CN105131835B - UV-cured POSS fluorine-containing acrylate segmented copolymer coating, preparation and application thereof - Google Patents
UV-cured POSS fluorine-containing acrylate segmented copolymer coating, preparation and application thereof Download PDFInfo
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- CN105131835B CN105131835B CN201510472230.2A CN201510472230A CN105131835B CN 105131835 B CN105131835 B CN 105131835B CN 201510472230 A CN201510472230 A CN 201510472230A CN 105131835 B CN105131835 B CN 105131835B
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Abstract
The invention provides a UV-cured POSS fluorine-containing acrylate segmented copolymer coating, preparation and application thereof. The coating is composed of the following components in percentage by weight: 1 to 30% of PMAPOSS-b-polyfluoroalkyl acrylate segmented copolymer with mercapto end groups, 30 to 50% of vinyl polysiloxane, 30 to 50% of mercapto polysiloxane, and 1 to 6% of photo-initiator. The preparation method comprises the following steps: dissolving PMAPOSS-b-polyfluoroalkyl acrylate segmented copolymer with mercapto end groups, mercapto polysiloxane, vinyl polysiloxane and photo-initiator into a solvent to prepare a solution with a mass concentration of 10 to 50%, painting the solution on the surface of a substrate, drying the substrate surface at a room temperature, and then curing the substrate surface under UV radiation for 10 to 30 minutes so as to obtain a UV-cured POSS fluorine-containing acrylate segmented copolymer composite organic silicon coating. The prepared light-cured coating has the advantages of quick curing speed, high transparency, good hydrophobicity, and low ice shearing strength, and can be applied to the field of hydrophobic and anti-icing coating.
Description
Technical field
The present invention relates to a kind of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating and system
Standby and application, belongs to hydrophobic anti-icing and applied technical field.
Background technology
In fields such as Aero-Space, power communication, communications and transportation, the surface icing of matrix gives people class and society brings great
Harm and economic loss.Although traditional physics deicing method (such as mechanical deicing, heating deicing) and chemical deicing method (sprinkling salt
Water, add freezing agent) etc. extensive utilization, but there are the problems such as low, the pollution environment of efficiency.Build in matrix surface anti-
The method of icing functional coating, low cost, power consumption are little, easy to implement, with great using value.
Fluorine material relies on its extremely low surface energy, relatively low dielectric constant, and can significantly reduce between coating and ice
The performance such as interaction force, be widely used in the preparation of ice-covering-proof coating.Sojoudi etc. using chemical vapor deposition method
Bilayer is formed in silicon chip or surface of steel plate, lower floor is polydivinylbenezene, upper strata is the fluorine last of the ten Heavenly stems ester of polyacrylic acid 17, silicon chip
185.3kPa and 158.5kPa are respectively with the ice addisive strength of surface of steel plate coating, ice addisive strength significantly reduces (Sojoudi
H,McKinley G H,Gleason K K.Linker-free grafting of fluorinated polymeric
cross-linked network bilayers for durable reduction of ice adhesion.Materials
Horizons,2015,2(1),91-99).Chinese patent (speed, Li Yan, Hu Mingjie, Zhao Yuming, Liu Xinghai, Li little Lin, Huang Rong by Huang
China, Luo Yunbai. a kind of ice-covering-proof coating and preparation method thereof .CN102205680B, 2014) disclose a kind of ice-covering-proof compound painting
Layer, altogether comprising three layers, internal layer is modifying epoxy resin by organosilicon layer, and intermediate layer is polyelectrolyte salt deposit, and outer layer is fluorinated silicone modified
Acrylate layer.
