CN111690103A - Water-and oil-repellent fluorine-containing silicon copolymer and preparation method and application thereof - Google Patents

Water-and oil-repellent fluorine-containing silicon copolymer and preparation method and application thereof Download PDF

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CN111690103A
CN111690103A CN201910187636.4A CN201910187636A CN111690103A CN 111690103 A CN111690103 A CN 111690103A CN 201910187636 A CN201910187636 A CN 201910187636A CN 111690103 A CN111690103 A CN 111690103A
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fluorine
containing silicon
water
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silicon copolymer
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CN111690103B (en
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姜标
张丁
邢萍
潘仁明
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Shanghai Institute of Organic Chemistry of CAS
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    • 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
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
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    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

The invention discloses a water-repellent oil-repellent fluorine-containing silicon copolymer and a preparation method and application thereof, wherein the water-repellent oil-repellent fluorine-containing silicon copolymer is a polymer with a chemical structure general formula I or a general formula II:
Figure DDA0001993374480000011
Figure DDA0001993374480000012
wherein: r is any one of C1-C18 alkyl1Is hydrogen or methyl, m is selected from any integer from 30 to 80, and n is selected from any integer from 10 to 30. The fluorine-containing silicon copolymer is prepared by mixing octavinyl semioctasiloxane with a copolymer represented by
Figure DDA0001993374480000013
And acrylic ester monomer represented by

Description

Water-and oil-repellent fluorine-containing silicon copolymer and preparation method and application thereof
Technical Field
The invention relates to a fluorine-containing silicon copolymer, a preparation method and application thereof, in particular to a water-repellent oil-repellent fluorine-containing silicon copolymer, a preparation method and application thereof in low surface energy coating.
Background
Surfaces with water and oil repellent properties are currently used in a wide variety of fields, such as self-cleaning coatings, sports and outdoor clothing, biomedical layers, integrated sensors, microfluidic channels, etc. These surfaces are typically achieved by a combination of substrate surface geometry and low surface energy chemical composition.
Since water has a high surface tension, lowering the surface free energy may achieve hydrophobicity or even superhydrophobicity of the surface. Since the surface tension of oil is 20 to 30mN/m, it is required that the surface free energy of the substrate is less than 20mN/m in order to achieve the oil-repellent effect. The low surface energy coating is a coating system which is rapidly developed in recent years, a low surface energy coating formed by the low surface energy coating can meet the requirements of water and oil repellency of the surface, and several types of low surface energy coatings, such as fluorine-containing acrylic polymer coatings, fluorine-containing siloxane polymer coatings, fluorine-containing polyurethane coatings and the like, are developed on the market at present.
Currently, long-chain perfluoroalkanes have been widely used for preparing low-surface-energy coatings to achieve water-and oil-repellency of surfaces, in which a long-chain fluoroalkyl group containing a POSS (oligomeric silsesquioxane) group can significantly enhance the hydrophobicity of materials, for example, blending a long-chain fluoroalkyl group having a POSS group with polymethyl methacrylate (PMMA) or polyethyl methacrylate (PEMA) can significantly enhance the hydrophobicity of a coating film, and further, for example, a POSS-terminated poly (3-caprolactone) epoxy resin to which POSS is added can significantly enhance the hydrophobicity. Therefore, the long-chain fluoroalkyl group-containing compound (polymer) containing POSS has excellent water-and oil-repellency, and can be used for preparing low-surface-energy coatings to realize water-and oil-repellency of the surface.
Although the long-chain fluoroalkyl group-containing compound has excellent water and oil repellency, the long-chain fluoroalkyl group-containing compound is difficult to degrade and has potential hazards to human health and the environment. For example, Perfluorooctanoate (PFOA), which has been fully detected in wild animals and plants as well as in humans and the environment, and studies have shown that PFOA, Perfluorooctylsulfonate (PFOS) and other perfluoroalkyl chain-containing molecules (CnF2n, n.gtoreq.8) can accumulate in wild animals and plants and in humans, with the potential for harm to human health and environmental pollution. Since 2000, the U.S. Environmental Protection Agency (EPA) has taken various measures to reduce the potential impact of long chain Perfluorochemicals (PFCs) on human health and the environment. Currently, the european union has banned the use of perfluorooctanesulfonic acid and is evaluating the risk of perfluorooctanoic acid exposure.
