CN115124670A - Fluorosiloxane block copolymer and preparation method and application thereof - Google Patents

Fluorosiloxane block copolymer and preparation method and application thereof Download PDF

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CN115124670A
CN115124670A CN202210636496.6A CN202210636496A CN115124670A CN 115124670 A CN115124670 A CN 115124670A CN 202210636496 A CN202210636496 A CN 202210636496A CN 115124670 A CN115124670 A CN 115124670A
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block copolymer
fluorine
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张丽芬
余青
程振平
成健楠
王玉薛
徐想
赵海涛
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Abstract

The invention relates to a fluorosilicone block 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: firstly, under the action of a photocatalyst, a silane reagent and a fluorine-containing alternating copolymer macromolecular initiator are subjected to light-operated living radical polymerization reaction in a solvent I under the protective atmosphere to obtain a main chain type fluorine-containing alternating copolymer block copolymer; and then, the block 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 block copolymer, so that the silicon fluoride nano particles and the super-hydrophobic coating are obtained. The method of the invention distributes the fluorine-containing part at the outer side of the nano particle, endows the nano particle with super hydrophobicity, and the nano particle has great application prospect for constructing a firm and large-area self-cleaning surface.

Description

Fluorosiloxane block copolymer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a fluorosilicone block copolymer, and a preparation method and application thereof.
Background
Superhydrophobic materials are defined as surfaces with water contact angles greater than 150 ° and rolling angles less than 10 °. The surface with extremely high 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., micro-or nano-scale roughness and low surface energy. To date, a variety of chemical preparation methods have been extensively studied to prepare superhydrophobic surfaces, including chemical vapor deposition techniques, solution dipping methods, electrochemical techniques, hydrothermal methods, and sol-gel methods. Among them, the sol-gel method is widely used for large-scale industrial production on various substrates (metal and its alloy, fabric, wood, glass, silicon wafer, etc.) of arbitrary shapes because of low cost and simple equipment. Transparent or semi-transparent superhydrophobic surfaces can be prepared by combining compounds with low surface energy structures with micro-topographical structures by sol-gel techniques.
The low surface energy compound generally refers to a fluorocarbon compound, and the fluorocarbon compound has special properties of three high two phobicity (namely high heat resistance, high weather resistance, high chemical stability, hydrophobicity and oleophobicity), so that the low surface energy compound has wide application prospects in the fields of antifouling coatings, hydrophobic materials and the like. The fluorine-containing siloxane and tetraethyl orthosilicate (TEOS) are condensed into nano particles under an alkaline condition by a sol-gel method, the nano particles can be independently prepared into a super-hydrophobic film, firstly, the introduction of a fluorine-containing chain segment reduces the surface tension of the nano particles, and secondly, the nano particles increase the surface roughness of a coating, so that the coating has super-hydrophobicity. However, at present, the fluorinated silicon nanoparticles are mainly prepared by co-condensing Perfluorooctyltriethoxysilane (PFOTS) or other small-molecule fluorosilane coupling agents with TEOS, but a fluorinated layer formed by the small-molecule fluorosilane is thin, and the hydrophobic property is not as good as that of a large molecule.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems that the preparation of the fluorinated silicon nanoparticles in the prior art mainly stays in the use of a micromolecule fluorosilane coupling agent, a fluorinated layer formed by the micromolecule fluorosilane is thinner, and the hydrophobic property is not as good as that of macromolecules.
In order to solve the technical problems, the invention provides a fluorosilicone block copolymer, and a preparation method and application thereof. The invention synthesizes the block copolymer of the main chain type fluorine-containing alternating copolymer by polymerizing the fluorine-containing alternating copolymer macromolecule initiator and a silane reagent, and then prepares the fluorosilicone block copolymer by a strong reducing agent. The fluorosilicone segmented copolymer has the advantages that firstly, the trialkoxysilane groups in grafting are rich, and condensation reaction is facilitated; second, the thick graft-crosslinked layer formed from the sol-gel is more stable than the thin layer formed from the conventional triethoxysilane and the thickness of the fluorinated layer can be varied by varying the molecular weight of the fluorine-containing segment.