Polyhedral oligomeric silsesquioxane (POSS) is that a class has nano molecular size and hybrid inorganic-organic structure
Compound.It is this with the framework that constitutes without switch as core, the special construction that periphery is surrounded by organic substituent gives its unique
Physical property and chemical reactivity.Meuler etc. by polyethyl methacrylate and 17 fluorine decyl POSS (F-POSS) with
Mass ratio is 80:20 blendings, and surface of steel plate is spun on, its surface ice addisive strength is 165kPa, and contact angle hysteresis is 5.6 °,
Show as preferable ice-covering-proof property (Meuler A J, Smith J D, Varanasi K K, Mabry J M, McKinley G
H,Cohen R E.Relationships between water wettability and ice adhesion.ACS
Applied Material Interfaces,2010,2(11):3100-3110).The present inventor's early stage is with functionalization POSS
Crosslinking agent, based on fluoroalkylpolysiloxane and vinyl polysiloxane, constructs the fluorine silicon tree with surface micro-nano structure
Fat coating, ice adhesive force be decreased obviously (Yuan Xiaoyan, Luo Cheng Hao, Tao Chao, Zhu Kongying, Zhao Yunhui, Li Xiaohui. a kind of POSS crosslinking
The preparation method of modified fluoro-silicone coating and hydrophobic anti-icing application .CN104277713A, 2015).
Ultraviolet light (UV) curing technology is to cause the low molecule performed polymer or oligomer in coating using the energy of ultraviolet light
And as the chain polymerization and cross-linking reaction between the monomer molecule of reactive diluent.Compared to conventional curing technology, UV solidifications
Technology possesses solidification rapidly, and solidification quality is high, and operating cost is low, and required storage area is little, the advantage such as clean and effective.For example, in
State's patent (section Jingjing. a kind of hydrophobic ultraviolet-cured paint .CN 103666207A, 2014) disclose a kind of employing photocuring
Mode, using silane-modified resin so that institute has hydrophobic method into paint film.Sulfydryl-alkene click-reaction is produced because of solidification
The features such as rate is high, oxygen inhibition effect is little, becomes a kind of UV curing method for receiving much concern.Goswami etc. utilizes sulfydryl-alkene
Reaction carries out polysiloxanes and sulfydryl polysiloxanes that vinyl is contained at two ends photocured cross-linked.The polysiloxanes bullet for being generated
Gonosome has relatively low viscous loss, with high resiliency (Goswami K, Skov A L, Daugaard A E.UV-cured,
platinum-free,soft poly(dimethylsiloxane)networks.Chemistry European Journal,
2014,20(30),9230-9233).Additionally, Xue etc. that side chain is contained the polysiloxanes of vinyl, sulfydryl polysiloxanes is gentle
Aerosil is blended, and the method using ultraviolet light polymerization is cross-linked to form silicon rubber.As a result show, the silicon rubber of generation has
Good mechanical performance and heat endurance (Xue L, Zhang Y, Zuo Y, Diao S, Zhang J, Feng,
S.Preparation and characterization of novel UV-curing silicone rubber via
thiol-ene reaction.Materials Letters,2013,106,425-427)。
At present, eight summits have been applied for the fluorination POSS of organic fluoride-containing group at ice-covering-proof aspect, Chinese patent (Yuan
Dawn swallow, Li Bo, Zhao Yunhui, Li Xiaohui. cross-linking poly- fluoroalkyl-b- polysiloxanes and preparation method .CN
103709344A, 2014) also discloses a kind of with reversible addion-fragmentation chain transfer (RAFT) polymerization fluorine of the synthesis containing POSS blocks
The method of silica acrylic acid ester block copolymer, and using the preparation with hydrophobic ice-phobic coating.But with POSS fluorinated acrylates two
Block copolymer as active additive, with strand two ends and side chain all polysiloxanes containing vinyl and the poly- silica of sulfydryl
Alkane has no relevant report as the case that the main body of photocuring obtains ice-covering-proof coating.This patent synthesizes end with RAFT polymerizations
Base is embedding for the poly- fluoroalkyls of polymethyl acyloxy isobutyl group oligomeric silsesquioxane (PMAPOSS)-b- of sulfydryl
Section copolymer.Then with vinyl polysiloxane, sulfydryl polysiloxanes to be crosslinked main component, by the method for ultraviolet light polymerization
Obtain coating.So far related content is rarely reported.
