CN105017966A - OVPOSS crosslinking fluorinated and silicified block copolymer ultraviolet curing coating, preparation and application - Google Patents
OVPOSS crosslinking fluorinated and silicified block copolymer ultraviolet curing coating, preparation and application Download PDFInfo
- Publication number
- CN105017966A CN105017966A CN201510472264.1A CN201510472264A CN105017966A CN 105017966 A CN105017966 A CN 105017966A CN 201510472264 A CN201510472264 A CN 201510472264A CN 105017966 A CN105017966 A CN 105017966A
- Authority
- CN
- China
- Prior art keywords
- segmented copolymer
- polydimethylsiloxane
- ovposs
- sulfydryl
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(C)C(C)(CN)C(**C(*)(C(C(F)(F)F)F)F)=O Chemical compound CC(C)C(C)(CN)C(**C(*)(C(C(F)(F)F)F)F)=O 0.000 description 1
- FHBWGXDQIOWTCK-UHFFFAOYSA-N CCCC(C)C#N Chemical compound CCCC(C)C#N FHBWGXDQIOWTCK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides an OVPOSS crosslinking fluorinated and silicified block copolymer ultraviolet curing coating, preparation and application. The coating is composed of, by mass, 1-90% of polydimethylsiloxane-b-(polyfluoroalkyl acrylate)2 block copolymer with a mercapto group as the end group, 1-90% of thiol polysiloxane, 1-10% of OVPOSS and 0.05-1% of photoinitiator. The polydimethylsiloxane-b-(polyfluoroalkyl acrylate)2 block copolymer with the mercapto group as the end group, the thiol polysiloxane, the OVPOSS and the photoinitiator are dissolved in solvent to be prepared into a solution with mass fraction of 10% to 50%, the surface of a base plate is coated with the components through dropwise coating or spray coating or immerse coating or spin coating, dried at a room temperature and then cured for 10 min to 20 min under the irradiation of ultraviolet light, and then the OVPOSS crosslinking fluorinated and silicified block copolymer ultraviolet curing coating is obtained. The coating is applied to the field of hydrophobic and anti-icing coating materials.
Description
Technical field
The present invention relates to the crosslinked fluorine silicon segmented copolymer ultraviolet curable coating of a kind of eight vinyl polysilsesquioxanes (OVPOSS) and Synthesis and applications, belong to light solidifying coating preparation and hydrophobic, ice-covering-proof coated material field.
Background technology
The Cumulate Sum attachment of ice on Infrastructure surfaces such as aircraft, steamer, aerogenerators can bring harm to the life of the mankind and property.Ice-covering-proof coating, owing to having the features such as cost is low, energy consumption is little, easy to implement, is solve ice-covering-proof good method.Existing ice-covering-proof coating technology is reach ice-covering-proof effect by preparing super-hydrophobic coat mostly.But in wet environment, super hydrophobic surface will lose ultra-hydrophobicity, once super hydrophobic surface freezes, the interlocked sticking power that can increase between ice and coating of ice and coatingsurface, be unfavorable for ice-covering-proof effect (Chen.J, Liu.J, He.M on the contrary, Li.K, Cui.D, Zhang.Q, Zeng.X, Zhang.Y, Wang.J, Song.Y, Superhydrophobic surfaces cannot reduce ice adhesion.Applied PhysicsLetters, 2012,101:111603).
Different from super-hydrophobic coat, low surface energy hydrophobic coating surface roughness is relatively little, is Nano grade, and the interlocked that can effectively reduce between ice and coating is used.Common low surface energy hydrophobic coating comprises organic silicon coating and fluorine-containing coat.Organic silicon coating is usually based on organosiloxane polymer, this polymkeric substance has low second-order transition temperature, and siloxanes segment kindliness is good under cryogenic, can reduce the sticking power of ice at material surface, but it is weak to there is mechanical strength, the shortcoming of poor solvent resistance.Fluorine-containing coat has lower specific inductivity (such as polytetrafluorethylecoatings coatings specific inductivity is 2.1), the electrostatic force between coatingsurface and ice body can be reduced, the fluoro-containing group on fluorine-containing coat surface significantly can reduce the surface energy of coating simultaneously, improves the solvent resistance of coating.But the reactive force between research discovery fluorine-containing groups and water molecules is three times of siloxanes segment and water molecules reactive force, be unfavorable for the further reduction (Murase.H of coatingsurface ice sticking power, Fujibayashi.T, Characterization of molecular interfaces in hydrophobic systems, Progress in OrganicCoatings, 1997,31:97-104).
