CN114316663B - Modified fluoroethanol ether surfactant and preparation method and application thereof - Google Patents
Modified fluoroethanol ether surfactant and preparation method and application thereof Download PDFInfo
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- CN114316663B CN114316663B CN202111672275.6A CN202111672275A CN114316663B CN 114316663 B CN114316663 B CN 114316663B CN 202111672275 A CN202111672275 A CN 202111672275A CN 114316663 B CN114316663 B CN 114316663B
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 128
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical class OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002086 nanomaterial Substances 0.000 claims abstract description 137
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 52
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims abstract description 48
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- -1 tris (hydroxymethyl) aminomethane amine Chemical class 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000009849 vacuum degassing Methods 0.000 claims description 8
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 8
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 235000009518 sodium iodide Nutrition 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- PSQZJKGXDGNDFP-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)(F)F PSQZJKGXDGNDFP-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- XNADMVZZZMSROL-UHFFFAOYSA-N OCC(C(C(Cl)(Cl)Cl)Cl)(Cl)Cl Chemical compound OCC(C(C(Cl)(Cl)Cl)Cl)(Cl)Cl XNADMVZZZMSROL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 230000005495 cold plasma Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000009616 inductively coupled plasma Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- GRJRKPMIRMSBNK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GRJRKPMIRMSBNK-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000909 polytetrahydrofuran Polymers 0.000 claims 1
- 238000003303 reheating Methods 0.000 claims 1
- 229910000275 saponite Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
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- 230000000052 comparative effect Effects 0.000 description 35
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000006073 displacement reaction Methods 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical class OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 4
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- VLHYAWNCTMZTSC-UHFFFAOYSA-N 1,1,3,3,3-pentafluoropropan-1-ol Chemical compound OC(F)(F)CC(F)(F)F VLHYAWNCTMZTSC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
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- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a modified fluoroether ether surfactant as well as a preparation method and application thereof, wherein the modified fluoroether ether surfactant comprises the following raw materials in parts by weight: 10-100 parts of a modified two-dimensional nano material; 20-80 parts of fluoroalcohol; 20-80 parts of ethylene oxide; 0.3-1 part of catalyst; the modified two-dimensional nano material simultaneously contains hydroxyl and amino. The modified fluoroethanol ether surfactant disclosed by the invention has high surface activity and high adhesive force, and can be used as an additive to play the functions of leveling, antifogging, cleaning and the like.
Description
Technical Field
The invention belongs to the technical field of surfactants, and relates to a modified fluoroether ether surfactant as well as a preparation method and application thereof.
Background
The fluorine-containing surfactant has the characteristics of high surface activity, high thermal stability, high chemical stability and hydrophobicity and oleophobicity, and is widely applied to a plurality of fields of chemistry, chemical engineering, spinning, leather, construction, petroleum, fire fighting and the like.
The fluorocarbon surfactant has special performances of high surface activity, high chemical stability, high heat-resistant stability, hydrophobicity, oleophobicity and the like, is widely applied to various fields of fire fighting, textile, leather, papermaking, mineral separation, electronics, pesticides, chemical industry and the like, and has more varieties and extremely wide application. Fluorocarbon surfactants are generally composed of perfluorinated chains and hydrophilic chains, the most common of which mainly comprise: perfluorooctane sulfonates with different hydrophobic chain lengths, perfluorooctanoic acids with different hydrophobic chain lengths, and the like. Research shows that the high surface activity of the fluorocarbon surfactant is caused by small van der Waals force among molecules, the tension required for the surfactant molecules to move from the aqueous solution to the surface of the solution is small, so that the surfactant molecules are greatly aggregated on the surface of the solution to form strong surface adsorption, and the fluorocarbon surfactant has small affinity to water and small affinity to hydrocarbon, so that the fluorocarbon surfactant has the characteristics of being hydrophobic and oleophobic.
In the fluorocarbon surfactant, the cost of perfluorooctane sulfonate and perfluorooctanoic acid is relatively low, so the fluorocarbon surfactant prepared by taking the perfluorooctane sulfonate and the perfluorooctanoic acid as the starting raw materials is more applied. However, relevant researches show that the perfluorooctane sulfonate/perfluorooctanoic acid is stable in property and extremely difficult to degrade, the fluorocarbon surfactant is easy to accumulate in organisms, has certain toxicity and certain harmfulness to the ecological environment, and therefore, the search for a proper brand-new degradable fluorocarbon surfactant to replace the existing perfluorooctane sulfonate/perfluorooctanoic acid surfactant is an important direction in the field.
CN111019120A discloses a preparation method and application of a novel fluorocarbon surfactant for a high-efficiency cleanup additive. The method comprises the following steps: (a) Dissolving perfluoropolyether acyl fluoride in a polar organic solvent, mixing with triethylene diamine, heating, and adding caustic alkali; (b) Mixing the bis-per-fluoropolyether amide obtained in the step (a) with trichloroethanol in an alcohol solvent; (c) Mixing the N-N-ethanol bis-perfluoropolyether amide obtained in the step (b) with chloric acid, and adding caustic alkali to obtain the novel fluorocarbon surfactant for the high-efficiency cleanup additive. The fluorocarbon surfactant prepared by the method has the advantages of high surface activity, good temperature resistance, good solubility, mild synthesis conditions and the like, can obviously reduce the surface tension of the fluorocarbon surfactant by adding a very small amount of the fluorocarbon surfactant into fracturing fluid or acid liquor when being added into a cleanup additive, reduces the capillary force, improves the flowback efficiency of injected fluid, has simple and easy preparation method, and is easy for industrial application. But the adhesion of the fluorocarbon surfactant of the present invention is to be further improved.
Therefore, in the art, it is desired to develop a fluorocarbon surfactant having both high surface activity and high adhesion, and having better antifogging duration and scratch resistance durability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified fluoroether ether surfactant as well as a preparation method and application thereof. The modified fluoroethanol ether surfactant disclosed by the invention has high surface activity and high adhesive force, and can be used as an additive to play functions of leveling, fog prevention, cleaning and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a modified fluoroether ether surfactant, which comprises the following components in parts by weight:
the modified two-dimensional nano material simultaneously contains hydroxyl and amino.
