CN115124670B - Fluorosilicone segmented copolymer and preparation method and application thereof - Google Patents

Fluorosilicone segmented copolymer and preparation method and application thereof Download PDF

Info

Publication number
CN115124670B
CN115124670B CN202210636496.6A CN202210636496A CN115124670B CN 115124670 B CN115124670 B CN 115124670B CN 202210636496 A CN202210636496 A CN 202210636496A CN 115124670 B CN115124670 B CN 115124670B
Authority
CN
China
Prior art keywords
fluorosilicone
copolymer
fluorine
solvent
segmented copolymer
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.)
Active
Application number
CN202210636496.6A
Other languages
Chinese (zh)
Other versions
CN115124670A (en
Inventor
张丽芬
余青
程振平
成健楠
王玉薛
徐想
赵海涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN202210636496.6A priority Critical patent/CN115124670B/en
Publication of CN115124670A publication Critical patent/CN115124670A/en
Application granted granted Critical
Publication of CN115124670B publication Critical patent/CN115124670B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/10705—Tetrafluoride
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/284—Halides
    • C03C2217/285—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings

Abstract

The invention relates to a fluorosilicone segmented copolymer, a preparation method and application thereof, and belongs to the technical field of polymers. The preparation method of the invention comprises the following steps: under the protection atmosphere, a silane reagent and a macromolecular initiator of the fluorine-containing alternating copolymer are subjected to light-controlled active free radical polymerization reaction in a solvent I under the action of a photocatalyst to obtain a segmented copolymer of the main chain type fluorine-containing alternating copolymer; and then the segmented copolymer of the main chain type fluorine-containing alternating copolymer reacts in a solvent II under the action of an initiator and a reducing agent to obtain the fluorosilicone segmented copolymer, so as to obtain the silicon fluoride nano particles and the super-hydrophobic coating. The method of the invention distributes fluorine-containing parts on the outer sides of the nano particles, endows the nano particles with superhydrophobicity, and has great application prospect for constructing firm and large-area self-cleaning surfaces.