The first purpose of the invention is to provide a fluorosilicone block copolymer, the structure of which is shown as the formula (1):
Figure RE-GDA0003801839600000021
wherein, z is 4-8; y is 2-5; x is 4-8; n is 1-100; m is 1-20; n, m, x and y are integers;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
The second object of the present invention is to provide a method for preparing the fluorosilicone block copolymer, comprising the steps of,
s1, under the protection atmosphere, carrying out photo-controlled living radical polymerization reaction on a silane reagent shown in a formula (2) and a fluorine-containing alternating copolymer macroinitiator shown in a formula (3) 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 and S1, under the action of an initiator and a reducing agent, the block copolymer of the main chain type fluorine-containing alternating copolymer shown in the formula (4) reacts in a solvent II at 70-90 ℃ to obtain the fluorosilicone block copolymer;
wherein, the structures of the formulas (2) to (4) are as follows:
Figure RE-GDA0003801839600000031
wherein, z is 4-8; y is 2-5; x is 4-8; n is 1-100; m is 1-20; n, m, x and y are integers;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
In one embodiment of the present invention, in S1, the fluorine-containing alternating copolymer is (AB) n Obtained by START polymerization of monomer A and 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 present invention, in S1, the silane reagent is methacryloxypropyltrimethoxysilane (TMAPMA), methacryloxypropyltriethoxysilane (EPMA), or methacryloxypropyltriisopropylsilane (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, tetramethylammonium iodide, sodium chloride, tetrabutylammonium bromide, and diphenylphosphine 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 present invention, in S1, the photocatalyst is tetramethylammonium iodide; the solvent I is dimethylacetamide.
In one embodiment of the present invention, in S1, the silane agent and fluorine-containing alternating copolymer macroinitiator are present in a molar ratio of 2 to 5: 1.
in one embodiment of the present invention, in S1, the polymerization reaction is carried out under 373-403nm illumination conditions for at least 0.5 h.
In one embodiment of the present 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 purpose of the invention is to provide a preparation method of fluorinated silicon nanoparticles (F-SNs), which comprises the following steps that a silicon source and the fluorosilicone block copolymer react in a solvent III at 55-65 ℃ to obtain the fluorinated silicon nanoparticles (F-SNs).
In one embodiment of the present 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 present invention, the silicon source and fluorosilicone block copolymer are present in a molar ratio of 500: 1.
In one embodiment of the invention, the solvent III is 1, 3-bistrifluorotoluene and/or toluene.
In one embodiment of the present invention, the solvent III is 1, 3-bistrifluorotoluene.
In one embodiment of the present 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 reacted to form a fluorinated layer around the monodisperse silicas.
In one embodiment of the invention, the sol-gel time is 1.5 to 12 hours.
In one embodiment of the invention, the sol-gel time is 4 h.
It is a fourth object of the present invention to provide fluorinated silicon nanoparticles (F-SNs) prepared by the method.
The fifth purpose of the invention is to provide a preparation method of the super-hydrophobic coating, which comprises the following steps of uniformly dispersing the silicon fluoride nano particles (F-SNs) in a solvent IV, coating the solution on a glass substrate, and carrying out heat treatment and curing to obtain the super-hydrophobic coating. The static contact angle of the coating and water is more than 150 degrees, and water drops are easy to fall off from the surface, which shows that the coating has super-hydrophobic property.
In one embodiment of the present 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 fluorinated silicon nanoparticles is 30-60 mg/mL.
In one embodiment of the present invention, the concentration of the fluorinated silicon nanoparticles is 40 mg/mL.
In one embodiment of the invention, the glass is 1cm by 1cm in size.
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 of using perfluorooctyl triethoxy silicone, the grafted crosslinking layer formed by triisopropyl siloxane sol-gel is thicker and more stable than the conventional crosslinking layer formed by triethoxy silane, and the thickness of the fluorinated layer can be changed by changing the molecular weight of the fluorine-containing chain segment, so that the anti-fouling performance of the nano particles can be improved; secondly, the quantity of siloxane in the fluorine-silicon polymer can be controlled by adjusting the polymerization molar ratio of the silane to the fluorine-containing polymer, and the higher the abundance 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 cocondensation method is formed by the simultaneous condensation of a silicon source precursor and one or more fluoroalkyl silanes, whereas 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, the fluorine-containing chain segments are more uniformly distributed on the outer sides of the nano particles.