Fluoropolyethers are another fluorine-containing substance that has been shown to have no potential for irritation or skin sensitization, no detectable genotoxic activity in vitro or in vivo, and excellent physical and chemical properties, such as high chemical resistance, high lubricity, low surface energy, and low toxicity, and thus, fluoropolyethers are considered as the most promising alternatives to long-chain perfluoroalkanes. At present, there have been reports on the use of fluoropolyethers as water-and oil-repellent agents.
Although there are reports related to the application of POSS modified fluoropolyether substances in low surface energy coatings at present, the POSS modified fluoropolyether substances containing short fluorine chains (the length of the fluorocarbon chain is less than 6) have poor water and oil repellency and cannot well meet application requirements, so the POSS modified fluoropolyether substances which are reported at present and can be used for constructing water and oil repellent surfaces all contain long fluorine chains (the length of the fluorocarbon chain is more than or equal to 6), and the substances have excellent water and oil repellency, but are not easy to degrade and have potential risks of harming human health and polluting the environment.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a degradable fluorine-containing silicon fluoride copolymer with short fluorine chain, water and oil repellency, a preparation method thereof and an application thereof in low surface energy coating, so as to overcome the defects of the existing fluorine-containing silicon fluoride copolymer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the water-repellent and oil-repellent fluorine-containing silicon copolymer is a polymer with a chemical structure general formula I or a general formula II:
Figure BDA0001993374470000021
wherein: r is selected from any one of C1-C18 alkyl (for example, methyl, ethyl, butyl, hexyl, octyl, lauryl, octadecyl, etc.), R1Is hydrogen or methyl, m is selected from any integer from 30 to 80, and n is selected from any integer from 10 to 30.
Preferably, the weight average molecular weight of the fluorine-containing silicon copolymer is 0.93 × 104～2.64×104。
Preferably, the fluorine-containing silicon copolymer has the following chemical structural formula:
Figure BDA0001993374470000031
or
Figure 1
The polymer of (1).
A process for producing the water-and oil-repellent fluorine-containing silicon copolymer of the present invention comprisesOctavinyl silsesquioxane is represented by
Figure BDA0001993374470000033
And acrylic ester monomer represented by
Figure BDA0001993374470000034
Or
Figure BDA0001993374470000035
The fluorine-containing unsaturated monomer is polymerized, and the reaction formula is shown as follows:
Figure BDA0001993374470000041
when the fluorine-containing silicon copolymer has the following chemical structural formula:
Figure BDA0001993374470000042
or
Figure 2
The water-and oil-repellent fluorine-containing silicon copolymer of (1) is prepared by: the octavinyl silsesquioxane is represented by the sum of monomers of octavinyl silsesquioxane and methyl methacrylate
Figure BDA0001993374470000051
The fluorine-containing unsaturated monomer is polymerized, and the reaction formula is shown as follows:
Figure BDA0001993374470000052
or
Figure 3
As one embodiment, the fluorine-containing silicon copolymer is prepared by first reacting octavinyl silsesquioxane (namely, octavinyl POSS, abbreviated as Ov-POSS)Is shown as
Figure BDA0001993374470000054
The acrylic ester monomer is polymerized and then reacts with the acrylic ester monomer shown as
Figure BDA0001993374470000055
The fluorine-containing unsaturated monomer (2) is polymerized.
As a preferred scheme, the compound is represented by
Figure BDA0001993374470000056
The acrylic ester monomer is selected from methyl methacrylate (R is methyl and R1Is methyl), ethyl methacrylate (R is methyl, R1Is ethyl), butyl methacrylate (R is methyl, R1Butyl), hexyl methacrylate (R is methyl, R1Hexyl), isooctyl methacrylate (R is methyl, R)1Is isooctyl), lauryl methacrylate (R is methyl, R1Lauryl), stearyl methacrylate (R is methyl, R1Octadecyl), methyl acrylate (R is hydrogen, R1Is methyl), ethyl acrylate (R is hydrogen, R1Is ethyl), butyl acrylate (R is hydrogen, R1Is butyl), hexyl acrylate (R is hydrogen, R1Hexyl), isooctyl acrylate (R is hydrogen, R1Is isooctyl), lauryl acrylate (R is hydrogen, R1Lauryl), stearyl acrylate (R is hydrogen, R1Octadecyl).
Preferably, the polymerization is carried out in an organic solvent in the presence of an initiator at a polymerization temperature of from 30 to 200 ℃.
Preferably, the polymerization reaction is carried out in an inert gas (e.g., nitrogen, argon, etc.) atmosphere.
Further preferably, the initiator is at least one selected from the group consisting of azo compounds (e.g., azobisisobutyronitrile, 1-t-amylazo-1-cyanocyclohexane, 1-t-butylazo-1-cyanocyclohexane), acyl peroxides (e.g., lauroyl peroxide), alkyl peroxides (e.g., di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyformate, t-butyl peroxyisooctanoate, t-butyl peroxy-2-ethylhexanoate), and hydroperoxides (e.g., diisopropylbenzene hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide).
In a further preferred embodiment, the organic solvent is at least one selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, esters, alcohols, ketones, dimethyl sulfoxide, and dimethylformamide.
As a further preferable mode, the organic solvent is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethyl acetate, butyl acetate, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, dimethylformamide, trichloroethane, trifluorotoluene, perfluoro-n-butyl methyl ether, and tetrahydrofuran; among them, low water-soluble organic solvents are preferable, for example, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone, and methyl isobutyl ketone.
As a further preferable scheme, the fluorine-containing silicon copolymer is prepared by firstly expressing octavinyl semiduplex siloxane (namely, octavinyl POSS, which is abbreviated as Ov-POSS) as
Figure BDA0001993374470000061
Carrying out polymerization reaction on the acrylate monomer and an initiator at the temperature of 30-200 ℃ to obtain a mixed solution containing a polymer intermediate; then adding the mixture containing the polymer intermediate as shown
Figure BDA0001993374470000071
And carrying out polymerization reaction on the fluorine-containing unsaturated monomer and the initiator at the temperature of 30-200 ℃ to obtain the fluorine-containing silicon copolymer.
As a further preferable scheme, when the octavinyl half-time siloxane and the acrylate monomer are polymerized, the molar weight of the added initiator is 0.1-5% of the molar weight of the acrylate monomer; when the polymer intermediate and the fluorine-containing unsaturated monomer are polymerized, the molar weight of the added initiator is 0.1-5% of the molar weight of the fluorine-containing unsaturated monomer.
As a further preferable scheme, after the reaction of the polymer intermediate and the fluorine-containing unsaturated monomer is finished, filtering is carried out, a filter cake is washed by a mixed solvent of methanol and chloroform, filtering and drying are carried out, and the fluorine-containing silicon copolymer is obtained.
As an embodiment, the
Figure BDA0001993374470000072
Is prepared from CF in the presence of alkali3CF2CF2(CF3)2COH (i.e. perfluoro-2-methyl-2-pentanol) with
Figure BDA0001993374470000073
Reaction to obtain (A)
Figure BDA0001993374470000074
Is composed of
Figure BDA0001993374470000075
When the temperature of the water is higher than the set temperature,
Figure BDA0001993374470000076
is composed of
Figure BDA0001993374470000077
(i.e., methacryloyl halide)), X is a halogen, preferably Br or Cl, more preferably Cl.
Preferably, the base is an organic base selected from any one of triethylamine, pyridine, N-diisopropylethylamine, diethylamine, piperidine and N-methylpiperidine.
Preferably, the reaction temperature is-30 ℃ to room temperature (preferably-10 ℃ to 0 ℃), and the reaction solvent is ethylene glycol dimethyl ether, diethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, DMF, benzene or 1, 2-dichloroethane.
Preferably, CF3CF2CF2(CF3)2COH：
Figure BDA0001993374470000078
The molar ratio of the alkali is 1 (1-1.5) to 1-1.5.
As an embodiment, the
Figure BDA0001993374470000081
Is composed of CF3CF2CF2(CF3)2COM (i.e. perfluoro-2-methyl-2-pentanolate) with
Figure BDA0001993374470000082
Reaction to obtain (A)
Figure BDA0001993374470000083
Is composed of
Figure BDA0001993374470000084
When the temperature of the water is higher than the set temperature,
Figure BDA0001993374470000085
is composed of
Figure BDA0001993374470000086
(i.e., 4-vinylbenzyl halide)), M is an alkali metal (e.g., Li, Na, K), and X is a halogen (preferably Br, Cl, more preferably Cl).
Preferably, the reaction temperature is-30 ℃ to 100 ℃ (preferably-10 ℃ to room temperature), CF3CF2CF2(CF3)2COM：
Figure BDA0001993374470000087
The molar ratio of (1-1.5) to (1).
Preferably, the reaction solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, DMF, DMAc, benzene, 1, 2-dichloroethane, methanol or ethanol.
Preferably, said CF3CF2CF2(CF3)2COM made of CF3CF2CF2(CF3)2COH is obtained by reaction with a strong base expressed as MOH, which is a hydroxide of an alkali metal (e.g., KOH, NaOH, LiOH).
More preferably, the reaction solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, methylene chloride, DMF, DMAc, benzene, 1, 2-dichloroethane, methanol or ethanol.
More preferably, the reaction temperature is from-30 ℃ to 100 ℃ (preferably from-10 ℃ to room temperature).
As a further preferable embodiment, MOH: CF (compact flash)3CF2CF2(CF3)2The molar ratio of COH is (1-1.5): 1.
The invention discloses an application of the water-repellent and oil-repellent fluorine-containing silicon copolymer as a coating main body for preparing a low-surface-energy coating.
Compared with the prior art, the invention has the following remarkable beneficial effects:
experiments prove that: the fluorine-containing silicon copolymer with the structure of the general formula I or the general formula II contains short fluorine chains, is degradable, has no potential harm to human health and environment, is safe and environment-friendly, has excellent water and oil repellency, can meet the performance requirement of preparing low-surface-energy paint, and can be used for constructing a water and oil repellent surface; in addition, the preparation method disclosed by the invention is simple to operate, the raw materials are easy to obtain, the cost is low, special equipment and a complex post-treatment process are not needed, the safety and the environmental protection are realized, the energy consumption is low, and the large-scale production is easy to realize; therefore, the invention has significant progress and outstanding advantages over the prior art.
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining the embodiment.
Example 1
Perfluoro-2-methyl-2-pentanol: CF (compact flash)3CF2CF2(CF3)2Preparation of COH:
5g (0.86mol) of dry potassium fluoride, 50ml of DMAC, 17.13g of perfluoro-2-methyl-2-pentene (0.0571mol) were charged into the reactorAfter stirring for 1 hour at below 7 ℃, 10.9gN was introduced under a weak oxygen flow2O4(0.118 mol) and reacted for 48 hours to terminate the reaction, H was added3PO30.62g H3PO3Adding 40ml of water) to carry out quenching reaction, and distilling at normal pressure to obtain the perfluoro-2-methyl-2-pentanol CF3CF2CF2(CF3)2COH (colorless liquid, 65.7% yield).
Through the test:1H NMR(400MHz,DMSO-d6,):10.93(d,J＝4.3Hz,1H)；
19F NMR(376MHz,DMSO-d6,):-71.45–-71.86(m,6F),-80.09(d,J＝11.7Hz,3F),-115.44(s,2F),-124.05(s,2F)；
LRMS(EI),m/z(％):69.1(100),297.0(36.9)。
example 2
Potassium perfluoro-2-methyl-2-pentanol: CF (compact flash)3CF2CF2(CF3)2Preparation of COK:
dissolving 0.92g KOH (16mmol,1eq) in 12ml absolute ethyl alcohol, stirring for half an hour in an ice-water bath, dropwise adding 5.768g (17.17mmol,1.1eq) perfluoro-2-methyl-2-pentanol, reacting for 2 hours at room temperature, performing pressure distillation on the clear solution under vacuum (3mpa), and performing vacuum drying on the obtained residue under the temperature of 80 ℃ by using an oil pump to obtain the potassium perfluoro-2-methyl-2-pentanol: CF (compact flash)3CF2CF2(CF3)2COK contains potassium 2-methyl-2-pentanolate (white crystal, 5.984g, yield 100%).
Through the test:19F NMR(376MHz,DMSO-d6):-73.82–-74.13(m,6F),-79.33(t,J＝11.0Hz, 3F),-115.03–-115.53(m,2F),-123.04–-123.75(m,2F)；
LRMS(ESI)m/z:334.85(M-K)；
HRMS(ESI)calcd.for C6F13O(M-K)334.9747,found.334.9740；
FT-IR(cm-1):1341.7,1204.8,1142.7,1114.0,955.8,817.0,751.9,734.2,715.0。
example 3
Fluorine-containing unsaturated monomer
Figure BDA0001993374470000101
The preparation of (1):
under the protection of nitrogen, 4g of perfluoro-2-methyl-2-pentanol (11.9mmol,1eq), 2.64ml (14.75mmol,1.24eq) of triethylamine and 20ml of diethyl ether are added into a reactor, stirred for 2 hours under a dry ice ethanol bath (the temperature is controlled to be about-10 ℃), then 1.49g (14.28mmol,1.2eq) of methacryloyl chloride is slowly dripped, the reaction is finished after the dripping, the reaction is carried out for 12 hours at room temperature, the reaction is finished, the reaction is quenched by 5 percent of dilute sulfuric acid under an ice water bath, an organic phase is washed by deionized water and saturated common salt solution, dried by anhydrous sodium sulfate, filtered, decompressed and distilled, and distilled at 8kPa, and 72 ℃ fractions are collected, thus obtaining the fluorine-containing unsaturated monomer
Figure BDA0001993374470000102
(colorless liquid, yield 98.17%).
Through the test:19F NMR(376MHz,CDCl3):-66.08–-66.35(m),-80.49(t,J＝12.4Hz),-112.57 –-113.13(m),-124.11,-124.73(m)；
1H NMR(400MHz,CDCl3):6.22(d,J＝0.7Hz,1H),5.82(t,J＝3.4Hz,1H),1.98(dd,J ＝6.8,0.7Hz,3H)；
13C NMR(101MHz,CDCl3):159.97,133.87,130.06,17.99.IR(cm-1):1789.5,1247.0, 1119.4,1078.7,995.9,736.2,720.0；
LRMS(EI),m/z(％):69.1(100),404.1(29.2)；
HRMS(EI),m/z(100％):calcd for C10H5O2F13 404.0082,found 404.0077。
example 4
Fluorine-containing unsaturated monomer
Figure BDA0001993374470000103
The preparation of (1):
under the protection of nitrogen, 3.93g of perfluoro-2-methyl-2-pentanol potassium (10.5mmol,1.05equiv.) and 1.56g of 4-vinyl benzyl chloride (10mmol,1.0equiv.) are dissolved in 10mL of anhydrous DMAc, stirred and reacted for 24 hours at room temperature, the reaction system is poured into diethyl ether, washed by deionized water and saturated common salt water in sequence, dried by anhydrous sodium sulfate, filtered, the solvent is dried by spinning, and the column is filled with the mixtureChromatography (EtOAc: PE ═ 1:40) to obtain the fluorine-containing unsaturated monomer
Figure BDA0001993374470000111
(colorless liquid, 4.16g, 92.1% yield).
Through the test:1H NMR(400MHz,CDCl3):7.43(d,J＝8.2Hz,2H),7.29(d,J＝8.2Hz,2H),6.72(dd,J＝17.6,10.9Hz,1H),5.78(d,J＝17.6Hz,1H),5.29(d,J＝10.9Hz,1H),5.02(s,2H)；
19F NMR(376MHz,CDCl3)-65.73–-67.82(m,6F),-80.46(t,J＝12.1Hz,3F),-112.04 –-115.03(m,2F),-122.51–-126.03(m,2F)；
13C NMR(101MHz,CDCl3)138.14,136.14,133.91,128.15,126.41,114.67,71.55；
LRMS(EI)m/z(％):117.1(100),452.1(92.2)；
HRMS(EI)m/z(％):calcd for C15H9OF13 452.0447,found 452.0446；
IR(cm-1):1247.2,1166.8,1146.3,829.7,737.9,716.4。
example 5
Example 5.1
Fluorine-containing silicon copolymer
Figure BDA0001993374470000112
The preparation of (1):
under the protection of argon, octavinyl hemisiloxane and methyl methacrylate are dissolved in THF, AIBN is added, and then the mixture is stirred and reacted for 24 hours at the temperature of 60 ℃ to obtain mixed liquid containing polymer intermediate; then, adding fluorine-containing unsaturated monomer into the mixed solution containing the polymer intermediate under the protection of argon
Figure BDA0001993374470000113
And AIBN, stirring at 60 deg.C for 24 hr, terminating reaction, filtering, and adding CHCl to filter cake3/CH3Washing with OH (volume ratio 1/30) solution, drying to obtain white powder solid, namely, the copolymer containing fluorine and silicon
Figure BDA0001993374470000121
In this example, when methyl methacrylate was added, the molar ratios of methyl methacrylate to octavinyl silsesquioxane were 20:1, 13.3:1, and 10:1 in this order, and the molar amount of AIBN added was 0.1% of that of methyl methacrylate; when the fluorine-containing unsaturated monomer is added, the molar ratio of the fluorine-containing unsaturated monomer to the initially added octavinyl half-time siloxane is 10:1, 6.7:1 and 5:1 in sequence, and the added molar amount of AIBN is 0.1 percent of that of the fluorine-containing unsaturated monomer; the obtained fluorine-containing silicon copolymer is named as P1, P2 and P3 in sequence.
Example 5.2
Fluorine-containing silicon copolymer
Figure 4
The preparation of (1):
under the protection of argon, octavinyl hemisiloxane and methyl methacrylate are dissolved in THF, AIBN is added, and then the mixture is stirred and reacted for 24 hours at the temperature of 60 ℃ to obtain mixed liquid containing polymer intermediate; then, adding fluorine-containing unsaturated monomer into the mixed solution containing the polymer intermediate under the protection of argon
Figure BDA0001993374470000123
And AIBN, stirring at 60 deg.C for 24 hr, terminating reaction, filtering, and adding CHCl to filter cake3/CH3Washing with OH (volume ratio 1/30) solution, drying to obtain white powder solid, namely, the copolymer containing fluorine and silicon
Figure 5
In this example, when methyl methacrylate was added, the molar ratio of methyl methacrylate to octavinyl silsesquioxane was 40:1, 20:1, and 13.3:1 in this order, and the molar amount of AIBN added was 0.1% of that of methyl methacrylate; when the fluorine-containing unsaturated monomer is added, the molar ratio of the fluorine-containing unsaturated monomer to the initially added octavinyl half-time siloxane is 20:1, 10:1 and 6.7:1 in sequence, and the added molar amount of AIBN is 0.1 percent of that of the fluorine-containing unsaturated monomer; the obtained fluorine-containing silicon copolymer is named as P4, P5 and P6 in sequence.
The average yield of P1-P6 in this example was 71.8%.
The water and oil repellency of the obtained fluorine-containing silicon copolymer is tested by the following test method:
coating solutions with mass concentration of 6% are respectively prepared by the fluorine-containing silicon copolymer and THF, rinsed cotton fabrics (8cm multiplied by 8cm) are immersed in the coating solutions, placed for 1 hour, taken out and baked for 1 hour at 80 ℃, baked for 5 minutes at 160 ℃, cooled at room temperature, contact angles of the films with water and n-hexadecane are respectively tested, three times of each solution are tested, and an average value is obtained by averaging the three times. And (3) testing conditions are as follows: the liquid volume was 3 microliters, the height was 0.5 centimeters, and the magnification was 7 times, and the test results are shown in table 1.
TABLE 1 Performance test data for fluorosilicone copolymers
Sample (I) m n Weight average molecular weight Water contact Angle (°) Contact Angle of n-hexadecane (°)
P1 68 26 17129 142 113
P2 57 21 14035 151 120
P3 47 18 11914 154 121
P4 30 21 12425 136 124
P5 32 20 12128 147 130
P6 35 19 11978 156 121
As can be seen from table 1: the contact angle of a coating film formed by the fluorine-containing silicon copolymer provided by the invention with water is as high as 156 degrees, and the contact angle of the coating film with n-hexadecane is as high as 130 degrees, which shows that the fluorine-containing silicon copolymer provided by the invention has excellent water and oil repellent performance, and the fluorine-containing silicon copolymer provided by the invention has short fluorine-containing chain, so that the fluorine-containing silicon copolymer is degradable, harmless to human bodies and environment, safe and environment-friendly, and can be used as a coating main body for preparing low surface energy coatings.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.

Claims (10)

1. A water-and oil-repellent fluorine-containing silicon copolymer is characterized in that the copolymer is a polymer with a chemical structure general formula I or a general formula II:
Figure FDA0001993374460000011
wherein: r is any one of C1-C18 alkyl1Is hydrogen or methyl, m is selected from any integer from 30 to 80, and n is selected from any integer from 10 to 30.
2. The water-and oil-repellent fluorine-containing silicon copolymer according to claim 1, wherein the weight average molecular weight of the fluorine-containing silicon copolymer is 0.93 × 104～2.64×104。
3. A process for producing the water-and oil-repellent fluorine-containing silicon copolymer according to claim 1, characterized in that octavinyl silsesquioxane is represented by formula
Figure FDA0001993374460000012
And acrylic ester monomer represented by
Figure FDA0001993374460000013
Figure FDA0001993374460000014
The fluorine-containing unsaturated monomer is polymerized, and the reaction formula is shown as follows:
Figure FDA0001993374460000021
4. the method of claim 3, wherein: is shown as
Figure FDA0001993374460000022
The acrylate monomer is selected from any one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate and stearyl acrylate.
5. The method of claim 3, wherein: the polymerization reaction is carried out in an organic solvent in the presence of an initiator, and the polymerization reaction temperature is 30-200 ℃.
6. The method of claim 5, wherein: the initiator is at least one selected from azo compounds, acyl peroxide, alkyl peroxide and hydroperoxide.
7. The method of claim 5, wherein: the organic solvent is at least one selected from aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, ether, ester, alcohol, ketone, dimethyl sulfoxide and dimethylformamide.
8. The method of claim 3, wherein: the above-mentioned
Figure FDA0001993374460000023
Is in the presence of alkaliIn the presence of a catalyst consisting of CF3CF2CF2(CF3)2COH and
Figure FDA0001993374460000024
obtained by reaction, X is halogen.
9. The method of claim 3, wherein: the above-mentioned
Figure FDA0001993374460000031
Is composed of CF3CF2CF2(CF3)2COM and
Figure FDA0001993374460000032
obtained by reaction, M is alkali metal, and X is halogen.
10. Use of the water-and oil-repellent fluorine-containing silicon copolymer according to claim 1, characterized in that: used as a coating main body for preparing low surface energy coating.
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