Fluorine silicon coating in conjunction with the advantage of organic silicon coating and fluorine-containing coat, both can keep the second-order transition temperature that organic silicon coating is lower, have again the feature of fluorine-containing coat low-k and low surface energy concurrently.In addition, fluorine element silicon also can produce fluorine silicon synergy in the enrichment of coatingsurface.Be conducive to reducing ice and the reactive force being coated with interlayer, improve the anti-icing performance (Murase.H of coatingsurface, Fujibayashi.T, Characterization ofmolecular interfaces in hydrophobic systems, Progress in Organic Coatings, 1997,31:97-104).Chinese patent CN 103709344A discloses a kind of preparation method of poly-fluoroalkyl-b-polysiloxane block copolymers, and gained segmented copolymer has good hydrophobicity.(Yuan Xiaoyan, Li Bo, Zhao Yunhui, Li Xiaohui.Crosslinkable gathers fluoroalkyl-b-polysiloxane and preparation method, and 2014).
Ultraviolet curable coating refers to a type coating of Quick cross-linking film-forming under ultraviolet light irradiation.Compare with heat-curable coating with traditional self-vulcanizing, ultraviolet curable coating has that curing speed is fast, energy consumption is low, film performance is excellent and the advantage such as environmental pollution is little, make its more and more concerned (Decker.C of application in coating curing field, Photoinitiated crosslinking polymerization.Progress in Polymer Science, 1996,21:593-650).
First the present invention prepares the polydimethylsiloxane-b-(poly-fluoroalkyl) that end group is sulfydryl
2then segmented copolymer is linking agent with OVPOSS, take end group as the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2segmented copolymer and sulfydryl polysiloxane are main ingredient, obtain fluorine silicon coating by the method for ultraviolet light polymerization.Owing to containing sulfydryl polysiloxane component in coating, can reduce coating use cost, the fluorine silicon coating film forming properties is simultaneously good, and have actual application value, up to the present associated viscera rarely has report.
Summary of the invention
A kind of OVPOSS is the object of the present invention is to provide to be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating and Synthesis and applications.Described ultraviolet curable coating curing speed is fast, and surface energy is low, and film forming properties is good, is applied to hydrophobic and ice-covering-proof coated material field.
The present invention is realized by the following technical programs, a kind of OVPOSS is cross-linked fluorine silicon segmented copolymer ultraviolet curable coating, it is characterized in that, by percentage to the quality, each component and mass content are (each constituent mass per-cent sum is 100%):
End group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2segmented copolymer: 1 ~ 90%;
Sulfydryl polysiloxane: 1 ~ 90%;
OVPOSS：1～10％；
Light trigger: 0.05 ~ 1%.
Each component preferred mass content is (each constituent mass per-cent sum is 100%):
End group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2segmented copolymer: 10 ~ 40%;
Sulfydryl polysiloxane: 50 ~ 80%;
OVPOSS：1～10％；
Light trigger: 0.05 ~ 1%.
Above-mentioned end group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2the molecular formula of segmented copolymer is:
M/n=0.02 ~ 1.6 in formula 1, molecular weight is 4000 ~ 70000;
R
ffor-CH
2cF
2cHFCF
3,-CH
2cF (CF
3) CFHCF (CF
3)
2,-CH
2cH
2(CF
2)
xcF
3in one, x is the integer of 5 or 7.
Above-mentioned sulfydryl polysiloxane molecule formula is:
P/q=10 ~ 50 in formula 2; Molecular weight is 2000 ~ 20000g/mol.
Above-mentioned OVPOSS molecular formula is:
Above-mentioned light trigger is 2,2-dimethoxy-2-phenyl acetophenone.
Above-mentioned end group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2the preparation method of segmented copolymer is as follows:
(1) preparation of polydimethylsiloxane (PDMS) macromole reversible addion-fragmentation chain transfer agent (CTA-PDMS-CTA):
Be that 2000-20000g/mol two hydroxyl-terminated injecting two methyl siloxane (HO-PDMS-OH), 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB), dicyclohexylcarbodiimide (DCC) and DMAP (DMAP) are according to mol ratio 1:(1 ~ 2 by molecular weight): (1 ~ 3): (0.2 ~ 0.8) is dissolved in q. s. methylene chloride; be configured to the solution that massfraction is 10 ~ 50%, react 10 ~ 48h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 10 ~ 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
(2) polydimethylsiloxane-b-(poly-fluoroalkyl)
2the preparation of segmented copolymer:
By fluorinated acrylate (one in Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems), CTA-PDMS-CTA and Diisopropyl azodicarboxylate (AIBN) according to mol ratio (20 ~ 200): (2 ~ 10): 1 is dissolved in phenylfluoroform, be configured to the solution that massfraction is 10 ~ 50%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath and react 6 ~ 20h at 65 ~ 80 DEG C.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 10 ~ 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(poly-fluoroalkyl)
2segmented copolymer, as shown in Equation 4:
M/n=0.02 ~ 1.6 in formula 4, molecular weight is 3000 ~ 70000;
R
ffor-CH
2cF
2cHFCF
3,-CH
2cF (CF
3) CFHCF (CF
3)
2,-CH
2cH
2(CF
2)
xcF
3in one, x is the integer of 5 or 7;
(3) end group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2the preparation of segmented copolymer
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(poly-fluoroalkyl)
2segmented copolymer is according to mol ratio (1 ~ 20): (1 ~ 10): 1 is dissolved in tetrahydrofuran (THF), is configured to the solution that massfraction is 10 ~ 50%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 1 ~ 8h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into vacuum drying oven drying 10 ~ 24h, obtain the polydimethylsiloxane-b-(poly-fluoroalkyl) that end group is sulfydryl
2segmented copolymer.