The content of the invention
The purpose of the present invention aims to provide a kind of ultraviolet light polymerization POSS fluorine-containing ester block copolymers and is compounded with machine
Silicon coating and preparation and application.Described coating surface has micro phase separation structure, and has certain roughness, its preparation method
Process is simple, and raw material is easy to get, and reaction condition is gentle, controllable, can be used for hydrophobic, ice-covering-proof material.
The present invention realized by the following technical programs, a kind of ultraviolet light polymerization POSS fluorinated acrylate blocks
Copolymer composite organic coating, it is characterised in that by mass percentage (each component mass percent sum is 100%),
Each component and mass content are：
End group is the poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl：1～30%；
Vinyl polysiloxane：30～50%；
Sulfydryl polysiloxanes：30～50%；
Light trigger：1～6%；
Described end group is that the molecular formula of the poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl is：
Wherein m/n=0.1～2；Molecular weight is 6000～35000g/mol.
RfFor-CH2CF(CF3)CFHCF(CF3)2、-CH2CH2(CF2)5CF3Or-CH2CH2(CF2)7CF3；
Described sulfydryl polysiloxanes, it is characterised in that sulfydryl polysiloxane molecule formula is：
Wherein p/q=10～20；Molecular weight is 3000～6000g/mol.
Described vinyl polysiloxane, it is characterised in that the molecular formula of vinyl polysiloxane is：
Wherein, a/b=10～20, molecular weight is 10000～20000g/mol.
Described light trigger is 2,2- dimethoxys -2- phenyl acetophenones (DMPA).
Above-mentioned end group is as follows for the preparation method of the poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl：
(1) preparation of PMAPOSS can adopt (Deng Y, Bernard J, Alcouffe P, Galy J, Dai L, G é
rard,J.F.Nanostructured hybrid polymer networks from in situ self-assembly of
RAFT-synthesized POSS-based block copolymers.Journal of Polymer Science Part
A:Polymer Chemistry,2011,49(20):It is prepared by following method 4343-4352)：
Weigh methacryloxy isobutyl group oligomeric silsesquioxane (MAPOSS) monomer, chain-transferring agent 4- cyano group -4-
(thio benzoyl) valeric acid (CPADB) and initiator azodiisobutyronitrile (AIBN), according to mol ratio (10～30):(2～10):
1 is completely dissolved in toluene solvant, is configured to 20%～50% solution, the protection of then air in emptying bottle, and nitrogen.60℃
Magnetic agitation reaction 5h～24h under the conditions of～80 DEG C of oil baths；Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating,
Unreacted monomer and solvent are removed, room temperature in vacuo is dried 24h, obtains PMAPOSS copolymers.
(2) preparation of the poly- fluoroalkyl block copolymers of PMAPOSS-b-：
By fluorinated acrylate (dodecafluoroheptyl methacrylate, the trifluoro monooctyl ester of methacrylic acid ten or metering system
One kind in sour 17 fluorine last of the ten Heavenly stems esters), PMAPOSS and azodiisobutyronitrile (AIBN) be according to mol ratio (20～100):(2～10):
1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 10%～50%, in being added to Schlenk bottles, then emptying bottle
Interior air, and nitrogen protection.Schlenk pipes are put into in constant temperature oil bath 6～24h of reaction at 65 DEG C～80 DEG C.Reaction terminates
Product is added drop-wise in a large amount of methyl alcohol is afterwards precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h.
(3) end group is the preparation of the poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl：
By the poly- fluoroalkyl block copolymer of hydrazine hydrate, 3,5-dimethylphenyl phosphorus and PMAPOSS-b- according to mol ratio
(10～30):(1～10):1 is dissolved in tetrahydrofuran, is made into the solution that mass fraction is 10%～50%, and fast under room temperature
Fast 1～5h of strong agitation.Reacted product adds excessive methanol extraction.Then room temperature in vacuo is dried 24h, obtains end group and is
The poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl.
