CN111454406A - Preparation method of fluorine-containing silicon compound, modified fabric and application thereof - Google Patents
Preparation method of fluorine-containing silicon compound, modified fabric and application thereof Download PDFInfo
- Publication number
- CN111454406A CN111454406A CN202010472243.0A CN202010472243A CN111454406A CN 111454406 A CN111454406 A CN 111454406A CN 202010472243 A CN202010472243 A CN 202010472243A CN 111454406 A CN111454406 A CN 111454406A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- silicon compound
- containing silicon
- mercapto
- equal
- 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.)
- Withdrawn
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 28
- 239000011737 fluorine Substances 0.000 title claims abstract description 28
- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000004945 silicone rubber Substances 0.000 claims abstract description 18
- 229920002545 silicone oil Polymers 0.000 claims abstract description 14
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 anthraquinone compound Chemical class 0.000 claims abstract description 12
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims abstract 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 27
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims 1
- 239000000987 azo dye Substances 0.000 abstract description 11
- 150000002823 nitrates Chemical class 0.000 abstract description 7
- 238000006065 biodegradation reaction Methods 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 29
- 239000000835 fiber Substances 0.000 description 21
- 229920001971 elastomer Polymers 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000009941 weaving Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241001147693 Staphylococcus sp. Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of a fluorine-containing silicon compound, a modified fabric and application thereof, wherein an anthraquinone compound containing unsaturated carbon-carbon double bonds and a fluorine-silicon polymer containing sulfydryl are subjected to sulfydryl-alkene click chemical reaction under the irradiation of ultraviolet light to obtain the fluorine-containing silicon compound; the fabric is obtained by crosslinking raw materials consisting of vinyl silicone rubber, the fluorine-containing silicon compound, the mercapto silicone oil and the photoinitiator under the irradiation of ultraviolet light. The fabric can be used for degrading azo dyes and nitrates and promoting and improving the biodegradation rate of the azo dyes and the nitrates.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a preparation method of a fluorine-containing silicon compound, a modified fabric and application thereof.
Background
Anthraquinone compounds and other compounds with the electron transfer capability can greatly improve the degradation of pollutants such as azo dyes, nitrates and the like by anaerobic microorganisms, have good application potential, but can cause 'secondary pollution' of a water body. Therefore, graft-fixing on a carrier is an effective method, and polymer films, fillers and the like are reported as carriers, but the further application is still limited due to low graft density and inconvenient recycling.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art and to provide a process for the preparation of fluorine-containing silicon compounds.
It is a further object of the present invention to provide a modified fabric.
It is a further object of the present invention to provide the use of the modified fabric.
The technical scheme of the invention is as follows:
adding an anthraquinone compound containing unsaturated carbon-carbon double bonds, a fluorine-silicon polymer containing sulfydryl and a photoinitiator into an organic solvent, stirring and dissolving, irradiating for 1-10 minutes under ultraviolet light, removing the ultraviolet light after the irradiation is finished, and removing the organic solvent to obtain the fluorine-containing silicon compound. The organic solvent may be at least one selected from the group consisting of tetrahydrofuran, acetone, 1, 4-dioxane, ethyl acetate, butyl acetate, methanol, isopropanol, and absolute ethanol.
Preferably, the anthraquinone compound containing unsaturated carbon-carbon double bonds is selected from one or two of 1-allyloxy-4-hydroxyanthraquinone-9, 10-diketone and 1-amino-4-allyloxy anthraquinone.
Preferably, the general formula of the fluorine-silicon polymer containing sulfhydryl is R1SiMe2O(SiOMeRf)m(SiOMe2)n(SiOMeRe)oSiMe2R1Wherein R is1Is methyl or hydroxy, Me is methyl, RfIs 3,3, 3-trifluoropropyl, ReIs 3-mercaptopropyl, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 3 and less than or equal to 10, and o is more than or equal to 4 and less than or equal to 8.
Preferably, the molar ratio of the unsaturated carbon-carbon double bond in the anthraquinone compound containing the unsaturated carbon-carbon double bond to the mercapto group in the fluorosilicone polymer containing the mercapto group is 1: 1.2-5. More preferably, the molar ratio is 1: 1.7-3.
Preferably, the dominant wavelength of the ultraviolet light is 365nm, and the light intensity is 1-10 mW/cm2。
A fluorine-containing silicon compound produced by the production method according to any one of the above embodiments.