The preparation method that above-mentioned OVPOSS is cross-linked fluorine silicon segmented copolymer ultraviolet curable coating is as follows:
Be the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl by end group
2segmented copolymer, sulfydryl polysiloxane, OVPOSS and light trigger are dissolved in solvent by above-mentioned mass percent and are configured to the solution that massfraction is 10 ~ 50%, be coated with by dripping, spraying, dip-coating or spin coating mode be coated in substrate surface, surface drying under room temperature, then at UV-light (wavelength 365nm, power 2 ~ 10mW/cm
2) solidification 10 ~ 20 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
Above-mentioned OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating, and solvent for use is toluene, dimethylbenzene, phenylfluoroform, the one in tetrahydrofuran (THF).
Coating is hydrophobic and anti-icing performance test is as follows:
Hydrophobicity testing method: take deionized water as test liquid, with sessile drop method at optical contact angle determinator (JC2000D, upper marine morning plant and instrument company limited) the upper static contact angle measuring coating, during test, liquid volume used is 3 μ L, temperature is 25 ± 1 DEG C, and each sample test is averaged for 5 times.
Anti-icing performance testing method: utilize thruster method to test coatingsurface ice shearing resistance.By moistening for aluminium flake (2cm × 2cm) bottom surface of applying coating, be placed in cold bench.To be placed on aluminium flake by the glass cylinder of 1H, 1H, 2H, 2H-perfluoro capryl trichlorosilane process, in cylinder, inject 450 μ L deionized waters, water and coating layer touch area are S=78.5mm
2, on cold bench, place plexiglass tent, and pass into nitrogen protection, prevent the formation of frost.Cold bench is cooled to-15 DEG C with the speed of 2 DEG C/min, and is incubated 3h, guarantee the water freeze in cylinder.Be fixed on electric moveable platform by pull and push dynamometer (Japanese Imada ZP-500N pull and push dynamometer), push ahead test ice shearing force with the speed of 0.5mm/s, pull and push dynamometer probe not higher than 2mm, records maximum shear stress F with aluminium sheet height.Calculate the shearing resistance σ of ice.Often organize experiment and get 9-12 Duplicate Samples, calculate average shear strength.
Preparation OVPOSS described above is cross-linked fluorine silicon segmented copolymer ultraviolet curable coating, and this coatings applications is in hydrophobic and ice-covering-proof coated material field.
The crosslinked fluorine silicon segmented copolymer ultraviolet curable coating of one eight vinyl polysilsesquioxane (OVPOSS) that the present invention proposes and Synthesis and applications.This coating is linking agent with OVPOSS, take end group as the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2segmented copolymer and sulfydryl polysiloxane are main ingredient, are obtained by the method for ultraviolet light polymerization.Owing to containing organosilicon and fluorine-containing groups in coating, coating is made both to have maintained the lower second-order transition temperature of organic silicon coating, have again the feature of fluoropolymer low-k and low surface energy concurrently, be conducive to reducing the reactive force between coatingsurface and ice, reduce the sticking power of ice.Simultaneously due to organosilicon and fluorine-containing groups surface energy low, easily to coatingsurface migration, make coating have good hydrophobicity.Prepared light solidifying coating curing speed is fast, energy consumption is low, and film performance is excellent, has actual application value.
The invention has the advantages that: (1) OVPOSS is cross-linked the advantage that fluorine silicon segmented copolymer ultraviolet curable coating combines organic silicon coating and fluoropolymer coating, both the lower second-order transition temperature of organic silicon coating can have been maintained, have again the feature of fluoropolymer low-k and low surface energy concurrently, be conducive to reducing the reactive force between coatingsurface and ice, reduce the sticking power of ice.(2) organosilicon contained in coating and fluorine-containing groups are low due to surface energy, easily to coatingsurface migration, make coating can obtain good hydrophobicity.(3) the light solidifying coating curing speed prepared by is fast, energy consumption is low, and film performance is excellent, has actual application value.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific examples.
Embodiment 1:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 2000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:2:2:0.4 by molecular weight, be configured to the solution that massfraction is 10%.React 10h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 10h of vacuum drying oven, obtains CTA-PDMS-CTA.