In the invention, the modified two-dimensional nano material is used as a template and is put into a fluoroethanol ether synthesis reaction, hydroxyl in the modified two-dimensional nano material can be polymerized with ethylene oxide in situ to form a polyether chain, and amino in the modified two-dimensional nano material can be grafted with fluoroalcohol. The modified fluoroethanol ether surfactant disclosed by the invention has the characteristics of high adhesive force and high strength of a nano material and high surface activity of a fluorocarbon surfactant material, and can be used as an additive to play the functions of leveling, fog prevention, cleaning and the like.
The modified two-dimensional nano material is introduced in the invention, so that the performances of leveling, barrier, water resistance and the like of the coating can be improved, for example, the antifogging coating uses a pure fluorine alcohol ether surfactant, so that an antifogging effect can be achieved, but the surfactant is easy to run off, and the antifogging is often long and the scrubbing resistance and durability are poor; the fluoroalcohol ether surfactant modified by the modified two-dimensional nanomaterial prepared by the invention can achieve an antifogging effect, and meanwhile, the modified two-dimensional nanomaterial has good barrier and water resistance and can slow down the loss of the surfactant, so that the antifogging duration and the scratch resistance are better.
In the invention, if the dosage of the fluoroalcohol and the ethylene oxide is too different, for example, the weight part of the fluoroalcohol is less than 20 parts, the weight part of the ethylene oxide is more than 80 parts, or the weight part of the fluoroalcohol is more than 80 parts, the weight part of the ethylene oxide is less than 20 parts, the grafting ratio of the fluoroalcohol and the ethylene oxide on the modified two-dimensional nanomaterial is too different, the polymerization degrees of the fluorocarbon chain and the polyether chain are more different, and finally the surface activity of the modified fluoroalcohol ether surfactant is not good.
In the invention, in the raw materials for preparing the modified fluoroalcohol ether surfactant, the modified two-dimensional nanomaterial may be used in an amount of 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, or the like.
In the present invention, in the raw material for preparing the modified fluoroalcohol ether surfactant, the amount of the fluoroalcohol may be 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, or 80 parts, etc.
In the present invention, the amount of ethylene oxide used in the raw materials for preparing the modified fluoroalcohol ether surfactant may be 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, or 80 parts, etc.
In the present invention, the amount of the catalyst used in the raw material for preparing the modified fluoroalcohol ether surfactant may be 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, or the like.
Preferably, the modified two-dimensional nanomaterial is prepared by the following preparation method:
(1) Dispersing a two-dimensional nano material into a solvent, adding a dispersing agent, and carrying out ultrasonic treatment to enable the two-dimensional nano material to be intercalated and stripped to obtain a suspension;
(2) Standing the obtained suspension, sucking the supernatant, performing superfine suction filtration on the supernatant by using a filter membrane, cleaning and suction filtration by using a solvent, and drying to obtain a two-dimensional nano material membrane;
(3) And (3) placing the two-dimensional nano material film in a plasma atmosphere for treatment, and then drying in vacuum to constant weight to obtain the modified two-dimensional nano material.
In the invention, the two-dimensional nanomaterial is deposited and spread to form a two-dimensional nanomaterial film, and the material top surface-OH is aminated by utilizing PLASMA treatment, so that the two-dimensional nanomaterial with the surface partially aminated and partially hydroxylated can be obtained.
Preferably, the two-dimensional nanomaterial is a two-dimensional nanomaterial with hydroxyl groups, and comprises any one of nano zirconium phosphate, modified graphene, a layered clay silicate material or two-dimensional titanium dioxide sheets, preferably nano zirconium phosphate.
Preferably, the modified graphene comprises any one of graphene oxide, fluorinated graphene or fluorinated graphene oxide or a combination of at least two of the same.
Preferably, the layered clay silicate material comprises montmorillonite or talc.
Preferably, the two-dimensional nanomaterial with hydroxyl groups has a particle size of 30-3000nm, such as 30nm, 50nm, 80nm, 100nm, 300nm, 500nm, 800nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, or the like.
If the particle size of the two-dimensional nanomaterial with hydroxyl is less than 30nm, the reaction yield of the fluoroalcohol and the ethylene oxide on the two-dimensional nanomaterial is greatly reduced, and if the particle size of the two-dimensional nanomaterial with hydroxyl is greater than 3000nm, the two-dimensional nanomaterial is more likely to agglomerate, so that the reaction cannot be carried out.
Preferably, the solvent in step (1) comprises water or an organic solvent, and the organic solvent comprises any one of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide or isopropanol.
Preferably, the dispersant comprises any one or a combination of at least two of an alkyl amine, an amino alcohol, or a polyether amine, preferably any one or a combination of at least two of oleylamine, ethanolamine, tetramethylammonium bromide, cetyltrimethylammonium bromide, tetrabutylammonium, aminopropanol, aminobutanol, diglycolamine, tris (hydroxymethyl) aminomethane amine, polyethylene glycol ether amine, polypropylene glycol ether amine, or polytetrahydrofuranether amine.
Preferably, the molar ratio of the dispersant to the two-dimensional nanomaterial is (0.5-2): 1, e.g., 0.5.
Preferably, the filtering membrane in the step (2) comprises a hybrid fiber membrane or a PTFE membrane.
Preferably, the pore size of the filter membrane in the step (2) is 0.22 μm or 0.47 μm.
Preferably, the thickness of the two-dimensional nanomaterial film of step (2) is 5-2000nm, such as 5nm, 8nm, 10nm, 20nm, 30nm, 50nm, 80nm, 100nm, 300nm, 500nm, 800nm, 1000nm, 1500nm, or 2000nm.
If the thickness of the two-dimensional nano material film is less than 5nm, the monodispersion layer is too thin, and the process difficulty is high; if the thickness of the two-dimensional nano material film is larger than 2000nm, the number of stacked layers is too large, and the modification efficiency of the middle layer is low during subsequent plasma treatment, so that the final grafting rate of the fluorine alcohol is low.
Preferably, the solvent of step (2) comprises alcohol or water.
Preferably, the plasma of step (3) comprises N 2 And/or NH 3 。
Preferably, the plasma of step (3) further comprises any one of He, ar, ne or Xe.
Preferably, the temperature of the vacuum drying in step (3) is 40-60 ℃, such as 40 ℃, 50 ℃ or 60 ℃, etc.
Preferably, the two-dimensional nano material film is placed in a plasma atmosphere for treatment in the step (3), specifically, the two-dimensional nano material film is placed on a plasma device, and plasma is sprayed on the surface of the two-dimensional nano material film in an open environment.