The modified fabric is prepared from methyl vinyl silicone rubber, the fluorine-containing silicon compound in the embodiment, mercapto silicone oil and a photoinitiator. The raw materials can be directly processed by an injection molding method and then vulcanized and crosslinked into fabrics after being uniformly mixed, or can be processed by extrusion molding and then vulcanized and crosslinked into fibers, and then the fibers are processed into fabrics or are processed into fabrics together with other fibers.
Preferably, the weight ratio of the methyl vinyl silicone rubber, the fluorine-containing silicon compound, the mercapto silicone oil and the photoinitiator is 100: 0.05-2: 1-10: 0.1-0.5. The photoinitiator in the present invention is not particularly limited as long as it can generate a radical upon initiation under ultraviolet irradiation, and a benzoin-based photoinitiator including benzoin dimethyl ether, benzoin butyl ether or benzoin ethyl ether is preferable.
Preferably, the raw material is crosslinked under ultraviolet irradiation. The dominant wavelength of the ultraviolet light is 365nm, and the light intensity is 5-20 mW/cm2The irradiation time is 30 s-5 min.
Use of a modified fabric according to any of the above embodiments in the field of wastewater treatment. More preferably, the method is applied to the field of wastewater treatment containing azo dyes and nitrates.
The invention has the beneficial effects that:
(1) the invention utilizes the principle that the incompatibility of the fluorine-silicon polymer and the silicon rubber can be separated out on the surface of the silicon rubber for enrichment, and improves the content of the fluorine-silicon polymer containing anthraquinone on the surface of the silicon rubber, thereby improving the biodegradation promotion effect on azo dyes and nitrates.
(2) The preparation method is simple, the process is simple and convenient, and a new way is provided for promoting the biodegradation of the azo dye and the nitrate.
(3) The invention adopts the silicon rubber fabric as the carrier, can be woven into different structures and shapes according to the requirements, has flexible and various application modes, is more convenient to recycle, and has the characteristic of lower cost.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Examples 1 to 3 are for the preparation of fluorine-containing silicon compounds, in which
The fluorine-silicon polymer A containing sulfydryl is SiMe3O(SiOMeRf)17.3(SiOMe2)9.9(SiOMeRe)4.7SiMe3，Me、Rf、ReAs described above.
The fluorine-silicon polymer B containing sulfydryl is SiMe3O(SiOMeRf)8.7(SiOMe2)7.9(SiOMeRe)7.2SiMe3，Me、Rf、ReAs described above.
The fluorine-silicon polymer C containing sulfydryl is HOSiMe2O(SiOMeRf)6.5(SiOMe2)8.4(SiOMeRe)5.3SiMe2OH，Me、Rf、ReAs described above.
Example 1
Adding 1-allyloxy-4-hydroxyanthraquinone-9, 10-diketone and mercapto-containing fluorosilicone polymer A into butyl acetate 10 times of the weight of the mercapto-containing fluorosilicone polymer A according to the molar ratio of 1:0.4, adding benzoin butyl ether 2% of the weight of the mercapto-containing fluorosilicone polymer A, stirring and dissolving the mixture, and dissolving the mixture in a condition that the dominant wavelength is 365nm and the light intensity is 5mW/cm2Is irradiated for 4 minutes under ultraviolet light, the ultraviolet light is removed, and butyl acetate is removed to obtain the fluorine-containing silicon compound which is marked as S-1.
Example 2
Adding 1-allyloxy-4-hydroxyanthraquinone-9, 10-diketone and mercapto-containing fluorosilicone polymer B into tetrahydrofuran in a molar ratio of 1:0.6, wherein the weight of the tetrahydrofuran is 10 times that of the mercapto-containing fluorosilicone polymer B, adding benzoin butyl ether accounting for 1.5 percent of the weight of the mercapto-containing fluorosilicone polymer B, stirring and dissolving the mixture, and dissolving the mixture in a solution with the dominant wavelength of 365nm and the light intensity of 10mW/cm2Ultraviolet light for 1 minuteAnd removing the ultraviolet light, and removing the tetrahydrofuran to obtain the fluorine-containing silicon compound which is marked as S-2.
Example 3
Adding 1-amino-4-allyloxyanthraquinone and mercapto-containing fluorosilicone polymer C into butanone 10 times of the weight of the mercapto-containing fluorosilicone polymer C according to the molar ratio of 1:0.3, adding benzoin dimethyl ether 1% of the weight of the mercapto-containing fluorosilicone polymer C, stirring for dissolving, and dissolving at the dominant wavelength of 365nm and the light intensity of 10mW/cm2Then the UV light is removed and butanone is removed to obtain the fluorine-containing silicon compound, which is marked as S-3.