Hexafluorobutyl mathacrylate, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 200:2:1, are configured to the solution that massfraction is 10%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 65 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 10h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 20:5:1, is configured to the solution that massfraction is 10%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 1h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 10h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=1.6 in formula, molecular weight is 25000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl
2segmented copolymer: 1%;
Sulfydryl polysiloxane: 90%;
OVPOSS：8％；
Light trigger: 1%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl by 0.1g end group
2segmented copolymer, 9g sulfydryl polysiloxane (molecular weight is 2000g/mol, p/q=10), 0.8g OVPOSS and 0.1g light trigger are dissolved in 90g toluene, are configured to the solution that massfraction is 10%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 2mW/cm by dripping painting mode
2) solidification 20 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 106.2 ± 0.3 °, and ice shearing resistance is 180 ± 15kPa.
Embodiment 2:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 20000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:1.5:2:0.2 by molecular weight, be configured to the solution that massfraction is 50%.React 48h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
Hexafluorobutyl mathacrylate, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 20:2:1, are configured to the solution that massfraction is 50%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 1:2:1, is configured to the solution that massfraction is 50%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 8h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.02 in formula, molecular weight is 22500.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl
2segmented copolymer: 80%;
Sulfydryl polysiloxane: 18.75%;
OVPOSS：1％；
Light trigger: 0.25%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl by 8g end group
2segmented copolymer, 1.875g sulfydryl polysiloxane (molecular weight is 20000g/mol, p/q=50), 0.1g OVPOSS and 0.025g light trigger are dissolved in 10g dimethylbenzene, are configured to the solution that massfraction is 50%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 5mW/cm by spin coating mode
2) solidification 15 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 105.1 ± 0.2 °, and ice shearing resistance is 220 ± 21kPa.
Embodiment 3:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 2000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:1:1:0.8 by molecular weight, be configured to the solution that massfraction is 30%.React 20h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 12h of vacuum drying oven, obtains CTA-PDMS-CTA.
Hexafluorobutyl mathacrylate, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 20:2:1, are configured to the solution that massfraction is 30%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 8h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 12h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 5:1:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 6h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 12h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.16 in formula, molecular weight is 4000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl
2segmented copolymer: 90%;
Sulfydryl polysiloxane: 1%;
OVPOSS：8.95％；
Light trigger: 0.05%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid hexafluoro butyl ester) of sulfydryl by 9g end group
2segmented copolymer, 0.1g sulfydryl polysiloxane (molecular weight is 10000g/mol, p/q=30), 0.895g OVPOSS and 0.005g light trigger are dissolved in 23.3g toluene, are configured to the solution that massfraction is 30%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 10mW/cm by spin coating mode
2) solidification 10 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 105.2 ± 0.3 °, and ice shearing resistance is 250 ± 16kPa.
Embodiment 4:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 10000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:2:3:0.5 by molecular weight, be configured to the solution that massfraction is 30%.React 30h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 18h of vacuum drying oven, obtains CTA-PDMS-CTA.
Dodecafluoroheptyl methacrylate, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 100:10:1, are configured to the solution that massfraction is 30%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 18h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 20:10:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 4h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 18h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.04 in formula, molecular weight is 14000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid ten difluoro heptyl ester) of sulfydryl
2segmented copolymer: 9.85%;
Sulfydryl polysiloxane: 80%;
OVPOSS：10％；
Light trigger: 0.15%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester) of sulfydryl by 0.985g end group
2segmented copolymer, 8g sulfydryl polysiloxane (molecular weight is 4000g/mol, p/q=15), 01g OVPOSS and 0.015g light trigger are dissolved in 40g phenylfluoroform, are configured to the solution that massfraction is 20%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 2mW/cm by spin coating mode
2) solidification 20 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 107.0 ± 0.5 °, and ice shearing resistance is 170 ± 20kPa.
Embodiment 5:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 4000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:1.5:3:0.2 by molecular weight, be configured to the solution that massfraction is 30%.React 32h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
Dodecafluoroheptyl methacrylate, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 200:2:1, are configured to the solution that massfraction is 30%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 1:2:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 5h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=1 in formula, molecular weight is 42000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid ten difluoro heptyl ester) of sulfydryl
2segmented copolymer: 40%;
Sulfydryl polysiloxane: 50%;
OVPOSS：9％；
Light trigger: 1%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid ten difluoro heptyl ester) of sulfydryl by 4g end group
2segmented copolymer, 5g sulfydryl polysiloxane (molecular weight is 4000g/mol, p/q=15), 0.9g OVPOSS and 0.1g light trigger are dissolved in 30g tetrahydrofuran (THF), are configured to the solution that massfraction is 25%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 2mW/cm by dip coating manner
2) solidification 20 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 107.2 ± 0.1 °, and ice shearing resistance is 180 ± 18kPa.