Preferably, the plasma device has a power of 100-1500W, such as 100W, 300W, 500W, 800W, 1000W, 1300W or 1500W, etc., and a processing time of 10-1000s, such as 10s, 30s, 50s, 80s, 100s, 200s, 300s, 400s, 500s, 600s, 700s, 800s, 900s or 1000s, etc.
Preferably, the plasma device comprises any one of a dielectric barrier discharge plasma source, a surface discharge plasma source, a volume discharge plasma source, a plasma torch source, an arc plasma torch, a sliding arc plasma torch, a cold plasma torch, a direct current plasma source, a pulsed plasma source, a magnetron plasma source, an inductively coupled plasma source, a helical tube plasma source, a helical resonator plasma source, a microwave plasma source, an atmospheric pressure plasma jet source, a corona discharge plasma source, a microplasma source, a low pressure plasma source, or a high pressure plasma source.
Preferably, the first and second electrodes are formed of a metal, the fluoroalcohols include 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and 2,2,3,4,4,4-hexachlorobutanol or 3,3,4,5,5,6,7,7,8,8, 8-tridecafluoro-1-octanol, or combinations of at least two thereof.
Preferably, the catalyst comprises any one or a combination of at least two of iodine, sodium iodide, sodium borohydride, boron trifluoride diethyl etherate, triethylamine or tri-n-butylamine, preferably a combination of iodine, sodium iodide and sodium borohydride. The selection of the catalyst can reduce the direct graft polymerization of the fluoroalcohol and the ethylene oxide, so that more fluoroalcohol and ethylene oxide can be grafted on the two-dimensional nano material.
In a second aspect, the present invention provides a process for the preparation of the modified fluoroether ether surfactant of the first aspect, the process comprising the steps of:
adding the fluoroalcohol into a reaction kettle, heating, dehydrating, then sequentially adding the catalyst and the modified two-dimensional nano material, heating again, then slowly adding the ethylene oxide, performing curing reaction, cooling, and performing vacuum degassing to obtain the modified fluoroalcohol ether surfactant.
The reaction process and the selection of the catalyst can reduce the direct graft polymerization of the fluoroalcohol and the ethylene oxide, so that more fluoroalcohol and ethylene oxide can be grafted on the two-dimensional nano material.
Preferably, the temperature rise is to 80-90 ℃, such as 80 ℃, 85 ℃ or 90 ℃ and the like.
Preferably, the time for dehydration is 0.5-1.5h, such as 0.5h, 1h, 1.5h, and the like.
Preferably, the addition of the catalyst is carried out under a protective atmosphere comprising nitrogen.
Preferably, the second heating is to 120-145 deg.C, such as 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C or 145 deg.C.
Preferably, the slow addition of ethylene oxide is performed by controlling the feed time of ethylene oxide to be 5-7h, such as 5h, 5.5h, 6h, 6.5h or 7 h.
Preferably, the temperature of the aging reaction is 130-135 ℃, such as 130 ℃, 133 ℃ or 135 ℃, and the time of the aging reaction is 1.5-2.5h, such as 1.5h, 2h or 2.5 h.
Preferably, the temperature reduction is to 110-120 ℃, such as 110 ℃, 112 ℃, 114 ℃, 115 ℃, 116 ℃, 118 ℃ or 120 ℃.
Preferably, the vacuum degassing is performed for a period of 20-40min, such as 20min, 25min, 30min, 35min or 40 min.
In a third aspect, the present invention provides the use of a modified fluoroether ether surfactant of the first aspect in a coating;
preferably, the coating comprises an anti-fog coating.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the modified two-dimensional nano material is used as a template and is put into a fluoroethanol ether synthesis reaction, hydroxyl in the modified two-dimensional nano material can be polymerized with ethylene oxide in situ to form a polyether chain, amino in the modified two-dimensional nano material can be grafted with fluoroalcohol to form a fluorocarbon chain, and finally a nano material 'block' fluoroalcohol ether surface active material is formed. The modified fluoroethanol ether surfactant disclosed by the invention has the characteristics of high adhesive force and high strength of a nano material and high surface activity of a fluorocarbon surfactant material, and can be used as an additive to play the functions of leveling, fog prevention, cleaning and the like (both the fog resistance and the fog prevention durability are level 1).
Drawings
Fig. 1 is a graph of the antifog test results for the modified fluoroether ether surfactants provided in example 1 (left panel) and example 2 (right panel).
Fig. 2 is a graph of the antifog test results for the modified fluoroether ether surfactants provided in example 3 (left panel) and example 4 (right panel).
Fig. 3 is a graph of antifog test results for the modified fluoroether ether surfactants provided in example 5 (left panel) and example 7 (right panel).
Fig. 4 to 6 are graphs showing the results of the antifogging test of the modified fluoroether ether surfactants provided in comparative examples 1 to 3, respectively.
Fig. 7 is a graph of antifog film water resistance test results for the modified fluoroether ether surfactants provided in example 1 (left panel) and example 2 (right panel).
Fig. 8 is a graph of antifog film water resistance test results for the modified fluoroether ether surfactants provided in example 3 (left panel) and example 4 (right panel).
Fig. 9 is a graph of the results of the antifogging film water resistance test for the modified fluoroether ether surfactants provided in example 5 (left panel) and example 7 (right panel).
Fig. 10 to 12 are graphs showing the results of the water resistance test of the antifogging film of the modified fluoroether ether surfactant provided in comparative examples 1 to 3, respectively.
Fig. 13 to 18 are graphs showing the results of the anti-fog durability test of the modified fluoroether ether surfactants provided in example 1, example 5, example 7, and comparative example 1 to comparative example 3, respectively.
Fig. 19 to 22 are graphs showing the results of the scrub resistance test at the 10 th time of the rubbing of the antifogging films made of the modified fluoroether ether surfactants provided in examples 1 to 4, respectively.
Fig. 23 is a graph showing the result of the abrasion resistance test of the antifogging film made of the modified fluoroether ether surfactant provided in comparative example 2 at the 2 nd friction time.
Fig. 24 to 28 are appearance diagrams of modified fluoroether ether surfactants provided in example 1, example 5, example 7, comparative example 1 and example 6, respectively.
Fig. 29 to 34 are water droplet contact angle test charts of the modified fluoroether ether surfactants provided in example 1, example 5, example 7 and comparative example 1 to 3, respectively.
FIG. 35 is an SEM image of the two-dimensional nanomaterial film prepared in example 1 after intercalation, exfoliation, suction filtration and drying.