Examples 4-10 to prepare modified fabrics
Example 4
The methyl vinyl silicone rubber is prepared by mixing methyl vinyl silicone raw rubber and fumed silica according to the weight ratio of 1: 0.32.
Uniformly mixing methyl vinyl silicone rubber, fluorine-containing silicon compound S-1, mercapto silicone oil and photoinitiator in a weight ratio of 100:0.1:2:0.1 on a three-roll mixing roll, extruding, and mixing at a dominant wavelength of 365nm and a light intensity of 5mW/cm2Irradiating for 5min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as F-1.
Example 5
The methyl vinyl silicone rubber is prepared by mixing methyl vinyl silicone raw rubber, fumed silica and tourmaline according to the weight ratio of 1:0.32: 0.2.
Uniformly mixing methyl vinyl silicone rubber, fluorine-containing silicon compound S-2, mercapto silicone oil and photoinitiator in a weight ratio of 100:0.8:5:0.3 on a three-roll mixing roll, extruding, wherein the dominant wavelength is 365nm, and the light intensity is 10mW/cm2Irradiating for 3min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as F-2.
Example 6
The methyl vinyl silicone rubber is methyl vinyl silicone crude rubber and is not filled with filler.
Uniformly mixing methyl vinyl silicone crude rubber, fluorine-containing silicon compound S-3, mercapto silicone oil and photoinitiator in a weight ratio of 100:1.1:3:0.1 on a three-roll mixing roll, extruding, and mixing at a dominant wavelength of 365nm and a light intensity of 20mW/cm2Irradiating the fiber for 30s by ultraviolet light to obtain the fiber, and weaving the fiber into a modified fabric, which is marked as F-3.
Example 7
The methyl vinyl silicone rubber is prepared by mixing methyl vinyl silicone raw rubber and aluminum oxide according to the weight ratio of 1:1.
Uniformly mixing methyl vinyl silicone rubber, fluorine-containing silicon compound S-1, mercapto silicone oil and photoinitiator in a weight ratio of 100:1.5:10:0.5 on a three-roll mixing roll, extruding, and mixing at a dominant wavelength of 365nm and a light intensity of 10mW/cm2Irradiating for 2min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as F-4.
Example 8
The methyl vinyl silicone rubber is methyl vinyl silicone crude rubber and is not filled with filler.
Uniformly mixing methyl vinyl silicone crude rubber, fluorine-containing silicon compound S-2, mercapto silicone oil and photoinitiator in a weight ratio of 100:2:6:0.2 on a three-roll mixing roll, extruding, and mixing at a dominant wavelength of 365nm and a light intensity of 5mW/cm2Irradiating for 2min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as F-5.
Example 9
The methyl vinyl silicone rubber is prepared by mixing methyl vinyl silicone crude rubber, fumed silica and alumina according to the weight ratio of 1:0.2: 0.3.
Uniformly mixing methyl vinyl silicone rubber, fluorine-containing silicon compound S-3, mercapto silicone oil and photoinitiator in a weight ratio of 100:1.3:7:0.3 on a three-roll mixing roll, extruding, and mixing at a dominant wavelength of 365nm and a light intensity of 12mW/cm2Irradiating for 2min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as F-6.
Example 10
The methyl vinyl silicone rubber is prepared by mixing methyl vinyl silicone raw rubber and precipitated silica white according to the weight ratio of 1: 0.2.
Uniformly mixing methyl vinyl silicone rubber, fluorine-containing silicon compound S-1, mercapto silicone oil and photoinitiator in a weight ratio of 100:1:2:0.1 on a three-roll mixing roll, extruding, wherein the dominant wavelength is 365nm, and the light intensity is 15mW/cm2Irradiating with ultraviolet light for 1.5min to obtain fiberThe fibers were re-woven into a modified fabric, designated F-7.
Comparative example 1
Anthraquinone-modified talc, denoted C-1, was prepared according to the method of example 3 in patent application publication No. CN 110040844A.
Comparative example 2
An anthraquinone-modified nylon membrane, designated C-2, was prepared according to the method of example 1 in the patent granted under publication No. CN 103936146B.
Comparative example 3
Uniformly mixing methyl vinyl silicone crude rubber, 1-amino-4-allyloxy anthraquinone, mercapto-containing fluorosilicone polymer C, mercapto silicone oil and photoinitiator in a weight ratio of 100:0.4:1.5:6:0.2 on a three-roll mixing roll, extruding, and mixing at a dominant wavelength of 365nm and a light intensity of 5mW/cm2Irradiating for 2min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as C-3.
