection, stir and heat up
To 90 DEG C react 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain polysiloxanes；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
Comparative example 4
(1) by 100 grams of polytetrafluoroethylene (PTFE), 35 grams of polysiloxanes, 18 grams of polymer modification nanofiller, 12 grams of aviation kerosine, molten
77 grams of agent (mixture of n,N-Dimethylformamide and isopropanol by weight 1:3), seven 5 grams of fluorine bytyry imidazoles of N-, 1,7-
5 grams of dibromo-heptane are stirred and are sufficiently mixed in blender, and to form mixed material, then the mixed material is stood at normal temperature
Curing 5 hours；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona；
Wherein, the polysiloxanes the preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Reaction is added in basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides (sulfonation degree 10%) and 0.2 gram of tetramethylammonium hydroxide
In device, lead to nitrogen protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain poly- silicon
Oxygen alkane；
The polymer modification nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 5 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 5 grams of hydroxyapatite (1 micron of average grain diameter) and 5 grams of silane coupling agent KH-
550, after maintenance is stirred at room temperature 2 hours, filters and obtained solid is sufficiently dry, obtain polymer modification nanofiller.
The performance for testing composite membrane obtained by above-described embodiment and comparative example, as a result see the table below 1.
Table 1
| Example | Water contact angle ° | Intensity |
| Embodiment 1 | 153 | 50Mpa |
| Embodiment 2 | 155 | 47Mpa |
| Embodiment 3 | 160 | 48Mpa |
| Embodiment 4 | 159 | 55Mpa |
| Comparative example 1 | 127 | 45Mpa |
| Comparative example 2 | 125 | 39Mpa |
| Comparative example 3 | 135 | 42Mpa |
| Comparative example 4 | 138 | 44Mpa |
| Pure PTFE film | 120 | 41Mpa |
Claims (10)
1. a kind of modified super-hydrophobic composite film of self-cleaning nona, which is characterized in that by weight, preparing raw material includes:
Polytetrafluoroethylene (PTFE) 100
Polysiloxanes 20-50
Polymer modification nanofiller 10-20
Lubricant 5-15
Solvent 60-80.
2. the modified super-hydrophobic composite film of self-cleaning nona according to claim 1, which is characterized in that by weight,
Preparing raw material includes:
Polytetrafluoroethylene (PTFE) 100
Polysiloxanes 30-40
Polymer modification nanofiller 15-20
Lubricant 10-15
70-80 parts of solvent.
3. the modified super-hydrophobic composite film of self-cleaning nona according to claim 2, which is characterized in that by weight,
Preparing raw material includes:
Polytetrafluoroethylene (PTFE) 100
Polysiloxanes 35
Polymer modification nanofiller 18
Lubricant 12
77 parts of solvent.
4. the modified super-hydrophobic composite film of self-cleaning nona according to claim 1, which is characterized in that the polysiloxanes
The preparation method comprises the following steps:
By 10 grams of 3- aminopropyltriethoxy dimethoxysilanes, 30 grams of perfluoro capryl triethoxysilanes, 55 grams of 1,3,5,7- tetramethyls
Basic ring tetrasiloxane, 5 grams of low sulfonation degree graphene oxides and 0.2 gram of tetramethylammonium hydroxide are added in reactor, lead to nitrogen
Protection, stir and be warming up to 90 DEG C reaction 2 hours after, then be warming up to 120 DEG C reaction 1 hour after, obtain polysiloxanes.