(4) preparation method of above-mentioned ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings
It is as follows：
By the poly- fluoroalkyl block copolymers of PMAPOSS-b-, sulfydryl polysiloxanes, ethene that end group is sulfydryl
Based polysiloxane and light trigger are dissolved in solvent by above-mentioned mass percent, and it is 10%～50% to be configured to mass concentration
Solution, is coated in substrate surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, 2～10mW/cm of power2) under irradiation
10～30min of solidification, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
Above-mentioned ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating, solvent for use is trifluoro
One kind in toluene, dichloromethane, chloroform and tetrahydrofuran；Painting method can using drop coating, using spin coating instrument spin coating,
Spraying or dip-coating etc..
(5) test of water contact angle, contact angle hysteresis and ice shear strength
The wetability numerical value such as contact angle using contact angle tester testing coating, contact angle tester model
JC2000D, it is delayed using water contact angle is determined with depletion method；
Ice shearing force testing is carried out to coating using side pushing manipulation.Test process is as follows：Every group of sample takes five, is positioned over cold
On platform, the hollow glass cylinder (internal diameter 8mm) that hydrophobic treatment is crossed is positioned over coated center position, instills 450 μ L ultra-pure waters.If
Temperature control program is put with the speed of 10 DEG C/min and be cooled to -15 DEG C and keep temperature 3h.Using pull and push dynamometer test from starting to connect
Tactile cylinder pushed away from the maximum of the power between coating surface to cylinder.Pull and push dynamometer model ZP-500N, side pushes away speed for 1
～10cm/min, five samples are averaged.
A kind of ultraviolet light polymerization POSS fluoroalkyls block copolymer composite organic coating disclosed by the invention
And prepare and apply.End group is the poly- fluorine of polymethyl acyloxy isobutyl group oligomeric silsesquioxane (PMAPOSS)-b- of sulfydryl
Alkyl acrylic ester block copolymer is realized using reversible addion-fragmentation chain transfer (RAFT) polymerization.With the poly- silicon of vinyl
Oxygen alkane, sulfydryl polysiloxanes are crosslinking key component, and by the method for ultraviolet light polymerization coating is obtained.Unique cage type knot of POSS
Structure, the less surface energy of fluoroalkyl so that the poly- fluoroalkyl block copolymers of PMAPOSS-b- easily to
Coating surface is migrated, and is conducive to forming micro phase separation structure on surface, gives the certain roughness of coating surface and pattern, is strengthened
The adhesive force of surface hydrophobic and reduction ice.Silicone backbone is submissive, and surface energy is low, film forming ability is strong.Therefore, using the method
Prepared light solidifying coating solidification is rapid, energy consumption is low, and the transparency is good, and with relatively low surface energy, good hydrophobicity and
Relatively low ice shear strength, can be applicable to hydrophobic, ice-phobic coating field.
It is an advantage of the current invention that：(1) polymethyl acyloxy isobutyl group oligomeric silsesquioxane (PMAPOSS)-b-
Poly- fluoroalkyl block copolymer is easy to surface migration, and because thermodynamics incompatibility between two blocks can be in table
Face forms micro phase separation structure.(2) organosilicon has low temperature elasticity for the coating of key component, and low-surface-energy has coating
There is good hydrophobicity.(3) the light solidifying coating solidification prepared by is simple efficiently, environmental protection and economy, and film performance is excellent, tool
There is actual application value.
Description of the drawings
The contact angle schematic diagram of the photocuring POSS fluorinated acrylate block copolymer coatings of Fig. 1 embodiments 5, water contact angle
Reach 105.5 ± 0.5 °.
The contact angle schematic diagram of the photocuring POSS fluorinated acrylate block copolymer coatings of Fig. 2 embodiments 8, water contact angle
Reach 116.0 ± 1.5 °.
Specific embodiment
Technical scheme is further illustrated with reference to instantiation.
Embodiment 1：
(1) end group is the preparation of the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten of sulfydryl
Weigh 0.40g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.008g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 10:2:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 20% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 10h under the conditions of 70 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
0.80g dodecafluoroheptyl methacrylates, 0.40g PMAPOSS and 2.2mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 40:2:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 50%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 6h at 65 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten.