Comparative example 4
Uniformly mixing methyl vinyl silicone rubber, 1-amino-4-allyloxy anthraquinone, mercapto silicone oil and photoinitiator in a weight ratio of 100:0.6:6:0.2 on a three-roll mixing roll, extruding, wherein the dominant wavelength is 365nm, and the light intensity is 5mW/cm2Irradiating for 2min by ultraviolet light to obtain fibers, and weaving the fibers into a modified fabric, which is marked as C-4.
The test of the effect of accelerating the degradation of the azo dye comprises the steps of respectively washing 2g of a sample to be tested with physiological saline for 3 times, adding the sample to 200ml of 120 mg/L acid red B containing azo dye degradation strain GYZ (staphylococcus sp.) in logarithmic phase for decolorization test, and measuring the change of the concentration of the acid red B along with the time, wherein the results are shown in Table 1.
TABLE 1 acid Red B concentration/mg/L
| 0h | 2h | 4h | 6h | 8h | |
| F-1 | 120 | 98 | 71 | 26 | 2 |
| F-2 | 120 | 94 | 60 | 17 | ＜1 |
| F-3 | 120 | 94 | 61 | 19 | 1 |
| F-4 | 120 | 92 | 58 | 17 | ＜1 |
| F-5 | 120 | 95 | 63 | 19 | 1 |
| F-6 | 120 | 94 | 62 | 18 | 1 |
| F-7 | 120 | 93 | 62 | 19 | 1 |
| C-1 | 120 | 104 | 82 | 48 | 13 |
| C-2 | 120 | 100 | 75 | 42 | 6 |
| C-3 | 120 | 106 | 94 | 76 | 51 |
| C-4 | 120 | 103 | 89 | 72 | 49 |
The nitrate degradation acceleration effect is tested by respectively washing 2g of samples to be tested with physiological saline for 3 times, adding the samples to 200ml of nitrate wastewater containing 150 mg/L of denitrifying microorganisms in logarithmic growth phase for testing, and measuring the change of the nitrate concentration along with time, wherein the results are shown in Table 2.
TABLE 2 nitrate concentration/mg/L
And (3) repeatedly using and testing, namely respectively washing 2g of a sample to be tested by using physiological saline for 3 times, adding the sample to be tested into 200ml of 120 mg/L acid red B containing azo dye degradation strains GYZ (staphylococcus sp) in logarithmic phase for carrying out decolorization test, measuring the concentration of the acid red B after 6 hours, washing and drying the sample to be tested by using clean water, carrying out decolorization test by using the acid red B for 6 hours according to the method, and repeatedly testing for 12 times, wherein the results are shown in Table 3.
TABLE 3 acid Red B concentration/mg/L
Therefore, the modified fabric obtained by adding the fluorine-containing silicon compound into the silicon rubber composition can obviously improve the biodegradation rate of the acid red B and the nitrate, and meanwhile, compared with filler particles and a polymeric membrane in a particle form, the fabric is more convenient to recover and can be repeatedly used.
Therefore, the modified fabric can be applied to the treatment of wastewater containing azo dyes, nitrates and the like, and can obviously improve the biodegradation rate of the azo dyes and the nitrates.
The foregoing has shown and described the fundamental principles, principal features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the fluorine-containing silicon compound is characterized in that an anthraquinone compound containing unsaturated carbon-carbon double bonds, a fluorine-silicon polymer containing sulfydryl and a photoinitiator are added into an organic solvent, stirred and dissolved, and irradiated under ultraviolet light for 1-10 minutes, after the irradiation, the ultraviolet light is removed, and the organic solvent is removed, so that the fluorine-containing silicon compound is obtained.
2. The process according to claim 1, wherein the unsaturated carbon-carbon double bond-containing anthraquinone compound is one or two selected from the group consisting of 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione and 1-amino-4-allyloxyanthraquinone.
3. The method according to claim 1, wherein the mercapto-containing fluorosilicone polymer has a general formula R1SiMe2O(SiOMeRf)m(SiOMe2)n(SiOMeRe)oSiMe2R1Wherein R is1Is methyl or hydrogen, Me is methyl, RfIs 3,3, 3-trifluoropropyl, ReIs 3-mercaptopropyl, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 3 and less than or equal to 10, and o is more than or equal to 4 and less than or equal to 8.
4. The preparation method according to claim 1, wherein the molar ratio of the unsaturated carbon-carbon double bond in the anthraquinone compound containing the unsaturated carbon-carbon double bond to the mercapto group in the fluorosilicone polymer containing the mercapto group is 1: 1.2-5.