Description

Fluorosilicone segmented copolymer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a fluorosilicone segmented copolymer, a preparation method and application thereof.
Background
Super-hydrophobic materials are defined as surfaces with a water contact angle greater than 150 degrees and a roll angle less than 10 degrees. The surface with extremely hydrophobicity has great application prospect in the fields of self-cleaning materials, waterproof textiles, ice accumulation prevention and the like. The superhydrophobic surface must satisfy two conditions, i.e., roughness on the order of micrometers or nanometers, and low surface energy. Various chemical preparation methods have been studied so far to prepare superhydrophobic surfaces, including chemical vapor deposition techniques, solution impregnation methods, electrochemical techniques, hydrothermal methods, and sol-gel methods. Among them, the sol-gel method is widely used for mass industrial production on various substrates (metals and their alloys, fabrics, wood, glass, silicon wafers, etc.) of arbitrary shapes due to low cost and simple equipment. The transparent or semitransparent super-hydrophobic surface can be prepared by combining a compound with a low surface energy structure with a microstructure through a sol-gel technology.
The low surface energy compound is generally fluorocarbon, and has wide application prospect in the fields of antifouling paint, hydrophobic material and the like due to the special performance of the fluorocarbon, namely, high heat resistance, high weather resistance, high chemical stability, hydrophobic and oleophobic property. The fluorine-containing siloxane and tetraethyl orthosilicate (TEOS) are condensed into nano particles under alkaline condition by a sol-gel method, and the nano particles can be independently prepared into a super-hydrophobic film. However, currently fluorinated silicon nanoparticles are mainly prepared by co-condensing perfluorooctyl triethoxysiloxane (PFOTS) or other small molecule fluorosilane coupling agents with TEOS, however, the fluorinated layers formed by small molecule fluorosilanes are thinner and less hydrophobic than macromolecules.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the preparation of the fluorinated silicon nano particles mainly stays in the use of a small-molecule fluorosilane coupling agent, the fluorinated layer formed by the small-molecule fluorosilane is thinner, and the hydrophobic property is inferior to that of a macromolecule in the prior art.
In order to solve the technical problems, the invention provides a fluorosilicone segmented copolymer and a preparation method and application thereof. The invention synthesizes the main chain type fluorine-containing alternating copolymer block copolymer by polymerizing the fluorine-containing alternating copolymer macromolecular initiator and the silane reagent, and prepares the fluorosilicone block copolymer through a strong reducing agent. The fluorosilicone segmented copolymer has the advantages that firstly, the trialkoxysilane groups in grafting are more abundant, and the condensation reaction is facilitated; second, the thick graft crosslinked layer formed by sol-gel is more stable than the thin layer formed by conventional triethoxysilane and the thickness of the fluorinated layer can be varied by varying the molecular weight of the fluorine-containing segment.
The first object of the present invention is to provide a fluorosilicone block copolymer having a structure represented by the formula (1):
wherein z=4-8; y=2-5; x=4-8; n=1-100; m=1-20; n, m, x, y is an integer;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
A second object of the present invention is to provide a process for the preparation of said fluorosilicone block copolymer, comprising the steps of,
s1, under a protective atmosphere, a silane reagent shown in a formula (2) and a fluorine-containing alternating copolymer macroinitiator shown in a formula (3) are subjected to light-controlled active free radical polymerization reaction in a solvent I under the action of a photocatalyst to obtain a main chain type fluorine-containing alternating copolymer shown in a formula (4);
s2, under the action of an initiator and a reducing agent, the segmented copolymer of the main chain type fluorine-containing alternating copolymer shown in the formula (4) reacts in a solvent II at the temperature of 70-90 ℃ to obtain the fluorosilicone segmented copolymer;
wherein the formulae (2) - (4) have the following structure:
wherein z=4-8; y=2-5; x=4-8; n=1-100; m=1-20; n, m, x, y is an integer;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
In one aspect of the inventionIn one embodiment, in S1, the fluorine-containing alternating copolymer is (AB) n Is obtained by the START polymerization of the monomer A and the monomer B.