Fig. 36 is a XRD test result chart of the original two-dimensional nanomaterial (before processing) provided in example 1 and the two-dimensional nanomaterial after intercalation, exfoliation, suction filtration and drying.
Fig. 37 is a graph of FTIR test results for the original two-dimensional nanomaterial (before processing) and the modified two-dimensional nanomaterial provided in example 1.
Fig. 38 is an SEM image of the modified fluoroethanol ether surfactant of example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the raw materials used in the examples and comparative examples of the present invention are as follows:
nano zirconium phosphate: prepared by the method of CN 108129927B;
montmorillonite: beijing Yiyu specialization science and technology development Co;
and (3) graphene oxide: liaoning Lanjing science and technology, inc.;
PET film: dongguan city, yihong industry Co., ltd.
Example 1
In this embodiment, a modified fluoroether ether surfactant is provided, and a preparation raw material of the modified fluoroether ether surfactant comprises the following components in parts by weight:
the modified two-dimensional nano material contains hydroxyl and amino at the same time.
Wherein, the fluorine alcohol is 2, 2-trifluoroethanol; the catalyst is iodine (0.2 part), sodium iodide (0.1 part) and sodium borohydride (0.2 part); the modified two-dimensional nano material is prepared by the following preparation method:
(1) Dispersing a two-dimensional nano material with hydroxyl into water (the mass concentration of the two-dimensional nano material in the water is 0.2%), adding a dispersing agent, and performing ultrasonic treatment to intercalate and strip the two-dimensional nano material to obtain a suspension; wherein the two-dimensional nano material with hydroxyl is nano zirconium phosphate with hydroxyl, the particle size is 1000nm, the dispersant is ethanolamine, and the molar ratio of the dispersant to the two-dimensional nano material is 1;
(2) Standing the obtained suspension for 2h, sucking the supernatant, performing superfine suction filtration on the supernatant by using a PTFE (polytetrafluoroethylene) membrane with the aperture of 0.47 mu m, cleaning and suction filtration by using a solvent (water), and drying to obtain a two-dimensional nano material membrane with the thickness of 1000 nm;
(3) Placing a two-dimensional film of nanomaterial on a plasma device and subjecting the plasma (N) to an open environment 2 ) Spraying the mixture on the surface of the two-dimensional nano material film, and then drying the treated two-dimensional nano material film in vacuum at 50 ℃ to constant weight to obtain the modified two-dimensional nano material. The plasma device is a direct current plasma source, the power is 1000W, and the processing time is 500s.
The preparation method of the modified fluoroethanol ether surfactant comprises the following steps:
at normal temperature, adding fluoroalcohol into a reaction kettle, sealing the kettle, starting stirring, vacuumizing the kettle to more than-0.098 MPa, performing nitrogen vacuum displacement for 3 times to ensure thorough air displacement in the kettle, heating to 80 ℃, vacuumizing to more than-0.099 MPa under negative pressure, performing nitrogen blowing dehydration for 1h by slightly introducing nitrogen flow, adding a catalyst under the protection of nitrogen after dehydration is completed, then adding a modified two-dimensional nano material, heating to 140 ℃, then slowly adding ethylene oxide, controlling the feeding time of the ethylene oxide to be 6h, curing and reacting at 130 ℃ for 2h after the feeding of the ethylene oxide is completed, then cooling to 110 ℃, performing vacuum degassing for 30min, cooling to 50 ℃, and discharging to obtain the modified fluoroalcohol ether surfactant.
Example 2
In this embodiment, a modified fluoroether ether surfactant is provided, and a preparation raw material of the modified fluoroether ether surfactant comprises the following components in parts by weight:
the modified two-dimensional nano material simultaneously contains hydroxyl and amino.
Wherein, the fluorine alcohol is 2, 2-trifluoroethanol; the catalyst is sodium iodide; the modified two-dimensional nano material is prepared by the following preparation method:
(1) Dispersing a two-dimensional nano material with hydroxyl into N-methyl pyrrolidone (the mass concentration of the two-dimensional nano material in the N-methyl pyrrolidone is 0.01%), adding a dispersing agent, and performing ultrasonic treatment to enable the two-dimensional nano material to be intercalated and stripped to obtain a suspension; wherein the two-dimensional nano material with hydroxyl is montmorillonite with hydroxyl, the particle size is 30nm, the dispersant is ethanolamine, and the molar ratio of the dispersant to the two-dimensional nano material is 1;
(2) Standing the obtained suspension for 1h, sucking the supernatant, performing superfine suction filtration on the supernatant by using a PTFE (polytetrafluoroethylene) membrane with the aperture of 0.22 mu m, cleaning and suction filtration by using a solvent (water), and drying to obtain a two-dimensional nano material membrane with the thickness of 5 nm;
(3) Placing a two-dimensional film of the nanomaterial on a plasma device and subjecting the plasma (NH) to an open environment 3 ) Spraying the mixture on the surface of the two-dimensional nano material film, and then drying the treated two-dimensional nano material film in vacuum at 40 ℃ to constant weight to obtain the modified two-dimensional nano material. Wherein, the plasma device is a direct current plasma source, the power is 100W, and the processing time is 1000s.
The preparation method of the modified fluoroether ether surfactant comprises the following steps:
at normal temperature, adding fluoroalcohol into a reaction kettle, sealing the kettle, starting stirring, vacuumizing the kettle to more than-0.098 MPa, performing nitrogen vacuum displacement for 3 times to ensure thorough air displacement in the kettle, heating to 80 ℃, vacuumizing to more than-0.099 MPa under negative pressure, performing nitrogen blowing dehydration for 1h by slightly introducing nitrogen flow, adding a catalyst under the protection of nitrogen after dehydration is completed, then adding a modified two-dimensional nano material, heating to 145 ℃, then slowly adding ethylene oxide, controlling the feeding time of the ethylene oxide to be 6h, curing and reacting at 135 ℃ for 2h after the feeding of the ethylene oxide is completed, then cooling to 115 ℃, performing vacuum degassing for 30min, cooling to 50 ℃, and discharging to obtain the modified fluoroalcohol ether surfactant.
Example 3
In this embodiment, a modified fluoroether ether surfactant is provided, and a preparation raw material of the modified fluoroether ether surfactant comprises the following components in parts by weight:
the modified two-dimensional nano material simultaneously contains hydroxyl and amino.