Embodiment 6:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 10000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:2:2:0.4 by molecular weight, be configured to the solution that massfraction is 20%.React 32h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
Methacrylic acid ten trifluoro monooctyl ester, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 100:5:1, are configured to the solution that massfraction is 30%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 75 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 1:2:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 5h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.08 in formula, molecular weight is 15000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid ten trifluoro monooctyl ester) of sulfydryl
2segmented copolymer: 34.5%;
Sulfydryl polysiloxane: 60%;
OVPOSS：5％；
Light trigger: 0.25%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester) of sulfydryl by 3.45g end group
2segmented copolymer, 6g sulfydryl polysiloxane (molecular weight is 4000g/mol, p/q=15), 0.5g OVPOSS and 0.025g light trigger are dissolved in 10g tetrahydrofuran (THF), are configured to the solution that massfraction is 50%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 3mW/cm by spraying method
2) solidification 15 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 106.5 ± 0.2 °, and ice shearing resistance is 200 ± 15kPa.
Embodiment 7:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 4000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:1.5:2:0.4 by molecular weight, be configured to the solution that massfraction is 20%.React 32h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
Methacrylic acid ten trifluoro monooctyl ester, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 50:5:1, are configured to the solution that massfraction is 50%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 1:2:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 5h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.1 in formula, molecular weight is 7000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid ten trifluoro monooctyl ester) of sulfydryl
2segmented copolymer: 16%;
Sulfydryl polysiloxane: 80%;
OVPOSS：3％；
Light trigger: 1%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid ten trifluoro monooctyl ester) of sulfydryl by 1.6g end group
2segmented copolymer, 8g sulfydryl polysiloxane (molecular weight is 10000g/mol, p/q=30), 0.3g OVPOSS and 0.1g light trigger are dissolved in 40g tetrahydrofuran (THF), are configured to the solution that massfraction is 20%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 2mW/cm by dripping painting mode
2) solidification 20 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 107.3 ± 0.3 °, and ice shearing resistance is 180 ± 15kPa.
Embodiment 8:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 20000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:1.5:2:0.4 by molecular weight, be configured to the solution that massfraction is 20%.React 32h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
Methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 200:2:1, are configured to the solution that massfraction is 50%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 80 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 1:2:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 5h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.2 in formula, molecular weight is 70000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) of sulfydryl
2segmented copolymer: 10%;
Sulfydryl polysiloxane: 80%;
OVPOSS：9％；
Light trigger: 1%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) of sulfydryl by 1g end group
2segmented copolymer, 8g sulfydryl polysiloxane (molecular weight is 10000g/mol, p/q=30), 0.9g OVPOSS and 0.1g light trigger are dissolved in 10g tetrahydrofuran (THF), are configured to the solution that massfraction is 10%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 2mW/cm by dripping painting mode
2) solidification 15 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 118.1 ± 0.2 °, and ice shearing resistance is 160 ± 12kPa.
Embodiment 9:
(1) end group is the polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) of sulfydryl
2the preparation of segmented copolymer
Be that two hydroxyl-terminated injecting two methyl siloxanes of 10000g/mol, 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are dissolved in methylene dichloride according to mol ratio 1:1.5:2:0.4 by molecular weight, be configured to the solution that massfraction is 20%.React 32h under nitrogen protection.Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 24h of vacuum drying oven, obtains CTA-PDMS-CTA.
Methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, CTA-PDMS-CTA and Diisopropyl azodicarboxylate are dissolved in phenylfluoroform according to mol ratio 100:10:1, are configured to the solution that massfraction is 50%, join in Schlenk bottle, then get rid of oxygen.Schlenk pipe is put into constant temperature oil bath at 80 DEG C, reacts 10h.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems)
2segmented copolymer.
By hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems)
2segmented copolymer is dissolved in tetrahydrofuran (THF) according to mol ratio 1:2:1, is configured to the solution that massfraction is 30%, joins in there-necked flask.At room temperature, stirred under nitrogen atmosphere reaction 5h.After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) that end group is sulfydryl
2segmented copolymer, its structural formula is:
M/n=0.04 in formula, molecular weight is 14000.
(2) OVPOSS is cross-linked the preparation of fluorine silicon segmented copolymer ultraviolet curable coating
Polydimethylsiloxane-the b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) of sulfydryl
2segmented copolymer: 1%;
Sulfydryl polysiloxane: 90%;
OVPOSS：8％；
Light trigger: 0.1%;
Be the polydimethylsiloxane-b-(polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems) of sulfydryl by 0.1g end group
2segmented copolymer, 9g sulfydryl polysiloxane (molecular weight is 10000g/mol, p/q=30), 0.8g OVPOSS and 0.01g light trigger are dissolved in 30g tetrahydrofuran (THF), are configured to the solution that massfraction is 25%.Aluminium flake surface is coated in, surface drying under room temperature, then at ultraviolet (wavelength 365nm, power 2mW/cm by spin coating mode
2) solidification 15 minutes under irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
The contact of gained coatingsurface water is 118.0 ± 0.1 °, and ice shearing resistance is 180 ± 15kPa.