(3) The preparation of the super-hydrophobic coating greatly reduces the consumption of the fluorosilicone, can greatly save the production cost, and the molar ratio of the silicon source to the fluorosilicone in the super-hydrophobic nano particles prepared by the condensation method in the prior art is 2-20: 1, the proportion of the fluorosilicone is very high, so that the super-hydrophobic effect can be achieved.
Drawings
In order that the manner in which the present invention is more fully understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, wherein:
FIG. 1 shows a schematic view of the embodiment 1 (AB) of the present invention n Reaction scheme (iv).
FIG. 2 shows a schematic view of a liquid crystal display device according to example 1 of the present invention (AB) n Is 1 H NMR test results.
FIG. 3 shows a schematic view of a liquid crystal display device according to example 1 of the present invention (AB) n Reaction scheme a.
FIG. 4 shows A (AB) in example 1 of the present invention n Is 1 H NMR test results.
FIG. 5 is a reaction scheme of a fluorosilicone block copolymer in example 1 of the present invention.
FIG. 6 shows A (AB) in example 1 of the present invention n -PIPSMA andA(AB) n of-PIPSMA-I 1 H NMR test results.
FIG. 7 shows A (AB) in example 1 of the present invention n And A (AB) n -GPC test results of pimsa.
FIG. 8 is a schematic diagram of the synthesis of F-SNs in example 2 of the present invention.
FIG. 9 shows fluorinated silicon nanoparticles (F-SNs) and comparative Silica Nanoparticles (SNs) and fluorosilicone block copolymer (A (AB)) n -infrared test results of the pimsa-I).
FIG. 10 shows the results of the water contact angle test in example 3 of the present invention; wherein (a) is the water contact angle of the silica nanoparticles, and (b) is the water contact angle of the fluorinated silica nanoparticles.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Chemical reagents used in the examples of the present invention:
the dimethyl acetamide and the toluene are subjected to dehydration operation (added with calcium hydride, dried overnight and then distilled under reduced pressure) before use and are sealed and stored in a desiccator; before use, the glass sheet is washed by acetone, deionized water and ethanol for 5min respectively and then is dried by argon. Other reagents and raw materials which are not described are purchased and used directly.
The detection method comprises the following steps:
1. of polymers 1 The H NMR spectrum was measured by a Bruker 300MHz Nuclear Magnetic Resonance (NMR) instrument. The test was carried out at room temperature (25 ℃) in CDCl 3 As deuterated reagent, Tetramethylsilane (TMS) was used as internal standard.
2. Molecular weight (M) of the Polymer n,GPC ) And molecular weight distribution index
Figure RE-GDA0003801839600000071
Determined using a TOSOH HLC-8320 Gel Permeation Chromatograph (GPC) equipped with a differential refractive index detector (TOSOH). Using DMF as eluentGPC was equipped with one TSKgel guard column (SuperAW-H) and two test columns (TSKgel SuperAWM-H), and the range of measurable polymer molecular weights was 1X 10 3 To 1X 10 6 g/mol. The eluent DMF contained a concentration of LiBr (0.01mol/L) at a flow rate of 0.6mL/min and was calibrated for polymer molecular weight using a linear Polystyrene (PS) from TOSOH as a standard. 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 (fully dissolved in DMF) directly from TOSOH and run the GPC instrument at 40 ℃ according to the requirements of TOSOH HLC-8320 GPC.
3. Fourier-Infrared Spectroscopy (FT-IR) measurements were performed on an infrared spectrometer (Bruker TENSOR-27, USA) using the KBr pellet method.
4. The Water Contact Angle (WCA) was measured by CA goniometer JC2000D5 (Shanghai morning digital technical Equipment Co., Ltd.).
Example 1
Synthesizing a fluorosilicone block copolymer based on the fluorine-containing alternating copolymer, specifically comprising the following steps:
(1) synthesis (AB) n : initial charge molar 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 (0.2769g), sodium iodide (0.0375g), 1, 7-octadiene (74 μ L), acetone (4mL) and a clean magnetic stir bar, respectively, by three freeze-pump-vac-argon applications 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. It is diluted with 0.5-1mL of tetrahydrofuran and precipitated in a large volume of methanol. Standing in refrigerator overnight, vacuum filtering, drying in 40 deg.C constant temperature vacuum oven, weighing to obtain fluorine-containing alternating copolymer (AB) n The reaction scheme is shown in FIG. 1.