Wherein the fluorine alcohol is 2, 3-pentafluoropropanol; the catalyst is sodium borohydride; the modified two-dimensional nano material is prepared by the following preparation method:
(1) Dispersing a two-dimensional nano material with hydroxyl into N, N-dimethylformamide (the mass concentration of the two-dimensional nano material in the N, N-dimethylformamide is 0.5%), adding a dispersing agent, and performing ultrasonic treatment to enable the two-dimensional nano material to be intercalated and stripped to obtain a suspension; the two-dimensional nanomaterial with hydroxyl is graphene oxide with hydroxyl, the particle size is 3000nm, the dispersant is ethanolamine, and the molar ratio of the dispersant to the two-dimensional nanomaterial is 1;
(2) Standing the obtained suspension for 5h, sucking the supernatant, performing superfine suction filtration on the supernatant by using a PTFE (polytetrafluoroethylene) membrane with the aperture of 0.47 mu m, cleaning and suction filtration by using a solvent (water), and drying to obtain a two-dimensional nano material membrane with the thickness of 2000 nm;
(3) Placing a two-dimensional film of nanomaterial on a plasma device and subjecting the plasma (N) to an open environment 2 And/or NH 3 ) Spraying the mixture on the surface of the two-dimensional nano material film, and then drying the treated two-dimensional nano material film in vacuum at the temperature of 60 ℃ to constant weight to obtain the modified two-dimensional nano material. The plasma device is a direct current plasma source, the power is 1500W, and the processing time is 10s.
The preparation method of the modified fluoroethanol ether surfactant comprises the following steps:
at normal temperature, adding fluoroalcohol into a reaction kettle, sealing the kettle, starting stirring, vacuumizing the kettle to be more than-0.098 MPa, performing nitrogen vacuum displacement for 3 times to ensure thorough air displacement in the kettle, heating to 80 ℃, vacuumizing to be more than-0.099 MPa under negative pressure, performing nitrogen blowing dehydration for 1h by slightly introducing nitrogen flow, after dehydration is completed, adding a catalyst under the protection of nitrogen, then adding a modified two-dimensional nanomaterial, heating to 140 ℃, then slowly adding ethylene oxide, controlling the feeding time of the ethylene oxide to be 6h, after the feeding of the ethylene oxide is finished, performing curing reaction at 135 ℃ for 2h, then cooling to 120 ℃, performing vacuum degassing for 30min, cooling to 50 ℃, and discharging to obtain the modified fluoroalcohol ether surfactant.
Example 4
In this embodiment, a modified fluoroether ether surfactant is provided, and a raw material for preparing the modified fluoroether ether surfactant comprises the following components in parts by weight:
the modified two-dimensional nano material simultaneously contains hydroxyl and amino.
Wherein, 2, 3-pentafluoropropanol, iodine (0.2 part), sodium iodide (0.1 part) and sodium borohydride (0.2 part) are used as catalysts; the modified two-dimensional nano material is prepared by the following preparation method:
(1) Dispersing a two-dimensional nano material with hydroxyl into water (the mass concentration of the two-dimensional nano material in the water is 0.1%), adding a dispersing agent, and performing ultrasonic treatment to intercalate and strip the two-dimensional nano material to obtain a suspension; the two-dimensional nano material with hydroxyl is nano zirconium phosphate with hydroxyl, the particle size is 500nm, the dispersing agent is ethanolamine, and the molar ratio of the dispersing agent to the two-dimensional nano material is 1;
(2) Standing the obtained suspension for 4h, sucking the supernatant, performing superfine suction filtration on the supernatant by using a PTFE (polytetrafluoroethylene) membrane with the aperture of 0.22 mu m, cleaning and suction filtration by using a solvent (water), and drying to obtain a two-dimensional nano material membrane with the thickness of 800 nm;
(3) Placing a two-dimensional film of nanomaterial on a plasma device and subjecting the plasma (N) to an open environment 2 、NH 3 And He) onto the surface of the two-dimensional nanomaterial film, and then vacuum-drying the treated two-dimensional nanomaterial film at 50 ℃ to constant weight to obtain the modified two-dimensional nanomaterial. Wherein, the plasma device is a direct current plasma source, the power is 500W, and the processing time is 800s.
The preparation method of the modified fluoroethanol ether surfactant comprises the following steps:
at normal temperature, adding fluoroalcohol into a reaction kettle, sealing the kettle, starting stirring, vacuumizing the kettle to more than-0.098 MPa, performing nitrogen vacuum displacement for 3 times to ensure thorough air displacement in the kettle, heating to 80 ℃, vacuumizing to more than-0.099 MPa under negative pressure, performing nitrogen blowing dehydration for 1h by slightly introducing nitrogen flow, adding a catalyst under the protection of nitrogen after dehydration is completed, then adding a modified two-dimensional nano material, heating to 145 ℃, then slowly adding ethylene oxide, controlling the feeding time of the ethylene oxide to be 6h, curing and reacting at 130 ℃ for 2h after the feeding of the ethylene oxide is completed, then cooling to 110 ℃, performing vacuum degassing for 30min, cooling to 50 ℃, and discharging to obtain the modified fluoroalcohol ether surfactant.
Example 5
The present example is different from example 1 only in that the particle size of the two-dimensional nanomaterial with hydroxyl groups is 20nm, and the other conditions are the same as example 1.
Example 6
This example is different from example 1 only in that the particle size of the two-dimensional nanomaterial having hydroxyl groups is 3200nm, and the other conditions are the same as example 1.
Example 7
This example is different from example 1 only in that the mass concentration of the modified two-dimensional nanomaterial in the solvent is large (1%), and the total amount of the solution is too large, so that the thickness of the prepared two-dimensional nanomaterial film is 3000nm, and other conditions are the same as example 1.
Comparative example 1
This comparative example differs from example 1 only in that the modified two-dimensional nanomaterial was replaced with an equivalent amount of unmodified two-dimensional nanomaterial (i.e., the zirconium phosphate nanoparticles bearing hydroxyl groups, but not subjected to plasma treatment), and the other conditions were the same as example 1.
Comparative example 2
This comparative example is different from example 1 only in that 10 parts by weight of fluoroalcohol and 90 parts by weight of ethylene oxide were used, and the other conditions were the same as example 1.
Comparative example 3
This comparative example is different from example 1 only in that the weight parts of the fluoroalcohol is 90 parts and the weight parts of the ethylene oxide is 10 parts, and the other conditions are the same as example 1.