Claims (10)
1. an OVPOSS is cross-linked fluorine silicon segmented copolymer ultraviolet curable coating; It is characterized in that, in mass, each component and mass percentage content as follows:
End group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2segmented copolymer: 1 ~ 90%;
Sulfydryl polysiloxane: 1 ~ 90%;
OVPOSS：1～10％；
Light trigger: 0.05 ~ 1%.
2. an OVPOSS is cross-linked fluorine silicon segmented copolymer ultraviolet curable coating; It is characterized in that, in mass, each component and mass percentage content as follows:
End group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2segmented copolymer: 10 ~ 40%;
Sulfydryl polysiloxane: 50 ~ 80%;
OVPOSS：1～10％；
Light trigger: 0.05 ~ 1%.
3. light solidifying coating as claimed in claim 1 or 2; It is characterized in that described end group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2the structural formula of segmented copolymer is:
M/n=0.02 ~ 1.6 in formula, molecular weight is 4000 ~ 70000;
R
ffor-CH
2cF
2cHFCF
3,-CH
2cF (CF
3) CFHCF (CF
3)
2,-CH
2cH
2(CF
2)
xcF
3in one, x is the integer of 5 or 7.
4. light solidifying coating as claimed in claim 1 or 2; It is characterized in that described sulfydryl polysiloxane structure formula is:
P/q=10 ~ 50 in formula; Molecular weight is 2000 ~ 20000g/mol.
5. light solidifying coating as claimed in claim 1 or 2; It is characterized in that described OVPOSS structural formula is:
6. light solidifying coating as claimed in claim 1 or 2; It is characterized in that described light trigger is 2,2-dimethoxy-2-phenyl acetophenone.
7. the preparation method of light solidifying coating as claimed in claim 1 or 2; It is characterized in that being the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl by end group
2segmented copolymer, sulfydryl polysiloxane, OVPOSS and light trigger are dissolved in by mass percentage in solvent and are configured to the solution that massfraction is 10 ~ 50%, be coated with by dripping, spraying, dip-coating or spin coating mode be coated in substrate surface, surface drying under room temperature, then solidify 10 ~ 20 minutes under ultraviolet light irradiation, obtain OVPOSS and be cross-linked fluorine silicon segmented copolymer ultraviolet curable coating.
8. method as claimed in claim 7, is characterized in that solvent for use is the one in toluene, dimethylbenzene, phenylfluoroform or tetrahydrofuran (THF).
9. method as claimed in claim 7, is characterized in that the end group stated used is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2the preparation method of segmented copolymer is as follows:
(1) preparation of polydimethylsiloxane macromer reversible addion-fragmentation chain transfer agent:
Be that 2000-20000g/mol two hydroxyl-terminated injecting two methyl siloxane (HO-PDMS-OH), 4-cyano group-4-(thiobenzoyl) valeric acid, dicyclohexylcarbodiimide and DMAP are according to mol ratio 1:(1 ~ 2 by molecular weight): (1 ~ 3): (0.2 ~ 0.8) is dissolved in methylene dichloride, be configured to the solution that massfraction is 10 ~ 50%, react 10 ~ 48h under nitrogen protection; Reaction terminates rear crude product with methanol and precipitates and be separated, and finally puts into the dry 10 ~ 24h of vacuum drying oven, obtains CTA-PDMS-CTA;
(2) polydimethylsiloxane-b-(poly-fluoroalkyl)
2the preparation of segmented copolymer:
By fluorinated acrylate, CTA-PDMS-CTA and Diisopropyl azodicarboxylate (AIBN) according to mol ratio (20 ~ 200): (2 ~ 10): 1 is dissolved in phenylfluoroform, be configured to the solution that massfraction is 10 ~ 50%, join in Schlenk bottle, then get rid of oxygen; Schlenk pipe is put into constant temperature oil bath and react 6 ~ 20h at 65 ~ 80 DEG C.Reaction terminates rear crude product with methanol precipitation, finally product is put into the dry 10 ~ 24h of vacuum drying oven, obtains polydimethylsiloxane-b-(poly-fluoroalkyl)
2segmented copolymer:
(3) end group is the polydimethylsiloxane-b-(poly-fluoroalkyl) of sulfydryl
2the preparation of segmented copolymer: by hydrazine hydrate, dimethylphenylphosphine and polydimethylsiloxane-b-(poly-fluoroalkyl)
2segmented copolymer is according to mol ratio (1 ~ 20): (1 ~ 10): 1 is dissolved in tetrahydrofuran (THF), is configured to the solution that massfraction is 10 ~ 50%, joins in there-necked flask; At room temperature, stirred under nitrogen atmosphere reaction 1 ~ 8h; After reaction terminates, crude product is poured in methyl alcohol and precipitates, then put into vacuum drying oven drying 10 ~ 24h, obtain the polydimethylsiloxane-b-(poly-fluoroalkyl) that end group is sulfydryl
2segmented copolymer.