By 10 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and the difluoro heptyl ester of 0.40g PMAPOSS-b- polymethylacrylic acid ten
Block copolymer is according to mol ratio 30:1:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 5h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(15000) m/n=0.1, molecular weight is to the difluoro heptyl ester of PMAPOSS-b- polymethylacrylic acid ten：1%；
Vinyl polysiloxane (a/b=10, molecular weight 10000)：47%；
Sulfydryl polysiloxanes (p/q=15, molecular weight 4500)：50%；
Light trigger：2%；
Film mode：Spin coating；
By the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten, 0.01g light that 0.01g end groups are sulfydryl
During initiator (DMPA) is completely dissolved in benzotrifluoride, 0.47g vinyl polysiloxanes, the poly- silica of 0.50g sulfydryls are subsequently adding
Alkane, continuously adds solvent and is made into the mixed solution that concentration is 30%.5s 3000r/min rotations again are revolved by spin coating mode 600r/min
10s is coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 2.5mW/cm2) solidify under irradiation
10min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 103.0 ± 1.0 °, and it is 19.5 ± 0.5 ° that water contact angle is delayed, and ice shear strength is
170.5±8.5kPa。
Embodiment 2：
(1) end group is the preparation of the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten of sulfydryl
Weigh 0.40g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.02g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 10:5:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 30% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 20h under the conditions of 60 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
1.00g dodecafluoroheptyl methacrylates, 0.80g PMAPOSS and 2.20mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 50:4:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 10h at 70 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten.
3 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and the difluoro heptyl ester of 0.40g PMAPOSS-b- polymethylacrylic acid ten is embedding
Section copolymer is according to mol ratio 10:1:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 30%, is added to three
In mouth bottle.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum drying oven
24h is dried, the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten that end group is sulfydryl is obtained, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(14000) m/n=1, molecular weight is to the difluoro heptyl ester of PMAPOSS-b- polymethylacrylic acid ten：5%；
Vinyl polysiloxane (a/b=15, molecular weight 15000)：45%；
Sulfydryl polysiloxanes (p/q=15, molecular weight 4500)：49%；
Light trigger：1%；
Film mode：Spin coating；
By the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten, 0.02g light that 0.05g end groups are sulfydryl
During initiator (DMPA) is completely dissolved in tetrahydrofuran solvent, 0.45g vinyl polysiloxanes are subsequently adding, 0.48g sulfydryls gather
Siloxanes, continuously adds solvent and is made into the mixed solution that concentration is 20%.5s 3000r/ again are revolved by spin coating mode 600r/min
Min rotation 10s are coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 2.5mW/cm2) under irradiation
Solidification 10min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 104.7 ± 1.5 °, and it is 17.0 ± 1.0 ° that water contact angle is delayed, and ice shear strength is
165.0±10.0kPa。
Embodiment 3：
(1) end group is the preparation of the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten of sulfydryl
Weigh 0.80g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.04g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 20:10:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 50% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 20h under the conditions of 70 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
2.00g dodecafluoroheptyl methacrylates, 2.00g PMAPOSS and 2.21mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 100:10:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles,
Then air in emptying bottle, and nitrogen is protected.Schlenk pipes are put in constant temperature oil bath and react 6h at 70 DEG C.Reaction terminates
Product is added drop-wise in a large amount of methyl alcohol is afterwards precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten.
