CN103450419B - A kind of amphipathic fluoride block copolymer resin and its preparation method and application - Google Patents
A kind of amphipathic fluoride block copolymer resin and its preparation method and application Download PDFInfo
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- CN103450419B CN103450419B CN201310339419.5A CN201310339419A CN103450419B CN 103450419 B CN103450419 B CN 103450419B CN 201310339419 A CN201310339419 A CN 201310339419A CN 103450419 B CN103450419 B CN 103450419B
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Abstract
The present invention relates to a kind of amphipathic fluoride block copolymer resin and its preparation method and application, the general structure of this amphipathic fluoride block copolymer resin such as formula (1), in formula, R=CH
3or H; X=15.0 ~ 50.0, y=3.0 ~ 20.0, z=3.0 ~ 10.0, p=1 or 4, m=3.0 ~ 25.0, n=3 or 5; X is-(CH
2)
k-or-(CH
2)
k-N (C
hh
2h+1)-SO
2-.Reversible addion-fragmentation chain transfer radical polymerization (RAFT) method of two steps is adopted to prepare, the first step adopts hydrophilic monomer and hydrophobic monomer to prepare random copolymers, then using it as Macromolecular chain transfer agent, fluorine component is added to generate amphipathic fluoride block copolymer.Amphipathic fluoride block copolymer resin preparation process of the present invention is simple, and nontoxic, anti-fouling effect is excellent, can be used for the base-material preparing marine antifouling coating,
Description
Technical field
The present invention relates to a kind of amphipathic fluoride block copolymer resin that can be applicable to marine anti-pollution and preparation method thereof.
Background technology
Marine antifouling coating is as a kind of special function protecting coating, bottom of ship, marine structure, offshore platform, submarine transport oil pipeline etc. are contained in for being coated with, to prevent halobiontic attachment stained, reduce the tremendous economic loss because biodeterioration brings and environmental disruption.
The development experience of marine antifouling coating is by the development course of traditional antifouling paint to environmental protection type anti-pollution paint.The stain control agent that traditional antifouling paint uses has toxicity, and create significant damage to environment and the ecosystem, countries in the world are forbidden in succession, and the development trend of present marine antifouling coating is the antifouling paint of nontoxic environment-friendly type.Wherein, low surface energy anti-fouling paint wherein studies a kind of environmental protection type anti-pollution paint the most active.Low surface energy anti-fouling paint is the material of the low surface energy utilizing coating surface to apply, to reduce the wettability of coating surface, even if make marine organisms be difficult to stick or have stick, in ship's navigation, also can make its desorption by the souring of current, play self-cleaning effect.
Marine ship low surface energy anti-fouling paint is mainly divided into organosilicon series and fluorochemical series.As the two-pack antifouling paint reported in CN1097447A, have employed polydimethylsiloxane and epoxy resin as base-material, the two-pack antifouling paint that tetrafluoroethylene and paraffin oil are formed as functional stuffing has good didirtresistance.The low surface energy for marine anti-fouling ship paint that hud typed fluorinated acrylate is prepared as low surface energy component is have employed in patent CN1388196A, this antifouling paint surface energy is low, property indices all meets environmental requirement, and painting process is simple, film forming ability ambient cure, and can ordinary organic solvents be dissolved in.But these simple low surface energy anti-fouling paints of research and development at present often can only make marine organisms adhere to loosely, need periodic cleaning, settled organism is once grow up very difficult removing, film can be destroyed in scale removal process, thus its range of application has significant limitation at present, be applied to speedster more, and method application be there is no to the large vessel being difficult to regularly go up depressed place cleaning.
Some large-scale marine animals of occurring in nature can not adhere to marine organisms as the epidermis of dolphin, shark, whale, have the characteristic of natural antibiont attachment, create based on bionic antifouling paint by this inspiration.At present, the direction of researching and developing biomimetic type antifouling paint mainly contains two: (1) extracts natural active matter as stain control agent; (2) epidermal structure of simulating large ocean animal realizes antifouling.The Main way of studies in China exploitation biomimetic type antifouling paint extracts natural active matter as stain control agent and the application of these stain control agents in coating.Picture capsaicine (capsicine), alkaloid, these natural active matters of peptides occur successively as the patent of stain control agent.As, CN02132491, CN03130372, CN200410018656 etc.But the antifouling patent of simulation large ocean animal cuticle configuration aspects also rarely has report.
There is the dual coarse structure of nano-micrometre level in the epidermal structure of large ocean animal, can secrete mucus, special open-minded liquid as oozy in dolphin epidermis, defines hydrophilic lower-surface-free-energy surface simultaneously, makes marine organisms be difficult to attachment.Can infer to have and receive microphase-separated and the polymkeric substance with hydrophobic and hydrophilic two kinds of characteristics can show unique anti-pollution characteristic from these marine animal epidermal structures.
Polyoxyethylene glycol shows the excellent patience for protein adsorption and cell adhesion owing to having very low polymkeric substance-water termination energy.Polyoxyethylene glycol is a kind of non-ionic water-soluble polymer, it is generally acknowledged, hydration remarkable between polyoxyethylene glycol and water molecules and steric repulsion effect, and these effects are most important to the absorption of resisting protein.Therefore, polyethylene glycols hydrophilic monomer has excellent antifouling property.Fluorocarbon polymer due to carbon fluorine chain extremely short, bond energy is higher, therefore molecular structure is more stable, polarity is low, and fluorine atom is very tight in the arrangement of carbon skeleton skin, effectively prevent the exposure of carbon atom and carbochain, therefore fluorocarbon shows very superior chemical stability, weathering resistance, erosion resistance, oxidation-resistance, hydro-oleophobicity etc.Hydrophilic anti-soil component is combined with it and is expected to form high performance anti-fouling material.
Summary of the invention
The object of the invention is simulation large ocean animal cuticle structure, provide a kind of nontoxic for marine anti-pollution, amphipathic fluoride block copolymer resin that anti-fouling effect is excellent and its preparation method and application.
Amphipathic fluoride block copolymer of the present invention, its general structure is such as formula (1):
Formula (1)
Wherein, R=CH
3or H; X=15.0 ~ 50.0, y=3.0 ~ 20.0, z=3.0 ~ 10.0, p=1 or 4, m=3.0 ~ 25.0, n=3 or 5; X is-(CH
2)
k-or-(CH
2)
k-N (C
hh
2h+1)-SO
2-.
The preparation method of amphipathic fluoride block copolymer of the present invention, it is reversible addion-fragmentation chain transfer radical polymerization (RAFT) method of employing two step, the first step adopts hydrophilic monomer and hydrophobic monomer to prepare random copolymers, then using it as Macromolecular chain transfer agent, add fluorine component to generate amphipathic fluoride block copolymer, specifically comprise the steps:
1) in a nitrogen atmosphere, by RAFT reagent, hydrophobic monomer, hydrophilic monomer, initiator Diisopropyl azodicarboxylate (AIBN) and solvent join in flask, hydrophobic monomer: the molar ratio of hydrophilic monomer is 1:0.2 ~ 10, Diisopropyl azodicarboxylate: the molar ratio of RAFT reagent is 1:2.0 ~ 5.0, described solvent is methyl-phenoxide, phenylate, dioxane or tetrahydrofuran (THF), the mass ratio of hydrophilic monomer and hydrophobic monomer sum and solvent is 1:1.5 ~ 5, at the temperature of 60 ~ 100 DEG C, reaction 2 ~ 6h, precipitation obtains Macromolecular chain transfer agent;
The skeleton symbol of said RAFT reagent is such as formula (2):
2) in the Macromolecular chain transfer agent that step 1) is obtained, fluorochemical monomer, Diisopropyl azodicarboxylate and solvent is added, fluorochemical monomer: the molar ratio of hydrophobic monomer is 0.06 ~ 1.0:1, Diisopropyl azodicarboxylate: the molar ratio of Macromolecular chain transfer agent is 1:2.0 ~ 5.0, described solvent is ethyl acetate or butylacetate, wherein the mass ratio of Macromolecular chain transfer agent and fluorochemical monomer sum and solvent is 1:1.5 ~ 5, again at the temperature of 60 ~ 100 DEG C, reaction 5 ~ 12h, obtains amphipathic fluoride block copolymer resin.
In the present invention, described hydrophilic monomer is polymerization single polymerization monomer methoxypolyethylene glycol acrylate or methoxypolyethylene glycol methacrylic ester.
In the present invention, described hydrophobic monomer is methyl acrylate, methyl methacrylate, butyl methacrylate or butyl acrylate.
In the present invention, described fluorochemical monomer is perfluoroethyl sulfoamido ethyl ester, methacrylic acid perfluor sulfonyl aminoethyl, dodecafluoroheptyl methacrylate or Hexafluorobutyl mathacrylate.
The application of amphipathic fluoride block copolymer of the present invention, as the base-material preparing marine antifouling coating.
Amphipathic fluoride block copolymer non-toxic of the present invention is harmless, and preparation technology is simple, due to segmented copolymer different blocks between polarity difference very big, therefore can form micro phase separation structure.The fluorine component of pole low surface energy makes this segmented copolymer have good anti-fouling effect and superior chemical stability, weathering resistance, erosion resistance, oxidation-resistance, hydro-oleophobicity etc. with the synergy of the hydrophilic monomer and surperficial micro phase separation structure with antifouling effect, can be used for the base-material preparing marine antifouling coating.
Accompanying drawing explanation
Fig. 1 is the adsorption strength of fluorescein isothiocyanate on amphipathic multipolymer B, C and silicon chip D.Wherein B and C represents amphipathic fluoride block copolymer, and D is silicon chip as a control group.
Embodiment
Below in conjunction with example, the present invention is further illustrated.
Embodiment 1:
(1) in a nitrogen atmosphere, by 0.21gRAFT reagent, 7.5g methoxypolyethylene glycol acrylate, 0.5g methyl acrylate, 0.04gAIBN, 12g methyl-phenoxide joins in 100ml there-necked flask.At the temperature of 60 DEG C, reaction 5h, precipitation obtains Macromolecular chain transfer agent.
(2) then get 0.8g Macromolecular chain transfer agent, add 0.92g perfluoroethyl sulfoamido ethyl ester, 0.006gAIBN, 5.17g butylacetate, at the temperature of 70 DEG C, reaction 10h, obtains amphipathic fluoride block copolymer resin.
Embodiment 2:
(1) in a nitrogen atmosphere, by 0.80gRAFT reagent, 5g methoxypolyethylene glycol methacrylic ester, 15g methyl acrylate, 0.10gAIBN, 55g phenylate joins in 100ml there-necked flask.At the temperature of 70 DEG C, reaction 4h, precipitation obtains Macromolecular chain transfer agent.
(2) then get 1.6g Macromolecular chain transfer agent, add 2.0g methacrylic acid perfluor sulfonyl aminoethyl, 0.01gAIBN, 10.2g butylacetate, at the temperature of 80 DEG C, reaction 10h, obtains amphipathic fluoride block copolymer resin.
Embodiment 3:
(1) in a nitrogen atmosphere, by 0.63gRAFT reagent, 3.82g methoxypolyethylene glycol methacrylic ester, 10.8g methyl acrylate, 0.09gAIBN, 43.5g methyl-phenoxide joins in 100ml there-necked flask.At the temperature of 80 DEG C, reaction 4h, precipitation obtains Macromolecular chain transfer agent.
(2) then get 1.2g Macromolecular chain transfer agent, add 1.8g methacrylic acid perfluor sulfonyl aminoethyl, 0.009gAIBN, 9.5g butylacetate, at the temperature of 90 DEG C, reaction 8h, obtains amphipathic fluoride block copolymer resin.
Embodiment 4:
(1) in a nitrogen atmosphere, by 0.69gRAFT reagent, 16g methoxypolyethylene glycol methacrylic ester, 4g methyl methacrylate, 0.10gAIBN, 46.7g dioxane joins in 100ml there-necked flask.At the temperature of 70 DEG C, reaction 5h, precipitation obtains Macromolecular chain transfer agent.
(2) then get 1.6g Macromolecular chain transfer agent, add 2.4g perfluoroethyl sulfoamido ethyl ester, 0.012gAIBN, 12.7g butylacetate, at the temperature of 100 DEG C, reaction 7h, obtains amphipathic fluoride block copolymer resin.
Embodiment 5:
(1) in a nitrogen atmosphere, by 0.69gRAFT reagent, 8g methoxypolyethylene glycol methacrylic ester, 12g methyl methacrylate, 0.10gAIBN, 46.7g phenylate joins in 100ml there-necked flask.At the temperature of 70 DEG C, reaction 5h, precipitation obtains Macromolecular chain transfer agent.
(2) then get 0.8g Macromolecular chain transfer agent, add 1.2g perfluoroethyl sulfoamido ethyl ester, 0.006gAIBN, 6.3g butylacetate, at the temperature of 90 DEG C, reaction 8h, obtains amphipathic fluoride block copolymer resin.
Embodiment 6:
(1) in a nitrogen atmosphere, by 0.34gRAFT reagent, 5g methoxypolyethylene glycol methacrylic ester, 5g methyl methacrylate, 0.05gAIBN, 23.3g methyl-phenoxide joins in 100ml there-necked flask.At the temperature of 70 DEG C, reaction 5h, precipitation obtains Macromolecular chain transfer agent.
(2) then get 1.6g Macromolecular chain transfer agent, add 2.4g perfluoroethyl sulfoamido ethyl ester, 0.012gAIBN, 12.7g butylacetate, at the temperature of 100 DEG C, reaction 7h, obtains amphipathic fluoride block copolymer resin.
Embodiment 7: the surface contact angle of amphipathic multipolymer film and surface energy
Respectively using distilled water and n-hexadecane as test liquid, the mensuration of surface contact angle is carried out to the amphipathic multipolymer film of preparation.The solution that amphipathic multipolymer is made into is spin-coated in substrate, by sample to be tested by measuring the surface contact angle of its static state after anneal, table 1 lists the static contact angle of each multipolymer of embodiment 1 to embodiment 6 to distilled water and n-hexadecane, can find out that the film of amphipathic multipolymer has very strong hydro-oleophobicity.The surface tension of each multipolymer film is also very low, even all lower than the surface energy of general fluorine-containing homopolymer.
The static contact angle of table 1 amphiphilic fluorinated block copolymer and surface tension data
θ
water, θ
n-Hexadecanerepresent the static contact angle of co-polymer membrane to water and n-hexadecane respectively; γ S, γ S
dwith γ S
prepresent the surface tension of co-polymer membrane, surface tension dispersive part and surface tension polar portion respectively, wherein γ S=γ S
d+ γ S
p.
Embodiment 8: the performance of amphipathic multipolymer resist coating film protein adsorption
After amphipathic multipolymer being prepared into the solution of proper concn, be spin-coated in substrate, then carry out anneal.The mixed phosphate salt buffer that above-mentioned multipolymer film is put into containing bovine serum albumin is cultivated for some time, then at fluorescence microscopy Microscopic observation, the opposing absorption property of multipolymer film to bovine serum albumin is probed into by the number of the fluorescein of count tag on bovine serum albumin.
As shown in Figure 1, B and C is amphipathic copolymer sample (corresponding respectively to the sample of embodiment 2 and 3 in table 1), and D is silicon chip as a control group.At the bottom of hydrophilic silicon wafer-based, amphipathic nature block polymer B and C to the adsorption strength of protein all much smaller than the protein adsorption amount on silicon chip, this has absolutely proved that the amphipathic nature block polymer in the present invention has the performance of excellent opposing protein adsorption, is a kind of desirable marine antifouling coating resin that can be used as environment-friendly type.
Claims (6)
1. an amphipathic fluoride block copolymer, is characterized in that, general structure is such as formula (1):
Wherein, R=CH
3or H; X=15.0 ~ 50.0, y=3.0 ~ 20.0, z=3.0 ~ 10.0, p=1 or 4, m=3.0 ~ 25.0, n=3 or 5; X is-(CH
2)
k-or-(CH
2)
k-N (C
hh
2h+1)-SO
2-.
2. prepare the method for amphipathic fluoride block copolymer according to claim 1, it is characterized in that comprising the steps:
1) in a nitrogen atmosphere, by RAFT reagent, hydrophobic monomer, hydrophilic monomer, initiator Diisopropyl azodicarboxylate and solvent join in flask, hydrophobic monomer: the molar ratio of hydrophilic monomer is 1:0.2 ~ 10, Diisopropyl azodicarboxylate: the molar ratio of RAFT reagent is 1:2.0 ~ 5.0, described solvent is methyl-phenoxide, phenylate, dioxane or tetrahydrofuran (THF), the mass ratio of hydrophilic monomer and hydrophobic monomer sum and solvent is 1:1.5 ~ 5, at the temperature of 60 ~ 100 DEG C, reaction 2 ~ 6h, precipitation obtains Macromolecular chain transfer agent;
The skeleton symbol of said RAFT reagent is such as formula (2):
2) in step 1) add fluorochemical monomer, Diisopropyl azodicarboxylate and solvent in obtained Macromolecular chain transfer agent, fluorochemical monomer: the molar ratio of hydrophobic monomer is 0.06 ~ 1.0:1, Diisopropyl azodicarboxylate: the molar ratio of Macromolecular chain transfer agent is 1:2.0 ~ 5.0, described solvent is ethyl acetate or butylacetate, wherein the mass ratio of Macromolecular chain transfer agent and fluorochemical monomer sum and solvent is 1:1.5 ~ 5, again at the temperature of 60 ~ 100 DEG C, reaction 5 ~ 12h, obtains amphipathic fluoride block copolymer resin.
3. the preparation method of amphipathic fluoride block copolymer according to claim 2, is characterized in that described hydrophilic monomer is polymerization single polymerization monomer methoxypolyethylene glycol acrylate or methoxypolyethylene glycol methacrylic ester.
4. the preparation method of amphipathic fluoride block copolymer according to claim 2, is characterized in that described hydrophobic monomer is methyl acrylate, methyl methacrylate, butyl methacrylate or butyl acrylate.
5. the preparation method of amphipathic fluoride block copolymer according to claim 2, is characterized in that described fluorochemical monomer is perfluoroethyl sulfoamido ethyl ester or methacrylic acid perfluor sulfonyl aminoethyl.
6. the application of amphipathic fluoride block copolymer according to claim 1, is characterized in that the base-material as preparing marine antifouling coating.
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| CN111171675A (en) * | 2020-01-19 | 2020-05-19 | 东华大学 | Preparation method of bionic composite marine antifouling coating based on long afterglow luminescence |
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| CN101456937A (en) * | 2008-12-30 | 2009-06-17 | 中国科学院上海有机化学研究所 | Polymethano-poly(methyl)acrylic ester two-block copolymer and preparation method thereof |
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