FIG. 2 is (AB) n Is/are as follows 1 H NMR test results.
(2) Synthesis (AB) n A: initial feed molar ratio [ (AB) n ] 0 ：[C 8 F 17 I] 0 ：[NaI] 0 ＝1：10：
0.5, Adding (AB) to a clean 5mL ampoule n 、C 8 F 17 I、Ru(bpy) 3 Cl 2 AsAc-Na, acetone and a clean magnetic stirrer were used, and the subsequent operation was as in step (1) of this example, the reaction route is shown in FIG. 3.
FIG. 4 is (AB) n A of 1 H NMR test results.
(3) Synthesis of Fluorosiloxane Block copolymer prepared based on fluorine-containing alternating copolymer (A (AB) n -PIPSMA-I)；
Initial feed molar ratio [ (AB) n A] 0 ：[IPSMA] 0 ：[TBAI] 0 1: 5: 0.5, Adding (AB) to a clean 5mL ampoule n A. Methacryloxypropyl triisopropylsilane (IPSMA), tetrabutyl ammonium iodide (TBAI), anhydrous dimethylacetamide (DMAc) and a clean magnetic stirrer, the ampoule is placed in liquid nitrogen to freeze the solution, then air is pumped for 50s, then argon protective gas is introduced while the ampoule is unfrozen and dissolved at room temperature, then freezing, air pumping, unfreezing and inflating are carried out, and three circulation processes are sequentially carried out to remove oxygen in the ampoule. And after deoxidizing, rapidly moving the ampoule bottle to the position of the spray gun port to seal the pipe by flame. Placing the ampoule bottle in 403nm purple light for reaction for a certain time, transferring the ampoule bottle to dark place, breaking the tube, and transferring about 50 μ L of the polymer stock solution in deuterated chloroform by using a liquid transfer gun 1 H NMR test to calculate monomer conversion rate, sucking a small amount of anhydrous tetrahydrofuran by a dropper, dissolving, precipitating in anhydrous methanol, centrifuging, pouring out supernatant, and oven drying the obtained polymer in an oven at 30 deg.C to obtain fluorosilicone block copolymer (A (AB)) n -PIPSMA), because the steric hindrance of iodine atoms on the side chains is large, the sequential arrangement of subsequent fluorine-containing chain segments is influenced, and the iodine on the side chains and the terminal iodine are in a strong reducing agent Bu 3 Reduction to hydrogen by SnH with initial charge molar ratio [ (A (AB)) n -PIPSMA)] 0 ：[AIBN] 0 ：[Bu 3 SnH] 0 1: 10: 30, separately, into a clean 5mL ampoule (A (AB) n -PIPSMA), Azobisisobutyronitrile (AIBN)) Tributyltin hydride (Bu) 3 SnH), anhydrous toluene and a clean magnetic stirrer were operated by three times of freezing, vacuum-pumping, argon-feeding, flame-sealing the tube. Placing the ampoule bottle in a magnetic stirrer at 80 ℃ for stirring, after reacting for a preset time, breaking the ampoule bottle, settling in anhydrous methanol, centrifuging, pouring out the supernatant, and then placing the obtained polymer in an oven at 30 ℃ for drying, wherein the reaction route is shown in figure 5.
FIG. 6 shows A (AB) n -PIPSMA and A (AB) n of-PIPSMA-I 1 H NMR test results. As can be seen from the NMR chart, after iodine is reduced to hydrogen, the original is assigned to a (-CH) 2 CH(I)CH 2 -) and b (-CH 2 CH(I)CH 2 -) completely disappeared.
FIG. 7 shows A (AB) n And A (AB) n The GPC test result of the PIPEMA shows that the fluoropolymer exhibits a significant increase in molecular weight after polymerization of methacryloxypropyltriisopropylsilane.