In one embodiment of the invention, the monomer A is 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane or 1, 8-diiodoperfluorooctane.
Preferably, the monomer A is 1, 6-diiodoperfluorohexane.
In one embodiment of the invention, the monomer B is 1, 7-octadiene.
In one embodiment of the invention, in S1, the silane reagent is methacryloxypropyl Trimethoxysilane (TMAPMA), methacryloxypropyl triethoxysilane (EPMA), or methacryloxypropyl triisopropylsilane (IPSMA).
Preferably, the silane reagent is methacryloxypropyl triisopropyl silane (IPSMA).
In one embodiment of the present invention, in S1, the photocatalyst is one or more of sodium iodide, tetramethyl ammonium iodide, sodium chloride, tetrabutyl ammonium bromide, and diphenyl phosphine chloride.
In one embodiment of the present invention, in S1, the solvent I is one or more of dimethylacetamide, acetone, 1, 4-dioxane, and dimethyl carbonate.
In one embodiment of the invention, in S1, the photocatalyst is tetramethyl ammonium iodide; the solvent I is dimethylacetamide.
In one embodiment of the invention, in S1, the molar ratio of the silane reagent and the fluorine-containing alternating copolymer macroinitiator is from 2 to 5:1.
in one embodiment of the invention, in S1, the polymerization is carried out under light conditions of 373-403nm for at least 0.5h.
In one embodiment of the invention, in S2, the initiator is Azobisisobutyronitrile (AIBN).
In one embodiment of the present invention, in S2, the reducing agent is tributyltin hydride (Bu 3 SnH)。
In one embodiment of the present invention, in S2, the solvent II is toluene.
The third object of the present invention is to provide a method for preparing silicon fluoride nano-particles (F-SNs), comprising the steps of reacting a silicon source with the fluorosilicone block copolymer in a solvent III at 55-65 ℃ to obtain the silicon fluoride nano-particles (F-SNs).
In one embodiment of the invention, the silicon source is tetraethyl orthosilicate (TEOS), silicon tetrachloride (SiCl 4 ) And Methyltrimethoxysilane (MTMS).
Preferably, the silicon source is tetraethyl orthosilicate (TEOS).
In one embodiment of the invention, the molar ratio of the silicon source to fluorosilicone block copolymer is 500: 1.
In one embodiment of the invention, the solvent III is 1, 3-bistrifluorotoluene and/or toluene.
In one embodiment of the invention, the solvent III is 1, 3-bistrifluorotoluene.
In one embodiment of the invention, a silicon source is first sol-gel condensed to form Silica Nanoparticles (SNs). The fluorosilicone block copolymer is then dissolved in a suitable solvent and added to react to form a fluorinated layer around the monodisperse silica.
In one embodiment of the invention, the sol-gel time is 1.5-12 hours.
In one embodiment of the invention, the sol-gel time is 4 hours.
A fourth object of the present invention is to provide silicon fluoride nanoparticles (F-SNs) prepared by the method.
The fifth object of the present invention is to provide a method for preparing a superhydrophobic coating, which comprises the steps of uniformly dispersing the silicon fluoride nano particles (F-SNs) in a solvent IV, coating the solvent IV on a glass substrate, and curing the solvent IV through heat treatment to obtain the superhydrophobic coating. The static contact angle of the coating and water is above 150 degrees, and water drops are easy to fall off from the surface, so that the coating has superhydrophobic performance.
In one embodiment of the invention, the solvent IV is one or more of methanol, ethanol and isopropanol.
In one embodiment of the invention, the solvent IV is isopropanol.
In one embodiment of the invention, the concentration of the silicon fluoride nanoparticles is 30-60mg/mL.
In one embodiment of the invention, the concentration of the silicon fluoride nanoparticles is 40mg/mL.
In one embodiment of the invention, the glass has a size of 1cm by 1cm.
A sixth object of the present invention is to provide a superhydrophobic coating prepared by the method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) Compared with the traditional method using perfluorooctyl triethoxy siloxane, the fluorosilicone segmented copolymer provided by the invention has the advantages that the graft crosslinking layer formed by triisopropyl siloxane sol-gel is thicker and more stable than the crosslinking layer formed by traditional triethoxy silane, and the thickness of the fluorinated layer can be changed by changing the molecular weight of a fluorine-containing chain segment, so that the anti-fouling performance of the nano particles can be improved; secondly, the quantity of siloxane in the fluorosilicone polymer can be controlled by adjusting the polymerization molar ratio of silane to the fluorine-containing polymer, and the higher the richness of alkoxy silane groups in grafting is, the more favorable the condensation reaction is.