10.OVPOSS is cross-linked fluorine silicon segmented copolymer ultraviolet curable coating for hydrophobic, ice-covering-proof material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510472264.1A CN105017966B (en) | 2015-08-04 | 2015-08-04 | OVPOSS is crosslinked fluorine silicon block copolymer ultraviolet curable coating and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510472264.1A CN105017966B (en) | 2015-08-04 | 2015-08-04 | OVPOSS is crosslinked fluorine silicon block copolymer ultraviolet curable coating and preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105017966A true CN105017966A (en) | 2015-11-04 |
| CN105017966B CN105017966B (en) | 2017-06-16 |
Family
ID=54408282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510472264.1A Expired - Fee Related CN105017966B (en) | 2015-08-04 | 2015-08-04 | OVPOSS is crosslinked fluorine silicon block copolymer ultraviolet curable coating and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105017966B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061770A (en) * | 2015-08-10 | 2015-11-18 | 广东博兴新材料科技有限公司 | Organic fluorine-silicon light-cured resin and preparation method therefor and application thereof |
| CN106674451A (en) * | 2016-12-09 | 2017-05-17 | 境洁环保科技（上海）有限公司 | Fluorosilicone epoxy and polystyrene tetrablock polymer and preparation method thereof |
| US9914848B1 (en) | 2016-10-31 | 2018-03-13 | Ppg Architectural Finishes, Inc. | Refinish coating composition |
| CN111825840A (en) * | 2020-06-23 | 2020-10-27 | 湖北航天化学技术研究所 | Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method |
| CN111892819A (en) * | 2020-02-17 | 2020-11-06 | 杭州师范大学 | Preparation method and application of UV (ultraviolet) curing transparent material |
| CN112831053A (en) * | 2021-02-24 | 2021-05-25 | 烟台大学 | Reactive organosilicon release agent and preparation method thereof |
| CN114891226A (en) * | 2022-05-11 | 2022-08-12 | 广东工业大学 | Ceramic precursor slurry for photocuring 3D printing, preparation method thereof and ceramization method |
| CN117343565A (en) * | 2023-12-05 | 2024-01-05 | 北京特思迪半导体设备有限公司 | Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403249A (en) * | 2008-11-17 | 2009-04-08 | 金勇云 | Anti-crack type energy-saving covering layer used for building exterior wall surface |
| CN103748179A (en) * | 2011-08-31 | 2014-04-23 | 陶氏环球技术有限责任公司 | Solar reflectance coating |
| CN104277713A (en) * | 2014-09-11 | 2015-01-14 | 天津大学 | Preparation method and hydrophobic anti-icing application of POSS (polyhedral oligomeric silsesquioxane) crosslinking modified fluorine-silicon coating |
-
2015
- 2015-08-04 CN CN201510472264.1A patent/CN105017966B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403249A (en) * | 2008-11-17 | 2009-04-08 | 金勇云 | Anti-crack type energy-saving covering layer used for building exterior wall surface |
| CN103748179A (en) * | 2011-08-31 | 2014-04-23 | 陶氏环球技术有限责任公司 | Solar reflectance coating |
| CN104277713A (en) * | 2014-09-11 | 2015-01-14 | 天津大学 | Preparation method and hydrophobic anti-icing application of POSS (polyhedral oligomeric silsesquioxane) crosslinking modified fluorine-silicon coating |
Non-Patent Citations (2)
| Title |
|---|
| AIZHAO PAN ET AL: "POSS-tethered fluorinated diblock copolymers with linear- and star-shaped topologies: synthesis, self-asseembled films and hydrophobic applications", 《RSC ADVANCES》 * |
| HUI LI ET AL.: "Icephobicity of polydimethylsiloxane-b-poly(fluorinated acrylate)", 《THIN SOLID FILMS》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061770A (en) * | 2015-08-10 | 2015-11-18 | 广东博兴新材料科技有限公司 | Organic fluorine-silicon light-cured resin and preparation method therefor and application thereof |
| CN105061770B (en) * | 2015-08-10 | 2017-08-04 | 广东博兴新材料科技有限公司 | A kind of organic fluorinated silicone light-cured resin and its preparation method and application |
| US9914848B1 (en) | 2016-10-31 | 2018-03-13 | Ppg Architectural Finishes, Inc. | Refinish coating composition |
| US10358573B2 (en) | 2016-10-31 | 2019-07-23 | Ppg Architectural Finishes, Inc. | Refinish coating composition |
| CN106674451A (en) * | 2016-12-09 | 2017-05-17 | 境洁环保科技（上海）有限公司 | Fluorosilicone epoxy and polystyrene tetrablock polymer and preparation method thereof |
| CN111892819A (en) * | 2020-02-17 | 2020-11-06 | 杭州师范大学 | Preparation method and application of UV (ultraviolet) curing transparent material |