Example 2
The preparation of fluorinated silicon nanoparticles (F-SNs) based on fluorosilicone block copolymers specifically comprises the following steps:
adding 0.21mL TEOS into 2.1mL isopropanol in a 10mL ampoule bottle, stirring to be homogeneous, adding 80 μ L ammonium hydroxide, stirring vigorously, and directly stirring in a stirrer at 60 ℃ for 24h to obtain Silica Nanoparticles (SNs); if after a certain period of time, the fluorosilicone block copolymer (A (AB)) dissolved in 1, 3-bistrifluorotoluene is dissolved n -PIPMA-I) was added to the reaction and stirred at 60 ℃ for 24 h. Centrifuging to remove supernatant after reaction, ultrasonic dissolving the product with toluene and isopropanol, centrifuging, removing supernatant, and oven drying at 120 deg.C for 1h to obtain silicon fluoride nanoparticles (F-SNs), wherein the synthesis diagram is shown in FIG. 8.
FIG. 9 shows fluorinated silicon nanoparticles (F-SNs) and comparative Silica Nanoparticles (SNs) and fluorosilicone block copolymer (A (AB)) n -infrared test results of the pimsa-I). The absorption peaks of the fluorinated silicon nanoparticles were consistent with those expected, corresponding to the silica nanoparticles and the fluorosilicone block copolymer, respectively.
Example 3
The super-hydrophobic coating prepared based on the fluorinated silicon nanoparticles specifically comprises the following steps:
silicon fluoride nanoparticles (F-SNs) were uniformly dispersed in isopropanol at a concentration of 40mg/mL, coated on a surface-cleaned glass substrate by spin coating, and the spin coating was repeated 3 times at 0.45. mu.L each time. Then the mixture is subjected to heat curing treatment for 1h in an oven at 120 ℃. Coatings of silica nanoparticles were prepared in the same manner as control experiments. FIG. 10 is a test result of water contact angle of the coating, wherein the water contact angle of the silica nanoparticle coating is very hydrophilic and the water drop spreads out completely; as can be seen from the results of the water contact angle test of the fluorinated silicon nanoparticle coating, the surface of the silica nanoparticle having hydrophilicity is superhydrophobic after fluorination.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Various other modifications and alterations will occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. A fluorosilicone block copolymer is characterized in that the structure is shown as a formula (1):
Figure FDA0003682308340000011
wherein, z is 4-8; y is 2-5; x is 4-8; n is 1-100; m is 1-20; n, m, x and y are integers;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
2. A method for preparing a fluorosilicone block copolymer according to claim 1, comprising the steps of,
s1, carrying out photo-controlled living radical polymerization reaction on a silane reagent shown in a formula (2) and a fluorine-containing alternating copolymer macroinitiator shown in a formula (3) 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 and S1, reacting the block copolymer of the main chain type fluorine-containing alternating copolymer shown in the formula (4) in a solvent II under the action of an initiator and a reducing agent to obtain the fluorosilicone block copolymer;
wherein, the structures of the formulas (2) to (4) are as follows:
Figure FDA0003682308340000012
Figure FDA0003682308340000021
wherein, z is 4-8; y is 2-5; x is 4-8; n is 1-100; m is 1-20; n, m, x and y are integers;
r is selected from-CH 3 、-CH 2 CH 3 or-CH (CH) 3 ) 2 。
3. The method of preparing a fluorosilicone block copolymer according to claim 2, wherein in S1, the photocatalyst is one or more of sodium iodide, tetramethylammonium iodide, sodium chloride, tetrabutylammonium bromide, and diphenylphosphinochloride.
4. The method of preparing a fluorosilicone block copolymer according to claim 2, wherein in S1, a molar ratio of the silane reagent to the fluorine-containing alternating copolymer macroinitiator is 2 to 5: 1.
5. the method of claim 2, wherein the polymerization reaction is carried out under 373-403nm illumination conditions for at least 0.5h in S1.
6. A method for preparing fluorinated silicon nanoparticles, characterized by comprising the step of reacting a silicon source and the fluorosilicone block copolymer of claim 1 in a solvent III at 55-65 ℃ to obtain the fluorinated silicon nanoparticles.
7. Fluorinated silicon nanoparticles prepared by the method of claim 6.
8. A preparation method of a super-hydrophobic coating is characterized by comprising the following steps of uniformly dispersing the silicon fluoride nano particles in a solvent IV, coating the solvent IV on a glass substrate, and carrying out heat treatment and curing to obtain the super-hydrophobic coating.
9. The method of claim 8, wherein the concentration of the fluorinated silica nanoparticles is 30-60 mg/mL.
10. A superhydrophobic coating prepared by the method of any one of claims 8-9.
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Citations (4)

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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

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