5. the modified super-hydrophobic composite film of self-cleaning nona according to claim 1, which is characterized in that the polymer modification
Nanofiller the preparation method comprises the following steps:
(1) by 1 mol of 1,2- propylene glycol, 1 mol of terephthalic acid (TPA), 0.5 mol of trimethylolpropane and Mono-n-butyltin
0.01mol is added in reactor, argon gas protect and be warming up to 90 DEG C react 2 hours after, then be warming up to 270 DEG C and by vacuum degree tune
Section is after the reaction was continued 6 hours, is cooled to room temperature, then N is added into reactor, N- dimethyl formyl after less than 0.02 megapascal
It is small to then heat to 110 DEG C of reactions 10 by amine 1000ml, beta-cyclodextrin 0.2mol and silane coupling agent KH-560 0.05mol
Reaction solution is poured into water by Shi Hou, after being washed with water obtained solid 3 times, the solid is sufficiently dry, and it is poly- to obtain cyclo-dextrin-modified
Ester；
(2) at room temperature, 20 grams of above-mentioned cyclo-dextrin-modified polyester are dissolved in the DMF of 1000ml, 2 grams of nano oxygen is then added
Change yttrium (300 nanometers of average grain diameter), 3 grams of nano silica (100 nanometers of average grain diameter), 5 grams of hydroxyapatite (averagely
1 micron of partial size) and 5 grams of silane resin acceptor kh-550, after maintenance is stirred at room temperature 2 hours, filter simultaneously that obtained solid is abundant
It is dry, obtain polymer modification nanofiller.
6. the modified super-hydrophobic composite film of self-cleaning nona according to claim 1, which is characterized in that the lubricant is boat
Empty kerosene.
7. the modified super-hydrophobic composite film of self-cleaning nona according to claim 1, which is characterized in that the solvent is selected from two
At least one of methyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, acetone, ethyl alcohol, isopropanol；It is preferred that
For the mixture of n,N-Dimethylformamide and isopropanol；More preferably n,N-Dimethylformamide and isopropanol are by weight 1:
3 mixture.
8. the modified super-hydrophobic composite film of self-cleaning nona according to claim 1, which is characterized in that by weight,
Prepare raw material further include:
Seven fluorine bytyry imidazoles 1-10 of N-
1,7- dibromo-heptane 1-10.
9. the preparation method of the modified super-hydrophobic composite film of self-cleaning nona, which comprises the following steps:
(1) raw material of any one of claim 1-8 is stirred and is sufficiently mixed in blender, to form mixed material, so
The mixed material stands curing 5 hours at normal temperature afterwards；
(2) at 60 DEG C, said mixture material is rolled into base band with calender；
(3) it at 150 DEG C, with spoke machine is expanded by after 2 times of above-mentioned base band elder generation longitudinal stretching, then 2 times of cross directional stretch, is sintered in 330 DEG C
Thermal finalization, sintering time are 2 hours, obtain the modified super-hydrophobic composite film of the self-cleaning nona.
10. according to the method described in claim 9, it is characterized in that, the stirring rate in the step (1) is 500-5000
Rev/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811393848.XA CN109504006B (en) | 2018-11-21 | 2018-11-21 | Self-cleaning nano modified super-hydrophobic composite membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811393848.XA CN109504006B (en) | 2018-11-21 | 2018-11-21 | Self-cleaning nano modified super-hydrophobic composite membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109504006A true CN109504006A (en) | 2019-03-22 |
| CN109504006B CN109504006B (en) | 2021-02-05 |
Family
ID=65749483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811393848.XA Expired - Fee Related CN109504006B (en) | 2018-11-21 | 2018-11-21 | Self-cleaning nano modified super-hydrophobic composite membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109504006B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110424000A (en) * | 2019-07-02 | 2019-11-08 | 重庆大学 | One kind having the preparation method on the dropwise condensation surface of " intelligence " self-powered characteristic |
| CN111117122A (en) * | 2019-12-30 | 2020-05-08 | 安徽元琛环保科技股份有限公司 | Preparation method of hydrophobic and oleophobic PTFE (Polytetrafluoroethylene) membrane, prepared PTFE membrane and application |
| CN115160877A (en) * | 2022-08-11 | 2022-10-11 | 君子兰涂料（天津）有限公司 | UV (ultraviolet) film-coated finish paint and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990008218A1 (en) * | 1989-01-17 | 1990-07-26 | W.L. Gore & Associates, Inc. | Waterproof water vapor permeable deodorizing membrane and clothing |