(2) The silicon fluoride nano particles are prepared by co-condensation. The co-condensation method is formed by condensing a silicon source precursor and one or more fluoroalkyl silanes simultaneously, while the traditional grafting method is to synthesize silica particles first and then fix the fluoroalkyl silanes on the silica particles. Compared with a grafting method, the co-condensation method is simpler in operation, and because the co-condensation method is synthesized by a one-pot method, fluorine-containing chain segments are distributed more uniformly on the outer sides of the nano particles.
(3) The preparation of the super-hydrophobic coating greatly reduces the dosage of fluorosilicone, can greatly save the production cost, and has the molar ratio of the silicon source to the fluorosilicone in the super-hydrophobic nano particles prepared by the co-condensation method in the prior art of 2-20:1, the super-hydrophobic effect can be achieved only when the fluorosilicone accounts for a very high proportion.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 shows the structure of example 1 (AB) of the present invention n Is a reaction scheme of (a).
FIG. 2 shows the structure of example 1 (AB) of the present invention n A kind of electronic device 1 H NMR test results.
FIG. 3 shows the structure of example 1 (AB) of the present invention n A reaction scheme of A.
FIG. 4 is A (AB) of example 1 of the present invention n A kind of electronic device 1 H NMR test results.
FIG. 5 is a reaction scheme of the fluorosilicone block copolymer of example 1 of the present invention.
FIG. 6 is A (AB) of example 1 of the present invention n PIPSMA and A (AB) n PIPSMA-I 1 H NMR test results.
FIG. 7 is A (AB) of example 1 of the present invention n And A (AB) n GPC test results of PIPSMA.
FIG. 8 is a schematic diagram showing the synthesis of F-SNs in example 2 of the present invention.
FIG. 9 shows the silicon fluoride nanoparticles (F-SNs) and the fluorosilicone block copolymer (A (AB) as a comparison of the silicon dioxide nanoparticles (SNs) in example 2 of the present invention n -ir test results of PIPSMA-I).
FIG. 10 is a graph showing the water contact angle test results in example 3 of the present invention; wherein (a) is the water contact angle of the silica nanoparticle and (b) is the water contact angle of the silicon fluoride nanoparticle.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The chemical reagents used in the examples of the present invention:
dimethylacetamide and toluene were subjected to a water removal operation (reduced pressure distillation after drying overnight with calcium hydride addition) and stored in a desiccator in a sealed manner before use; before using, the glass sheet is respectively washed for 5min by acetone, deionized water and ethanol, and then dried by argon. Other reagents and raw materials not described are all used directly after purchase.
The detection method of the invention comprises the following steps:
1. of polymers 1 The H NMR spectrum was measured by Bruker 300MHz Nuclear Magnetic Resonance (NMR) apparatus. The test was carried out at room temperature (25 ℃) with CDCl 3 As deuterated reagent, tetramethylsilane (TMS) is an internal standard.
2. Molecular weight of Polymer (M n,GPC ) And molecular weight distribution indexDetermined using a TOSOH HLC-8320 Gel Permeation Chromatograph (GPC) equipped with a differential refractive detector (TOSOH). GPC with DMF as eluent was equipped with one TSKgel guard column (SuperAW-H) and two test columns (TSKgel SuperAWM-H), the molecular weight of the polymer being measured in the range of 1X 10 3 Up to 1X 10 6 g/mol. The eluent DMF contained LiBr (0.01 mol/L) at a concentration and a flow rate of 0.6mL/min, and was used as a standard for polymer molecular weight calibration using linear Polystyrene (PS) from TOSOH. It has to be mentioned that DMF is not a good solvent for PS at room temperature, but we purchased PS standard solutions of different molecular weights directly from TOSOH (completely dissolved in DMF) and run GPC equipment at 40℃according to TOSOH HLC-8320GPC requirements.
3. Fourier-IR Spectroscopy (FT-IR) was measured using KBr pellet method on an infrared spectrometer (Bruker TENSOR-27, USA).
4. The Water Contact Angle (WCA) was measured by a CA goniometer JC2000D5 (Shanghai morning digital technical equipment limited).
Example 1
The fluorosilicone block copolymer is synthesized based on the fluorine-containing alternating copolymer, and specifically comprises the following steps:
(1) Synthesis (AB) n : initial charge mole ratio [ C 6 F 12 I 2 ] 0 ：[C 8 H 14 ] 0 ：[NaI] 0 =1: 1:0.5 to a clean 5mL ampoule was added dodecafluoro-1, 6-diiodohexane (0.2769 g), sodium iodide (0.0375 g), 1, 7-octadiene (74. Mu.L), acetone (4 mL) and a clean magnetic stirrer, and the mixture was subjected to three freeze-evacuation-argon-introduction operations, and flame-sealed. And (3) placing the ampoule bottle under the irradiation of a purple light LED, stirring, reacting for a preset time, and taking out. 0.5-1mL tetrahydrofuran was added for dilution and precipitation into large amounts of methanol. Standing in refrigerator overnight, vacuum filtering, drying the obtained white product in vacuum oven at 40deg.C, weighing after constant weight, and finally obtaining fluorine-containing alternating copolymer (AB) n The reaction scheme is shown in FIG. 1.
FIG. 2 is (AB) n A kind of electronic device 1 H NMR test results.
(2) Synthesis (AB) n A: initial charge molar ratio [ (AB) n ] 0 ：[C 8 F 17 I] 0 ：[NaI] 0 ＝1：10：
0.5, adding (AB) to clean 5mL ampoule bottles respectively n 、C 8 F 17 I、Ru(bpy) 3 Cl 2 The procedure of step (1) of this example was followed by AsAc-Na, acetone and a clean magnetic stirrer, and the reaction scheme is shown in FIG. 3.
FIG. 4 is (AB) n A is a combination of 1 H NMR test results.
(3) Synthesis of fluorosilicone Block copolymers (A (AB) prepared based on fluorine-containing alternating copolymers n -PIPSMA-I)；
Initial charge molar ratio [ (AB) n A] 0 ：[IPSMA] 0 ：[TBAI] 0 =1: 5:0.5, adding (AB) to clean 5mL ampoule bottles respectively n A. Methacryloxypropyl triisopropyl silane (IPSM), tetrabutyl iodized amine (TBAI), anhydrous dimethylacetamide (DMAc) and a clean magnetic stirrer, placing ampoule bottle in liquid nitrogen to freeze the solution, pumping air for 50s, thawing at room temperature, and introducingArgon gas is used for protecting gas, then the ampoule bottle is frozen, pumped out, thawed and inflated, and three circulation processes are sequentially carried out to remove oxygen in the ampoule bottle. After deoxidization, the ampoule bottle is quickly moved to a spray gun port for flame sealing. Placing ampoule bottle in 403nm violet light for reaction for a certain time, transferring ampoule bottle to dark place, breaking tube, transferring about 50 μl of polymer stock solution into deuterated chloroform with a pipette 1 H NMR test to calculate the monomer conversion, dissolving a small amount of anhydrous tetrahydrofuran by a dropper, precipitating in anhydrous methanol, centrifuging, pouring out the supernatant, and oven drying the resulting polymer at 30deg.C to give fluorosilicone block copolymer (A (AB) n PIPSMA), the ordered arrangement of the subsequent fluorine-containing chain segments is affected due to the large steric hindrance of the iodine atoms of the side chains, and the side chains and the terminal iodine are reacted in a strong reducing agent Bu 3 Reduction to hydrogen under the action of SnH, initial charge molar ratio [ (A (AB) n -PIPSMA)] 0 ：[AIBN] 0 ：[Bu 3 SnH] 0 =1: 10:30, into clean 5mL ampoules (A (AB) n PIPSMA), azobisisobutyronitrile (AIBN), tributyltin hydride (Bu) 3 SnH), anhydrous toluene and a clean magnetic stirrer are subjected to three freezing-vacuumizing-argon-introducing operations, and the tube is sealed by flame. The ampoule was stirred under a magnetic stirrer at 80 ℃, after a predetermined time of reaction, the ampoule was broken into tubes, settled in absolute methanol, then centrifuged, and the resulting polymer was dried in an oven at 30 ℃ after the supernatant was poured off, the reaction route being shown in fig. 5.
FIG. 6 is A (AB) n PIPSMA and A (AB) n PIPSMA-I 1 H NMR test results. As can be seen from the nuclear magnetic pattern, after iodine is reduced to hydrogen, the iodine is originally attributed to a (-CH) 2 CH(I)CH 2 (-) and b (-CH) 2 CH(I)CH 2 The peak of (-) completely disappeared.
FIG. 7 is A (AB) n And A (AB) n As a result of GPC test of PIPSMA, the molecular weight of the fluoropolymer after polymerization of methacryloxypropyl triisopropyl silane is significantly increased.
Example 2
The preparation of the fluorinated silicon nanoparticles (F-SNs) based on fluorosilicone block copolymers comprises the following steps:
after adding 0.21mL of TEOS into 2.1mL of isopropanol in a 10mL ampoule bottle and stirring to be homogeneous, adding 80 mu L of amine hydroxide and stirring vigorously, and directly stirring in a stirrer at 60 ℃ for 24 hours to obtain Silica Nanoparticles (SNs); if after a period of time, fluorosilicone block copolymers (A (AB) dissolved in 1, 3-bistrifluorotoluene are used n PIPSMA-I) was added to the reaction and stirred at 60℃for 24h. Centrifuging to remove supernatant after the reaction is finished, respectively ultrasonically dissolving the product with toluene and isopropanol, centrifuging, removing supernatant, and oven drying at 120deg.C for 1 hr to obtain silicon fluoride nanoparticles (F-SNs), wherein the synthetic diagram is shown in figure 8.