Coating the modified fluoroethanol ether surfactant in the embodiment and the proportion on the surface of the PET film, wherein the coating thickness is 10 mu m, preparing an antifogging film sample, and carrying out a relevant antifogging performance test, wherein the test method comprises the following steps:
(1) Antifogging test: and (3) sticking the sample on glass, wherein the distance between the sample and the glass is 20cm, carrying out steam injection by using high-temperature steam at 100 ℃, and immediately penetrating the sample to obtain the antifogging effect.
(2) And (3) testing the antifogging durability: adding 200mL of water into a beaker with the volume of 250mL, covering the opening of the beaker with a sample, and placing the beaker in a constant-temperature water bath kettle at 50 ℃; after 30 minutes, the samples were visually observed for fogging.
(3) And (3) testing the antifogging durability in an extreme environment: 500mL of water was added to a beaker having a volume of 1000mL, the sample was covered on the cup mouth, the beaker was placed on a hot plate, and the water was continuously boiled, and after 30 minutes, the sample was visually observed for fogging.
(4) Testing the scratch resistance of the antifogging film: adhering a sample on glass, rubbing the sample by a finger for 5 times to-and-fro, keeping the distance from the sample to 10cm, carrying out steam-spraying for 5 seconds at the high temperature of 100 ℃, and repeatedly carrying out finger rubbing-steam-spraying for 5 seconds to observe the antifogging effect test at the same position after observing the antifogging effect; and recording the hand rubbing times when water drops and mist appear at the same position of the sample.
(5) Testing the water resistance of the antifogging film: and (3) soaking the sample in deionized water at normal temperature for 30min, taking out the sample, drying the sample at room temperature for 1 hour, and carrying out antifogging test.
Evaluation criteria for fogging:
grade 1 represents completely clear without water droplets;
grade 3 represents substantially transparent, with more water droplets, the area of water droplets present not exceeding 30%;
grade 4 represents translucence, a plurality of small water drops exist, and the area of the water drops is more than 50%;
(6) Contact angle test: and measuring the water drop contact angle of the antifogging film sample by using a contact angle measuring instrument (model SDC-200S) of Chengding precision instrument Limited in Dongguan city.
The results of the performance tests are shown in table 1.
TABLE 1
As can be seen from table 1, the modified fluoroethanol ethers prepared in examples 1 to 4 of the present invention all had excellent antifogging property, antifogging durability, antifogging film friction resistance and antifogging film water resistance, and all had excellent hydrophilicity.
Compared with the example 1, the antifogging effect of the modified fluoroethanol ether surfactant prepared in the example 5 is obviously reduced; example 6 precipitation occurred due to too large particle size of the modified two-dimensional nanomaterial, and the test could not be performed; the antifogging effect of the modified fluoroethanol ether surfactant prepared in example 7 was significantly reduced.
Compared with the example 1, the two-dimensional nano material in the comparative example 1 is not subjected to plasma treatment, and the antifogging property and the antifogging durability of the prepared modified fluoroethanol ether surfactant are obviously reduced; compared with the prior art, the modified fluoroethanol ether surfactant prepared by the method has poor adhesion due to excessive addition of ethylene oxide in the comparative example 2, so that the antifogging durability is reduced; comparative example 3 added too much fluoroalcohol, and the prepared modified fluoroalcohol ether surfactant was hydrophobic, resulting in significant decrease in both antifogging property and antifogging durability.
As can also be seen from the results of the antifogging test in fig. 1 to 6, the modified fluoroether ether surfactants prepared in examples 1 to 4 (fig. 1 and 2) and comparative example 2 (fig. 5) have excellent antifogging properties, and the modified fluoroether ether surfactants prepared in examples 5 and 7 (fig. 3), comparative example 1 (fig. 4) and comparative example 3 (fig. 6) have significantly deteriorated antifogging properties. In the figures, the black square frames are encircled by the antifogging films, and the black square frames appearing in other figures are encircled by the antifogging films, so that the antifogging films are not described one by one.
As can be seen from the results of the antifogging film water resistance test of fig. 7-12, the modified fluoroether ether surfactants prepared in examples 1-4 (fig. 7 and 8) have excellent antifogging film water resistance, and the antifogging film water resistance of the modified fluoroether ether surfactants prepared in examples 5 and 7 (fig. 9), comparative example 1 (fig. 10) and comparative example 3 (fig. 12) is significantly deteriorated.
As can be seen from the results of the antifog durability test of fig. 13 to 18, the modified fluoroether ether surfactant prepared in example 1 (fig. 13) has excellent antifog durability, and the antifog durability of the modified fluoroether ether surfactant prepared in example 5 (fig. 14), example 7 (fig. 15), comparative example 1 to comparative example 3 (fig. 16 to 18) is significantly deteriorated.
As can be seen from the graphs of the results of the scratch resistance test of the antifogging films of fig. 19 to 23, the antifogging films prepared from the modified fluoroether ether surfactants prepared in examples 1 to 4 (fig. 19 to 22) still have excellent antifogging effect at the 10 th rubbing, while the antifogging films of comparative example 2 (fig. 23) show water drops and fog at the 2 nd rubbing.
The modified fluoroether ether surfactants prepared in examples 1-4, 5, 7 and comparative examples 1-3 of the present invention were all clear liquids, whereas the modified fluoroether ether surfactant prepared in example 6 was precipitated (as shown in fig. 28).
As can be seen from the water drop contact angle test charts of fig. 29 to 34, the modified fluoroether ether surfactants prepared in example 1 (fig. 29) and comparative example 2 (fig. 33) have better hydrophilicity, while the modified fluoroether ether surfactants prepared in example 5 (fig. 30), example 7 (fig. 31), comparative example 1 (fig. 32) and comparative example 3 (fig. 34) have poorer hydrophilicity.
An antifogging coating added with the modified fluoroethanol ether surfactant in the embodiment and the proportion is coated on the surface of the PET film (the antifogging coating specifically comprises the following components of polyurethane: 80 wt%, modified fluoroethanol ether surfactant: 20 wt%, wherein the polyurethane is anionic single-component waterborne polyurethane, and a manufacturer is Basff), the coating thickness is 10 mu m, an antifogging film sample is prepared, and other related performance tests are carried out, wherein the test method comprises the following steps:
(1) Adhesion force: the adhesive force adopts a cross-cut method according to the GB/T9286-1998 standard.
(2) Hardness: pencil hardness test
And (4) judging standard: after the sample is completely cured, the length of the paint film is drawn for 5 times by using a vertical pressure of 1 kg and a 45-degree oblique angle, the paint film has no scratch, and the pencil-grade hardness is the hardness of the paint film.