| CN111825840A (en) * | 2020-06-23 | 2020-10-27 | 湖北航天化学技术研究所 | Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method |
| CN111825840B (en) * | 2020-06-23 | 2022-04-22 | 湖北航天化学技术研究所 | Sulfydryl-containing fluorosilicone resin, UV (ultraviolet) photocuring super-hydrophobic protective coating and preparation method |
| CN112831053A (en) * | 2021-02-24 | 2021-05-25 | 烟台大学 | Reactive organosilicon release agent and preparation method thereof |
| CN112831053B (en) * | 2021-02-24 | 2022-04-29 | 烟台大学 | Reactive organosilicon release agent and preparation method thereof |
| CN114891226A (en) * | 2022-05-11 | 2022-08-12 | 广东工业大学 | Ceramic precursor slurry for photocuring 3D printing, preparation method thereof and ceramization method |
| CN114891226B (en) * | 2022-05-11 | 2023-08-15 | 广东工业大学 | Photo-curing 3D-printed ceramic precursor slurry, preparation method thereof and ceramic method |
| CN117343565A (en) * | 2023-12-05 | 2024-01-05 | 北京特思迪半导体设备有限公司 | Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof |
| CN117343565B (en) * | 2023-12-05 | 2024-02-13 | 北京特思迪半导体设备有限公司 | Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105017966B (en) | 2017-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105017966A (en) | OVPOSS crosslinking fluorinated and silicified block copolymer ultraviolet curing coating, preparation and application | |
| Yu et al. | Highly stable amphiphilic organogel with exceptional anti-icing performance | |
| Zheng et al. | Magnetic responsive and flexible composite superhydrophobic photothermal film for passive anti-icing/active deicing | |
| Liu et al. | Strategies for anti-icing: low surface energy or liquid-infused? | |
| Tao et al. | Formation of zwitterionic coatings with an aqueous lubricating layer for antifogging/anti-icing applications | |
| CN104277713B (en) | The preparation method of a kind of POSS cross-linking modified fluorine silicon coating and hydrophobic anti-icing application | |
| Liu et al. | Design and preparation of a multi-fluorination organic superhydrophobic coating with high mechanical robustness and icing delay ability | |
| CN106519968B (en) | A kind of ice-covering-proof coating and its preparation method and application of low ice adhesion | |
| Li et al. | Preparation and icephobic properties of polymethyltrifluoropropylsiloxane–polyacrylate block copolymers | |
| WO2016037403A1 (en) | Fluorinated poss composite organosilicon coating, preparation method and anti-icing application | |
| CN105131835B (en) | UV-cured POSS fluorine-containing acrylate segmented copolymer coating, preparation and application thereof | |
| Huang et al. | Preparation and characterization of silica/fluorinated acrylate copolymers hybrid films and the investigation of their icephobicity | |
| CN105315888B (en) | The cold curing fluorine silicon coating and preparation method and application of the cage-type silsesquioxane containing fluorination | |
| CN104987803B (en) | Anti-freeze ionic liquid gel film and preparation method thereof | |
| WO2015109466A1 (en) | Methods for preparing aqueous ice-covering resistant mono-component hybrid coating and coating layer thereof, and use thereof | |
| Li et al. | An extreme‐environment‐resistant self‐healing anti‐icing coating | |
| Li et al. | One-pot synthesis of superhydrophobic photothermal materials with self-healing for efficient ice removal | |
| CN108641593A (en) | A kind of preparation method of the durable organosilicon ice-covering-proof coating of " two-step method " lubricity | |
| WO2015100753A1 (en) | Two-component aqueous coating and coating layer with wear-resistance, low ice adhesiveness and anti-icing, and preparation method and use thereof | |
| CN102149667B (en) | Fluorine-based compounds and coating compositions comprising the same | |
| Jiang et al. | Strong mechanical and durable superhydrophobic photothermal MWCNTs/SiO2/PDMS/PVDF composite coating for anti-icing and de-icing | |
| CN107298906B (en) | High-weather-resistance anti-icing protective coating and preparation method thereof | |
| CN101555385B (en) | Water-reducible silicone coating and preparation method thereof | |
| Esfahani et al. | Transparent hydrophobic, self-cleaning, anti-icing and anti-dust nano-structured silica based thin film on cover glass solar cell | |
| CN103725199A (en) | Addition fluorinated silicone rubber nano antifreezing adhesive paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170616 Termination date: 20210804 |