FIG. 9 is a graph of fluorinated silicon nanoparticles (F-SNs) and Silica Nanoparticles (SNs) and fluorosilicone block copolymer (A (AB) as a comparison n -ir test results of PIPSMA-I). The absorption peaks of the fluorinated silicon nanoparticles were consistent with the expectations, corresponding to the silica nanoparticles and fluorosilicone block copolymers, respectively.
Example 3
The super-hydrophobic coating prepared based on the silicon fluoride nano particles specifically comprises the following steps:
silicon fluoride nanoparticles (F-SNs) were uniformly dispersed in isopropyl alcohol at a concentration of 40mg/mL, coated on a glass substrate with a clean surface by spin coating, and spin coating was repeated 3 times at 0.45. Mu.L each time. Then heat-curing treatment is carried out in an oven at 120 ℃ for 1h. The same procedure was used to prepare a coating of silica nanoparticles as a control experiment. FIG. 10 is a test result of the water contact angle of a coating wherein the water contact angle of the silica nanoparticle coating is very hydrophilic and the water drops spread out completely; from the test results of the water contact angle of the silicon fluoride nanoparticle coating, it can be seen that the surface of the silicon dioxide nanoparticle with hydrophilicity is fluorinated and then has superhydrophobicity.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1. A fluorosilicone block copolymer is characterized in that the structure is shown as a formula (1):
wherein z=4-8; y=2-5; x=4-8; n=1-100; m=1-20; n, m, x, y is an integer;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
2. A process for preparing fluorosilicone block copolymers according to claim 1, comprising the steps of,
s1, a silane reagent shown in a formula (2) and a fluorine-containing alternating copolymer macromolecular initiator shown in a formula (3) are subjected to light-controlled active free radical polymerization reaction in a solvent I under the action of a photocatalyst to obtain a main chain type fluorine-containing alternating copolymer block copolymer shown in a formula (4);
s2, S1, under the action of an initiator and a reducing agent, reacting a segmented copolymer of the main chain type fluorine-containing alternating copolymer shown in the formula (4) in a solvent II to obtain the fluorosilicone segmented copolymer;
wherein the formulae (2) - (4) have the following structure:
wherein z=4-8; y=2-5; x=4-8; n=1-100; m=1-20; n, m, x, y is an integer;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
3. The method for producing a fluorosilicone block copolymer according to claim 2, wherein in S1, the photocatalyst is one or more of sodium iodide, tetramethyl ammonium iodide, sodium chloride, tetrabutyl ammonium bromide, and diphenyl phosphine chloride.
4. The method of preparing fluorosilicone block copolymers according to claim 2, wherein in S1, the molar ratio of the silane reagent to the fluorine-containing alternating copolymer macroinitiator is 2-5:1.
5. the method for producing a fluorosilicone block copolymer according to claim 2, wherein in S1, the polymerization reaction is carried out under an illumination condition of 373 to 403nm for at least 0.5 hours.
6. A method for preparing silicon fluoride nano-particles, which is characterized by comprising the following steps of reacting a silicon source with the fluorosilicone segmented copolymer of claim 1 in a solvent III at 55-65 ℃ to obtain the silicon fluoride nano-particles; the silicon source is one or more of tetraethyl orthosilicate, silicon tetrachloride and methyltrimethoxysilane.
7. A silicon fluoride nanoparticle prepared by the method of claim 6.
8. The preparation method of the superhydrophobic coating is characterized by comprising the following steps of uniformly dispersing the silicon fluoride nano particles in a solvent IV, coating the silicon fluoride nano particles on a glass substrate, and carrying out heat treatment and solidification to obtain the superhydrophobic coating.
9. The method for preparing a superhydrophobic coating according to claim 8, wherein the concentration of the silicon fluoride nanoparticle is 30-60mg/mL.
10. A superhydrophobic coating prepared according to the method of any one of claims 8-9.
CN202210636496.6A 2022-06-07 2022-06-07 Fluorosilicone segmented copolymer and preparation method and application thereof Active CN115124670B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210636496.6A CN115124670B (en) 2022-06-07 2022-06-07 Fluorosilicone segmented copolymer and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210636496.6A CN115124670B (en) 2022-06-07 2022-06-07 Fluorosilicone segmented copolymer and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115124670A CN115124670A (en) 2022-09-30
CN115124670B true CN115124670B (en) 2023-09-29