The pencil hardness grades are 6B, 5B, 4B, 3B, 2B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H and 9H.
(3) Light transmittance: using a light transmittance haze tester, cutting the sample into a size of a square of 5cm × 5cm, selecting the center and four vertexes of the sample, respectively testing the light transmittance, and taking an average value.
The performance test results are shown in table 2:
TABLE 2
| Thickness (nm) | Adhesion (grade) | Hardness (grade) | Light transmittance (%) | |
| Example 1 | 1000 | 0 | 3H | 93.5 |
| Example 2 | 5 | 0 | 2H | 94.0 |
| Example 3 | 2000 | 0 | 3H | 93.0 |
| Example 4 | 800 | 0 | 2H | 94.0 |
| Example 5 | 1000 | 1 | H | 94.5 |
| Example 6 | — | — | — | — |
| Example 7 | 3000 | 0 | 3H | 91.0 |
| Comparative example 1 | 1000 | 4 | H | 90.5 |
| Comparative example 2 | 1000 | 5 | 2H | 92.0 |
| Comparative example 3 | 1000 | 1 | 3H | 93.5 |
As can be seen from Table 2, the modified fluoroethanol ether surfactants provided by the embodiments 1 to 4 of the invention have excellent adhesion and hardness (2H-3H), and the light transmittance (93.5% -94.0%) can meet the use requirements.
The two-dimensional nanomaterial film prepared in example 1 after intercalation, exfoliation, suction filtration and drying is subjected to SEM (scanning electron microscope) test, the model of the instrument is a TESCAN desktop electron microscope, and the test result is shown in fig. 35.
XRD (X-ray diffraction, instrument model: BRUKER D8) is carried out on the original two-dimensional nano material (before treatment) in the example 1 and the two-dimensional nano material after intercalation, stripping, suction filtration and drying, and the test result is shown in figure 36, so that the characteristic peak of (0, 2) is shifted from-12 degrees to a low angle, which shows that the interlayer spacing of the material is enlarged due to intercalation and partial stripping; (1,1,0) and (1,1,2) the large-angle peaks were weakened and flattened, indicating that the two-dimensional nanomaterial was exfoliated to some extent.
The original two-dimensional nanomaterial of example 1 (before processing) and the modified two-dimensional nanomaterial were subjected to FTIR testing (Fourier Transform I)nfrared Spectrometer, fourier transform infrared spectroscopy test, instrument model: lambda 7600), the test results are shown in FIG. 37, wherein, the length is 900-1200 cm -1 The absorption peak belongs to the absorption of asymmetric and symmetric telescopic vibration of phosphate radical groups, and is 3500-3580 cm -1 The absorption peak of (1) is the asymmetric and symmetric telescopic vibration absorption of water, 3150cm -1 The absorption peak is the hydroxyl stretching vibration absorption of the P-O-H group. As can be seen from the figure, in the processed nanomaterial: 3150cm -1 The absorption peak disappears, which indicates that P-O-H in the material is grafted by reaction; at 985cm -1 An obvious absorption peak appears at the position, which is the stretching vibration of-C-O-C-in polyether; 3500-3580 cm -1 The absorption peak is obviously reduced, which shows that the content of the crystal water of the material is reduced after the grafting reaction, and the absorption peak is towards 3500cm -1 The direction is moved, and the absorption peak is a primary alcohol-OH bond absorption peak; 1190 to 1300cm -1 Has a distinct absorption peak of-CF 3 、-CF 2 The stretching vibration of-CF-proves that the grafting reaction of the two-dimensional material, the fluoroalcohol and the ethylene oxide occurs.
The modified fluoroethanol ether surfactant prepared in example 1 was subjected to SEM test and EDS (Energy dispersion spectroscopy, X-ray micro-area analysis) test, wherein SEM test instrument: TESCAN desktop electron microscope, EDS test instrument: BRUKER EDS QUANTAX, SEM test results are shown in FIG. 38, EDS point scans of the surfactant at the cross in the SEM are shown in Table 3:
TABLE 3
| Element(s) | Thread system | Mass content (wt.%) | Atomic content (at.%) | Error (wt.%) |
| Zr | System of K-wires | 44.04 | 13.11 | 5.97 |
| F | K-line system | 10.76 | 15.35 | 2.26 |
| P | System of K-wires | 15.49 | 13.54 | 6.21 |
| C | K-line system | 13.38 | 30.22 | 3.16 |
| O | System of K-wires | 15.67 | 26.53 | 5.23 |
| N | K-line system | 0.65 | 1.25 | 1.39 |
From the EDS test results, it can be seen that the modified fluoroether ether surfactant prepared in example 1 contains F and N. In combination with the comparison of the results of example 1 and comparative example 1 in table 1 (compared with example 1, the antifogging property, antifogging durability, antifogging film scratch resistance and antifogging film water resistance of the modified fluoroethanol ether surfactant prepared in comparative example 1 are all reduced), it can be seen that the fluoroalcohol and ethylene oxide in example 1 are successfully grafted on the modified two-dimensional nanomaterial, while the two-dimensional nanomaterial of comparative example 1 is not modified, the fluoroalcohol is not grafted on the two-dimensional nanomaterial, and part of the fluoroalcohol and part of the ethylene oxide react, so that the antifogging effect of the prepared surfactant is poor.
The applicants state that the present invention is illustrated by the above examples for the modified fluoroether ether surfactants and methods of making and using the same, but the present invention is not limited to the above examples, which is not meant to imply that the present invention must be practiced in any way. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (33)
1. The modified fluoroalcohol ether surfactant is characterized in that the modified fluoroalcohol ether surfactant comprises the following components in parts by weight:
10-100 parts of modified two-dimensional nano material;
20-80 parts of fluoroalcohol;
20-80 parts of ethylene oxide;
0.3-1 part of catalyst;
the modified two-dimensional nano material simultaneously contains hydroxyl and amino;
the modified two-dimensional nano material is prepared by the following preparation method:
(1) Dispersing a two-dimensional nano material into a solvent, adding a dispersing agent, and carrying out ultrasonic treatment to enable the two-dimensional nano material to be intercalated and stripped to obtain a suspension;
(2) Standing the obtained suspension, sucking the supernatant, performing superfine suction filtration on the supernatant by using a filter membrane, cleaning, suction filtration and drying by using a solvent to obtain a two-dimensional nano material membrane;
(3) Placing the two-dimensional nano material film in a plasma atmosphere for treatment, and then drying the two-dimensional nano material film in vacuum to constant weight to obtain the modified two-dimensional nano material;
the two-dimensional nano material is a two-dimensional nano material with hydroxyl, and comprises any one of nano zirconium phosphate, modified graphene, a layered clay silicate material or a two-dimensional titanium dioxide sheet.