5. The preparation method according to claim 1, wherein the dominant wavelength of the ultraviolet light is 365nm, and the light intensity is 1-10 mW/cm2。
6. A fluorine-containing silicon compound produced by the production method according to any one of claims 1 to 5.
7. A modified fabric, characterized in that the raw material consists of methyl vinyl silicone rubber, the fluorine-containing silicon compound according to claim 5, mercapto silicone oil and a photoinitiator.
8. The modified fabric according to claim 7, wherein the weight ratio of the methyl vinyl silicone rubber, the fluorine-containing silicon compound, the mercapto silicone oil and the photoinitiator is 100: 0.05-2: 1-10: 0.1-0.5.
9. The modified fabric of claim 7, wherein said material is crosslinked under UV irradiation.
10. Use of the modified fabric according to any one of claims 7 to 9 in the field of wastewater treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010472243.0A CN111454406A (en) | 2020-05-29 | 2020-05-29 | Preparation method of fluorine-containing silicon compound, modified fabric and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010472243.0A CN111454406A (en) | 2020-05-29 | 2020-05-29 | Preparation method of fluorine-containing silicon compound, modified fabric and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111454406A true CN111454406A (en) | 2020-07-28 |
Family
ID=71676076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010472243.0A Withdrawn CN111454406A (en) | 2020-05-29 | 2020-05-29 | Preparation method of fluorine-containing silicon compound, modified fabric and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111454406A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114164656A (en) * | 2022-01-26 | 2022-03-11 | 王永涛 | Preparation method of modified fiber and fabric |
-
2020
- 2020-05-29 CN CN202010472243.0A patent/CN111454406A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114164656A (en) * | 2022-01-26 | 2022-03-11 | 王永涛 | Preparation method of modified fiber and fabric |
| CN114164656B (en) * | 2022-01-26 | 2024-04-12 | 深圳市卡熙赫服饰有限公司 | Preparation method of modified fiber and fabric |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111548632B (en) | Modified silicone rubber composition, textile fabric and application thereof | |
| CN111518395B (en) | Modified silicone rubber, silicone rubber textile and application thereof | |
| WO2020221243A1 (en) | Method for preparing inorganic filler with anthraquinone compound grafted onto the surface thereof and use thereof | |
| WO2020221242A1 (en) | Method for preparing inorganic filler with anthraquinone compound fixed on surface thereof and use thereof | |
| CN112973653B (en) | Preparation method of Mxene membrane adsorbing material based on polyamidoxime and uranium extraction method | |
| CN108560259B (en) | Method for improving bonding fastness of nano ZnO on modified polyester fabric | |
| CN111454406A (en) | Preparation method of fluorine-containing silicon compound, modified fabric and application thereof | |
| CN109880178A (en) | A kind of nano-cellulose enhancing graphene oxide/poly-dopamine layered bionic material and preparation method thereof | |
| CN111593435B (en) | Composite material, fiber, woven fabric based on silicon rubber and application thereof | |
| CN112426893A (en) | Nanofiber membrane, preparation method and application of nanofiber membrane in dye wastewater treatment | |
| WO2020221240A1 (en) | Method for preparing tourmaline containing anthraquinone compound by means of thiol-ene click chemistry and application thereof | |
| CN110128571B (en) | Preparation method and application of modified polystyrene resin | |
| CN111471179B (en) | Preparation method of modified fluorosilicone polymer, fabric and application thereof | |
| CN112358059B (en) | Application method of pyrite in sewage treatment | |
| CN111549393B (en) | Fiber, preparation method, textile fabric and application thereof | |
| CN115611432A (en) | Method for preparing reinforced denitrification slow-release carbon source filler by using corncob-polycaprolactone powder mixed system | |
| CN111472065B (en) | Preparation method and application of textile | |
| CN108295678B (en) | Sewage treatment membrane material and preparation method thereof | |
| CN110694655A (en) | Preparation method of silver sulfide/silver phosphate/graphene oxide composite photocatalyst | |
| CN112409799B (en) | Modified silicone rubber composition and application thereof in sewage treatment | |
| CN112538264A (en) | Electromagnetic shielding plastic and preparation method thereof | |
| CN112980193B (en) | Hydrophilic silicone rubber composition and application thereof | |
| CN112480461A (en) | Preparation method and application of modified foaming polyurethane | |
| CN113004610B (en) | Preparation method and application of carbon nanotube modified polypropylene material | |
| CN114574104B (en) | Ultraviolet light cured rosin resin and preparation method and application 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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200728 |