Family

ID=83378147

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210636496.6A Active CN115124670B (en) 2022-06-07 2022-06-07 Fluorosilicone segmented copolymer and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115124670B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300609A (en) * 1992-03-31 1994-04-05 Dow Corning Toray Silicone Co., Ltd. Fluorosilicone block copolymers
CN103524752A (en) * 2013-10-09 2014-01-22 济南大学 Fluorosiloxane-POSS acrylate block copolymers, blood-compatible coating thereof and preparation method of the fluorosiloxane-POSS acrylate block copolymers
CN110183598A (en) * 2019-06-28 2019-08-30 苏州大学 The illumination polymerization of the block copolymer of backbone chain type " half fluorine " alternate copolymer
CN113354593A (en) * 2021-06-28 2021-09-07 苏州大学 Fluorine-containing graft copolymer, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300609A (en) * 1992-03-31 1994-04-05 Dow Corning Toray Silicone Co., Ltd. Fluorosilicone block copolymers
CN103524752A (en) * 2013-10-09 2014-01-22 济南大学 Fluorosiloxane-POSS acrylate block copolymers, blood-compatible coating thereof and preparation method of the fluorosiloxane-POSS acrylate block copolymers
CN110183598A (en) * 2019-06-28 2019-08-30 苏州大学 The illumination polymerization of the block copolymer of backbone chain type " half fluorine " alternate copolymer
CN113354593A (en) * 2021-06-28 2021-09-07 苏州大学 Fluorine-containing graft copolymer, and preparation method and application thereof

Also Published As

Publication number Publication date
CN115124670A (en) 2022-09-30

Similar Documents

Publication Publication Date Title
Li et al. Synthesis of polymeric fluorinated sol–gel precursor for fabrication of superhydrophobic coating
JP5927743B2 (en) Method for producing composition for forming low refractive index film and method for forming low refractive index film
US20100080903A1 (en) Fluoropolymer thin film and method for its production
Bai et al. Synthesis and characterization of core–shell polysilsesquioxane-poly (styrene-butyl acrylate-fluorinated acrylate) hybrid latex particles
Li et al. Synthesis of POSS-containing fluorosilicone block copolymers via RAFT polymerization for application as non-wetting coating materials
CN103724558B (en) A kind of strawberry type structure inorganic/organic fluoride-containing microballoon and preparation method thereof and application
CN102351983A (en) Fluorine silicon acrylate copolymer, preparation process thereof and application thereof
CN111574899B (en) Organic-inorganic hybrid antifogging coating and preparation method thereof
US20100119774A1 (en) Water-repellent, oil-repellent, and antifouling antireflection film and method for manufacturing the same, lens, glass sheet, and glass coated with the same, and optical apparatus, solar energy system, and display equipped with these components
EP0837901A1 (en) Fluoropolymer nanocomposites
Park et al. Preparation and optical properties of silica-poly (ethylene oxide) hybrid materials
Huang et al. Preparation and thermal property of poly (methyl methacrylate)/silicate hybrid materials by the in-situ sol-gel process
Lim et al. Preparation and properties of poly (vinyl alcohol)/vinyltrimethoxysilane (PVA/VTMS) hybrid films with enhanced thermal stability and oxygen barrier properties
Wu et al. Synthesis of aqueous highly branched silica sol as underlying crosslinker for corrosion protection
CN111542550A (en) Base for forming polymer brush, method for producing the base, and precursor liquid used in the method
CN102782015B (en) For the preparation of the method for silicon-fluorine polymer thing
Sjoeblom et al. Hydrolysis and condensation of alkylmethoxysilanes. Studied by means of the Langmuir-Blodgett technique and electron spectroscopy for chemical analysis
CN115368762A (en) Hydrophobic and oleophobic coating, preparation method and application thereof
CN115124670B (en) Fluorosilicone segmented copolymer and preparation method and application thereof
JP3603133B2 (en) Polyhedral organosilicon compound having an organic fluorine group and a reactive functional group, a method for producing the same, and a film forming material and a formed film
CN110387191B (en) Hydrophobic coating, preparation method thereof and hydrophobic coating solution
Jeon et al. Hard coating films based on organosilane-modified boehmite nanoparticles under UV/thermal dual curing
US6566456B1 (en) Method of preparing a hybrid of polyvinylimidazole and silica
CN101511847B (en) Composition for hydrophobic treatment and glazing
Zhang et al. A double-layer moisture barrier & antireflective film based on bridged polysilsesquioxane and porous silica

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant