CN103450419A - Amphiphilic fluorine-containing block copolymer resin, and preparation method and application thereof - Google Patents
Amphiphilic fluorine-containing block copolymer resin, and preparation method and application thereof Download PDFInfo
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 30
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000011737 fluorine Substances 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 30
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229940043232 butyl acetate Drugs 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 Hexafluorobutyl Chemical group 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical group CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 17
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 229920005604 random copolymer Polymers 0.000 abstract description 3
- 238000013467 fragmentation Methods 0.000 abstract description 2
- 238000006062 fragmentation reaction Methods 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 7
- 241001465754 Metazoa Species 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
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- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 description 2
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 239000005662 Paraffin oil Chemical group 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
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- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
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- 230000036571 hydration Effects 0.000 description 1
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- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an amphiphilic fluorine-containing block copolymer resin, and a preparation method and application thereof. The structural general formula of the amphiphilic fluorine-containing block copolymer resin is as shown in formula (1). In the formula, R=CH3 or 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, and n=3 or 5; and X is -(CH2)k- or -(CH2)k-N(ChH2h+1)-SO2-. The amphiphilic fluorine-containing block copolymer resin is prepared through a two-step reversible addition-fragmentation chain transfer-free radical polymerization (RAFT) method. The method comprises the following steps: preparing a random copolymer from a hydrophilic monomer and a hydrophobic monomer, and adding fluorine-containing components into the random copolymer serving as a macromolecular chain transfer agent to generate the amphiphilic fluorine-containing block copolymer. The amphiphilic fluorine-containing block copolymer resin is simple in preparation process, non-toxic, harmless and favorable in anti-fouling effect, and can be used for preparation of base materials of marine anti-fouling paint. Formula (1) is shown in the specification.
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, be contained in bottom of ship, marine structure, offshore platform, submarine transport oil pipeline etc. for being coated with, to prevent halobionticly adhering to stainedly, reduce the tremendous economic loss and the environmental disruption that bring because of biodeterioration.
The development experience of marine antifouling coating by traditional antifouling paint the development course to environmental protection type anti-pollution paint.The stain control agent that traditional antifouling paint is used has toxicity, and environment and the ecosystem have been produced to significant damage, and countries in the world are forbidding in succession, and the development trend of marine antifouling coating is the antifouling paint of nontoxic environment-friendly type now.Wherein, low surface energy anti-fouling paint is wherein to study the most active a kind of environmental protection type anti-pollution paint.Low surface energy anti-fouling paint is the material that utilizes the low surface energy of coating surface coating, to reduce the wettability of coating surface, even make marine organisms be difficult to stick or have, stick, the souring by current in ship's navigation also can make its desorption, plays self-cleaning effect.
Marine ship mainly is divided into organosilicon series and fluorochemical series with low surface energy anti-fouling paint.As the two-pack antifouling paint of reporting in CN1097447A, adopted polydimethylsiloxane and epoxy resin as base-material, the two-pack antifouling paint that tetrafluoroethylene and paraffin oil form as functional stuffing has didirtresistance preferably.The low surface energy for marine anti-fouling ship paint that has adopted hud typed fluorinated acrylate to prepare as the low surface energy component in patent CN1388196A, this antifouling paint surface can be low, property indices all meets environmental requirement, and the brushing process is simple, the film forming ability ambient cure, and can be dissolved in ordinary organic solvents.It is not firm that but these simple low surface energy anti-fouling paints of researching and developing at present often can only make marine organisms adhere to, need periodic cleaning, once growing up, settled organism removes being difficult to, can destroy and film in scale removal process, thereby its range of application has significant limitation at present, be applied to speedster more, and there is no the method application to being difficult to regularly to go up the large vessel of clearing up in depressed place.
Some large-scale marine animals of occurring in nature, as the epidermis of dolphin, shark, whale can not adhere to marine organisms, have the characteristic that natural antibiont adheres to, and produced based on bionic antifouling paint by this inspiration.At present, the direction of research and development biomimetic type antifouling paint mainly contains two: (1) extracts natural active matter as stain control agent; (2) epidermal structure of simulation large ocean animal is realized antifouling.The main direction of domestic research and development biomimetic type antifouling paint is to extract 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, and special open-minded liquid as oozy as the dolphin epidermis, formed hydrophilic low surface energy surface, makes marine organisms be difficult to adhere to simultaneously.From these marine animal epidermal structures, can infer, the polymkeric substance that has the microphase-separated received and have hydrophobic and hydrophilic two specific characters can show unique anti-pollution characteristic.
Polyoxyethylene glycol shows the good 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, and hydration and the steric repulsion effect of brilliance between polyoxyethylene glycol and water molecules, these effects are most important to the absorption of resisting protein.Therefore, the polyethylene glycols hydrophilic monomer has excellent antifouling property.Fluorocarbon polymer is because carbon fluorine chain is extremely short, bond energy is higher, therefore molecular structure is more stable, polarity is low, and fluorine atom is very tight in the outer arrangement of carbon skeleton, effectively prevented the exposure of carbon atom and carbochain, therefore fluorocarbon shows very superior chemical stability, weathering resistance, erosion resistance, oxidation-resistance, hydro-oleophobicity etc.By hydrophilic anti-soil component with it in conjunction with being expected to form high performance anti-fouling material.
Summary of the invention
The objective of the invention is to simulate large ocean animal cuticle structure, provide a kind of nontoxic for marine anti-pollution, amphipathic fluoride block copolymer resin that anti-fouling effect is good and its preparation method and application.
Amphipathic fluoride block copolymer of the present invention, its general structure is suc as formula (1):
Formula (1)
Wherein, R=CH
3perhaps 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 addition-fragmentation chain transfer free radical polymerization (RAFT) method that adopts two steps, the first step adopts hydrophilic monomer and hydrophobic monomer to prepare random copolymers, then using it as the macromolecular chain transfer agent, add fluorine component to generate amphipathic fluoride block copolymer, specifically comprise the steps:
1) under 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 ℃, reaction 2～6h, precipitation obtains the macromolecular chain transfer agent;
The skeleton symbol of said RAFT reagent is suc as formula (2):
2) in the macromolecular chain transfer agent made in step 1), add fluorochemical monomer, Diisopropyl azodicarboxylate and solvent, 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 ℃, reaction 5～12h, obtain the 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 vinylformic acid perfluor sulfonyl amido ethyl ester, methacrylic acid perfluor sulfonyl amido ethyl ester, dodecafluoroheptyl methacrylate or Hexafluorobutyl mathacrylate.
The application of amphipathic fluoride block copolymer of the present invention, as the base-material for preparing marine antifouling coating.
Amphipathic fluoride block copolymer non-toxic of the present invention is harmless, and preparation technology is simple, because polarity difference between the different blocks of segmented copolymer is very big, therefore can form micro phase separation structure.The fluorine component of utmost point low surface energy and have the hydrophilic monomer of antifouling effect and the synergy of surperficial micro phase separation structure makes this segmented copolymer have good anti-fouling effect and superior chemical stability, weathering resistance, erosion resistance, oxidation-resistance, hydro-oleophobicity etc., can be used for preparing the base-material of marine antifouling coating.
The accompanying drawing explanation
Fig. 1 is the adsorption strength of amphipathic multipolymer B, C and the upper fluorescein isothiocyanate of silicon chip D.Wherein B and C represent 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), under nitrogen atmosphere, by 0.21gRAFT reagent, 7.5g methoxypolyethylene glycol acrylate, 0.5g methyl acrylate, 0.04gAIBN, 12g methyl-phenoxide join in the 100ml there-necked flask.At the temperature of 60 ℃, reaction 5h, precipitation obtains the macromolecular chain transfer agent.
(2) then get 0.8g macromolecular chain transfer agent, add 0.92g vinylformic acid perfluor sulfonyl amido ethyl ester, 0.006gAIBN, 5.17g butylacetate, at the temperature of 70 ℃, reaction 10h, obtain the amphipathic fluoride block copolymer resin.
Embodiment 2:
(1), under nitrogen atmosphere, by 0.80gRAFT reagent, 5g methoxypolyethylene glycol methacrylic ester, 15g methyl acrylate, 0.10gAIBN, 55g phenylate join in the 100ml there-necked flask.At the temperature of 70 ℃, reaction 4h, precipitation obtains the macromolecular chain transfer agent.
(2) then get 1.6g macromolecular chain transfer agent, add 2.0g methacrylic acid perfluor sulfonyl amido ethyl ester, 0.01gAIBN, 10.2g butylacetate, at the temperature of 80 ℃, reaction 10h, obtain the amphipathic fluoride block copolymer resin.
Embodiment 3:
(1), under nitrogen atmosphere, by 0.63gRAFT reagent, 3.82g methoxypolyethylene glycol methacrylic ester, 10.8g methyl acrylate, 0.09gAIBN, 43.5g methyl-phenoxide join in the 100ml there-necked flask.At the temperature of 80 ℃, reaction 4h, precipitation obtains the macromolecular chain transfer agent.
(2) then get 1.2g macromolecular chain transfer agent, add 1.8g methacrylic acid perfluor sulfonyl amido ethyl ester, 0.009gAIBN, 9.5g butylacetate, at the temperature of 90 ℃, reaction 8h, obtain the amphipathic fluoride block copolymer resin.
Embodiment 4:
(1), under nitrogen atmosphere, by 0.69gRAFT reagent, 16g methoxypolyethylene glycol methacrylic ester, 4g methyl methacrylate, 0.10gAIBN, 46.7g dioxane join in the 100ml there-necked flask.At the temperature of 70 ℃, reaction 5h, precipitation obtains the macromolecular chain transfer agent.
(2) then get 1.6g macromolecular chain transfer agent, add 2.4g vinylformic acid perfluor sulfonyl amido ethyl ester, 0.012gAIBN, 12.7g butylacetate, at the temperature of 100 ℃, reaction 7h, obtain the amphipathic fluoride block copolymer resin.
Embodiment 5:
(1), under nitrogen atmosphere, by 0.69gRAFT reagent, 8g methoxypolyethylene glycol methacrylic ester, 12g methyl methacrylate, 0.10gAIBN, 46.7g phenylate join in the 100ml there-necked flask.At the temperature of 70 ℃, reaction 5h, precipitation obtains the macromolecular chain transfer agent.
(2) then get 0.8g macromolecular chain transfer agent, add 1.2g vinylformic acid perfluor sulfonyl amido ethyl ester, 0.006gAIBN, 6.3g butylacetate, at the temperature of 90 ℃, reaction 8h, obtain the amphipathic fluoride block copolymer resin.
Embodiment 6:
(1), under nitrogen atmosphere, by 0.34gRAFT reagent, 5g methoxypolyethylene glycol methacrylic ester, 5g methyl methacrylate, 0.05gAIBN, 23.3g methyl-phenoxide join in the 100ml there-necked flask.At the temperature of 70 ℃, reaction 5h, precipitation obtains the macromolecular chain transfer agent.
(2) then get 1.6g macromolecular chain transfer agent, add 2.4g vinylformic acid perfluor sulfonyl amido ethyl ester, 0.012gAIBN, 12.7g butylacetate, at the temperature of 100 ℃, reaction 7h, obtain the amphipathic fluoride block copolymer resin.
Embodiment 7: the surface contact angle that amphipathic multipolymer is filmed and surperficial energy
Using distilled water and n-hexadecane respectively as test liquid, the amphipathic multipolymer of preparation is filmed and carried out the mensuration of surface contact angle.The solution that amphipathic multipolymer is made into is spin-coated in substrate, sample to be tested is passed through to measure its static surface contact angle after anneal, table 1 has been listed the static contact angle of embodiment 1 to embodiment 6 each multipolymer to distilled water and n-hexadecane, can find out that filming of amphipathic multipolymer has very strong hydro-oleophobicity.The surface tension that each multipolymer is filmed 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-Hexadecanemean respectively the static contact angle of co-polymer membrane to water and n-hexadecane; γ S, γ S
dwith γ S
pthe surface tension, surface tension dispersion part and surface tension polar portion, wherein the γ S=γ S that mean respectively co-polymer membrane
d+ γ S
p.
Embodiment 8: the performance of amphipathic multipolymer resist coating film protein adsorption
After amphipathic multipolymer being prepared into to the solution of proper concn, be spin-coated in substrate, then carry out anneal.Above-mentioned multipolymer is filmed and put into the mixed phosphate salt buffer that contains bovine serum albumin and cultivate for some time, then at the fluorescence microscopy Microscopic observation, the number of the fluorescein by count tag on bovine serum albumin is probed into multipolymer and is filmed to the opposing absorption property of bovine serum albumin.
As shown in Figure 1, B and C are amphipathic copolymer sample (corresponding respectively to the sample of embodiment 2 in table 1 and 3), 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 suc as formula (1):
Formula (1)
Wherein, R=CH
3perhaps 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. the method for preparing amphipathic fluoride block copolymer claimed in claim 1, is characterized in that comprising the steps:
1) under 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 ℃, reaction 2～6h, precipitation obtains the macromolecular chain transfer agent;
The skeleton symbol of said RAFT reagent is suc as formula (2):
2) in the macromolecular chain transfer agent made in step 1), add fluorochemical monomer, Diisopropyl azodicarboxylate and solvent, 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 ℃, reaction 5～12 h, obtain the amphipathic fluoride block copolymer resin.
3. the preparation method of amphipathic fluoride block copolymer according to claim 1, 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 1, 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 1, is characterized in that described fluorochemical monomer is vinylformic acid perfluor sulfonyl amido ethyl ester, methacrylic acid perfluor sulfonyl amido ethyl ester, dodecafluoroheptyl methacrylate or Hexafluorobutyl mathacrylate.
6. the application of amphipathic fluoride block copolymer claimed in claim 1, is characterized in that as the base-material for preparing marine antifouling coating.
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