2. The modified fluoroethanol ether surfactant of claim 1, wherein the two-dimensional nanomaterial is nano zirconium phosphate.
3. The modified fluoroethanol ether surfactant of claim 1, wherein the modified graphene comprises graphene oxide and/or graphene fluoride.
4. The modified fluoroalcohol ether surfactant of claim 1, wherein said layered clay silicate material comprises montmorillonite or saponite.
5. The modified fluoroethanol ether surfactant of claim 1, wherein the two-dimensional nanomaterial comprising hydroxyl groups has a particle size of 30 to 3000 nm.
6. The modified fluoroether ether surfactant of claim 1, wherein the solvent of step (1) comprises water or an organic solvent comprising any one of N-methylpyrrolidone, N-dimethylformamide, dimethylsulfoxide, or isopropanol.
7. The modified fluoroalcohol ether surfactant of claim 1, wherein the dispersant comprises any one or a combination of at least two of an alkyl amine, an amino alcohol or a polyether amine.
8. The modified fluoroethanol ether surfactant of claim 1, wherein the dispersant comprises any one or a combination of at least two of oleylamine, ethanolamine, tetramethylammonium bromide, cetyltrimethylammonium bromide, tetrabutylammonium, aminopropanol, aminobutanol, diglycolamine, tris (hydroxymethyl) aminomethane amine, polyethyleneglycol ether amine, polypropyleneglycol ether amine or polytetrahydrofuran ether amine.
9. The modified fluoroether ether surfactant of claim 1, wherein the molar ratio of the dispersant to the two-dimensional nanomaterial is (0.5-2): 1.
10. The modified fluoroether ether surfactant of claim 1, wherein the filtering membrane of step (2) comprises a hybrid fiber membrane or a PTFE membrane.
11. The modified fluoroethanol ether surfactant of claim 1, wherein the pore size of the filtration membrane of step (2) is 0.22 μm or 0.47 μm.
12. The modified fluoroethanol ether surfactant of claim 1, wherein the thickness of the two-dimensional nanomaterial film of step (2) is from 5 to 2000nm.
13. The modified fluoroether ether surfactant of claim 1, wherein the solvent of step (2) comprises alcohol or water.
14. The modified fluoroether ether surfactant according to claim 1,the plasma of step (3) comprises N 2 And/or NH 3 。
15. The modified fluoroether ether surfactant of claim 14, wherein the plasma of step (3) further comprises any one of He, ar, ne or Xe.
16. The modified fluoroether ether surfactant of claim 1, wherein the temperature for vacuum drying in step (3) is 40-60 ℃.
17. The modified fluoroethanol ether surfactant of claim 1, wherein the two-dimensional nanomaterial film of step (3) is treated by placing the two-dimensional nanomaterial film on a plasma device and spraying plasma on the surface of the two-dimensional nanomaterial film in an open environment.
18. The modified fluoroalcohol ether surfactant of claim 17, wherein said plasma device has a power of 100-1500W and a treatment time of 10-1000 s.
19. The modified fluoroalcohol ether surfactant of claim 17, wherein said plasma device comprises any one of a dielectric barrier discharge plasma source, a surface discharge plasma source, a bulk discharge plasma source, a plasma torch source, an arc plasma torch, a cold plasma torch, a direct current plasma source, a pulsed plasma source, a magnetron plasma source, an inductively coupled plasma source, a helical tube plasma source, a helical resonator plasma source, a microwave plasma source, an atmospheric pressure plasma jet source, a corona discharge plasma source, a microplasma source, a low pressure plasma source or a high pressure plasma source.
20. The modified fluoroethanol ether surfactant of claim 1, wherein the fluoroalcohol comprises any one of 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,4,4,4-hexachlorobutanol or 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, or a combination of at least two thereof.
21. The modified fluoroether ether surfactant of claim 1, wherein the catalyst comprises any one or a combination of at least two of iodine, sodium iodide, sodium borohydride, boron trifluoride etherate, triethylamine or tri-n-butylamine.
22. The modified fluoroether ether surfactant of claim 21, wherein said catalyst comprises a combination of iodine, sodium iodide and sodium borohydride.
23. The method of making a modified fluoroether ether surfactant according to any one of claims 1-22, comprising the steps of:
adding the fluoroalcohol into a reaction kettle, heating, dehydrating, then sequentially adding the catalyst and the modified two-dimensional nano material, heating again, then slowly adding the ethylene oxide, performing curing reaction, cooling, and performing vacuum degassing to obtain the modified fluoroalcohol ether surfactant.
24. The method according to claim 23, wherein the temperature is raised to 80 to 90 ℃.
25. The method of claim 23, wherein the dehydration time is 0.5 to 1.5 hours.
26. The method of claim 23, wherein the introducing is performed under a protective atmosphere comprising nitrogen.
27. The method according to claim 23, wherein the reheating is carried out at 120 to 145 ℃.
28. The method of claim 23, wherein the slow feeding of ethylene oxide is performed by controlling the feeding time of ethylene oxide to be 5 to 7 hours.
29. The method according to claim 23, wherein the temperature of the aging reaction is 130 to 135 ℃ and the time of the aging reaction is 1.5 to 2.5 hours.
30. The method of claim 23, wherein the temperature reduction is to 110-120 ℃.
31. The method of claim 23, wherein the vacuum degassing is performed for a period of 20-40 min.
32. Use of the modified fluoroethanol ether surfactant of any one of claims 1-22 in a coating.
33. The use of claim 32, wherein the coating comprises an anti-fog coating.
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| CN106867290A (en) * | 2015-12-11 | 2017-06-20 | 张美玲 | A kind of anti-fog coating |
| CN111234200A (en) * | 2020-03-23 | 2020-06-05 | 东北石油大学 | A kind of preparation method of modified perfluoroalcohol polyoxyethylene ether demulsifier for heavy oil |
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| CN106867290A (en) * | 2015-12-11 | 2017-06-20 | 张美玲 | A kind of anti-fog coating |
| CN111234200A (en) * | 2020-03-23 | 2020-06-05 | 东北石油大学 | A kind of preparation method of modified perfluoroalcohol polyoxyethylene ether demulsifier for heavy oil |
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