| 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 |
| 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 |
| CN107626211A (en) * | 2017-09-29 | 2018-01-26 | 华南理工大学 | A kind of film for possessing self-cleaning performance and preparation method thereof |
-
2018
- 2018-11-21 CN CN201811393848.XA patent/CN109504006B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990008218A1 (en) * | 1989-01-17 | 1990-07-26 | W.L. Gore & Associates, Inc. | Waterproof water vapor permeable deodorizing membrane and clothing |
| 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 |
| CN107626211A (en) * | 2017-09-29 | 2018-01-26 | 华南理工大学 | A kind of film for possessing self-cleaning performance and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110424000A (en) * | 2019-07-02 | 2019-11-08 | 重庆大学 | One kind having the preparation method on the dropwise condensation surface of " intelligence " self-powered characteristic |
| CN111117122A (en) * | 2019-12-30 | 2020-05-08 | 安徽元琛环保科技股份有限公司 | Preparation method of hydrophobic and oleophobic PTFE (Polytetrafluoroethylene) membrane, prepared PTFE membrane and application |
| CN111117122B (en) * | 2019-12-30 | 2022-04-08 | 安徽元琛环保科技股份有限公司 | Preparation method of hydrophobic and oleophobic PTFE (Polytetrafluoroethylene) membrane, prepared PTFE membrane and application |
| CN115160877A (en) * | 2022-08-11 | 2022-10-11 | 君子兰涂料（天津）有限公司 | UV (ultraviolet) film-coated finish paint and preparation method thereof |
| CN115160877B (en) * | 2022-08-11 | 2023-04-07 | 君子兰涂料（天津）有限公司 | UV (ultraviolet) film-coated finish paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109504006B (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109504006A (en) | Modified super-hydrophobic composite film of a kind of self-cleaning nona and preparation method thereof | |
| CN111925194B (en) | High-temperature-resistant high-performance aerogel composite material and preparation method thereof | |
| Daoud et al. | Superhydrophobic silica nanocomposite coating by a low‐temperature process | |
| CN105176066B (en) | A kind of heat-proof combustion-resistant polyurethane foam | |
| CN114045071B (en) | Building aluminum veneer curtain wall finish paint and preparation method thereof | |
| CN111943654B (en) | High-temperature-resistant and radiation-resistant aerogel composite material and preparation method thereof | |
| CN107641221B (en) | A kind of hydroxide-modified expansible graphite fire retardant and preparation method thereof | |
| KR20210149690A (en) | Coatings, Composites and Coatings | |
| CN114230379B (en) | Preparation method of SiC aerogel/ceramic coating structure integrated heat-insulation-preventing composite material | |
| CN113087729B (en) | Lanthanum complex precursor, lanthanum oxide fiber and preparation method and application of lanthanum zirconate fiber derived from lanthanum oxide fiber | |
| CN105944738A (en) | Preparation method of TiO2/MoS2 composite material based on surface modification | |
| CN105000567A (en) | Preparation method for high-dispersity nano-silica | |
| CN114273188B (en) | Fluorine-carbon aluminum veneer and preparation method thereof | |
| CN107558181B (en) | Graphene-doped ammonium polyphosphate flame-retardant coating fabric and preparation method thereof | |
| CN103614915A (en) | Super-hydrophobic natural fiber fabric and preparation method thereof | |
| CN104497852A (en) | Preparation methods of superhydrophobic methyltrimethoxysilane/ZnO composite sol and composite coating | |
| CN109437780A (en) | A kind of super-hydrophobic automatic cleaning recycled cement and preparation method thereof | |
| CN116082696B (en) | Water-based phenolic aerogel composite material and preparation method thereof | |
| CN105505293B (en) | Antibacterial flame-retardant silicone sealant and preparation method thereof | |
| CN114657789B (en) | Organic silicon super-hydrophobic coating, super-hydrophobic coating based on organic silicon super-hydrophobic coating and application of organic silicon super-hydrophobic coating | |
| CN105970617A (en) | Textile waterproofing agent and preparation method thereof | |
| CN110079056A (en) | A kind of anti-corrosive thermal insulation material and preparation method thereof | |
| CN109535594A (en) | A kind of super-hydrophobic tubing and preparation method thereof | |
| CN115011195A (en) | Water-based heat-insulation reflective composite coating with low heat conductivity coefficient and preparation process thereof | |
| CN105968798A (en) | Fiber-reinforced nano-silicon dioxide material 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210205 |