By 30 μ l hydrazine hydrates, 40 μ l dimethylphenylphosphines and the difluoro heptyl ester of 0.40g PMAPOSS-b- polymethylacrylic acid ten
Block copolymer is according to mol ratio 30:10:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten that end group is sulfydryl, and its structure is
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(6000) m/n=0.3, molecular weight is to the difluoro heptyl ester of PMAPOSS-b- polymethylacrylic acid ten：30%；
Vinyl polysiloxane (a/b=10, molecular weight 10000)：35%；
Sulfydryl polysiloxanes (p/q=10, molecular weight 3000)：30%；
Light trigger：5%；
Film mode：Dip-coating；
By the difluoro heptyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten, 0.05g light that 0.30g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of tetrahydrofuran, is subsequently adding 0.35g ethene
Based polysiloxane, 0.30g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 50%.By dip-coating side
Formula is coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 5mW/cm2) solidify under irradiation
20min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 105.0 ± 1.2 °, and it is 15.0 ± 1.0 ° that water contact angle is delayed, and ice shear strength is
155.0±15.0kPa。
Embodiment 4：
(1) end group is the preparation of the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten of sulfydryl
Weigh 0.80g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.04g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 20:10:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 50% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 20h under the conditions of 70 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
The trifluoro monooctyl ester of 0.43g methacrylic acids ten, 0.40g PMAPOSS and 2.21mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 20:2:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 30%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 24h at 65 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten.
By 30 μ l hydrazine hydrates, 40 μ l dimethylphenylphosphines and the trifluoro monooctyl ester of 0.40g PMAPOSS-b- polymethylacrylic acid ten
Block copolymer is according to mol ratio 30:10:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(14000) m/n=1, molecular weight is to the trifluoro monooctyl ester of PMAPOSS-b- polymethylacrylic acid ten：20%；
Vinyl polysiloxane (a/b=15, molecular weight 15000)：30%；
Sulfydryl polysiloxanes (p/q=20, molecular weight 6000)：47%；
Light trigger：3%；
Film mode：Spraying；
By the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten, 0.03g light that 0.20g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of dichloromethane, is subsequently adding 0.30g ethene
Based polysiloxane, 0.47g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 30%.By spraying side
Formula is coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 6mW/cm2) solidify under irradiation
20min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 106.0 ± 1.2 °, and it is 16.2 ± 1.3 ° that water contact angle is delayed, and ice shear strength is
145.0±12.0kPa。
Embodiment 5：
(1) end group is the preparation of the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten of sulfydryl
Weigh 0.40g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.008g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 10:2:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 20% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 10h under the conditions of 70 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
The trifluoro monooctyl ester of 1.08g methacrylic acids ten, 0.80g PMAPOSS and 2.2mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 50:4:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 10h at 70 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten.
By 30 μ l hydrazine hydrates, 20 μ l dimethylphenylphosphines and the trifluoro monooctyl ester of 0.40g PMAPOSS-b- polymethylacrylic acid ten
Block copolymer is according to mol ratio 30:5:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(14000) m/n=1, molecular weight is to the trifluoro monooctyl ester of PMAPOSS-b- polymethylacrylic acid ten：30%；
Vinyl polysiloxane (a/b=15, molecular weight 15000)：40%；
Sulfydryl polysiloxanes (p/q=20, molecular weight 6000)：28%；
Light trigger：2%；
Film mode：Spin coating；
By the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten, 0.02g light that 0.30g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of tetrahydrofuran, is subsequently adding 0.40g ethene
Based polysiloxane, 0.28g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 30%.By spin coating side
Again 3000r/min rotations 10s is coated in aluminum flake surface to formula 600r/min rotation 5s, then in ultraviolet light (wavelength 365nm, power 5mW/
cm2) solidify 30min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 105.5 ± 0.5 °, and it is 13.2 ± 0.5 ° that water contact angle is delayed, and ice shear strength is
130.5±10.2kPa。
Embodiment 6：
(1) end group is the preparation of the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten of sulfydryl
Weigh 1.20g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.02g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 30:5:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 30% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 20h under the conditions of 60 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
The trifluoro monooctyl ester of 0.86g methacrylic acids ten, 0.80g PMAPOSS and 2.21mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 40:4:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 12h at 70 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten.
By 30 μ l hydrazine hydrates, 20 μ l dimethylphenylphosphines and the trifluoro monooctyl ester of 0.40g PMAPOSS-b- polymethylacrylic acid ten
Block copolymer is according to mol ratio 30:5:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(23000) m/n=2, molecular weight is to the trifluoro monooctyl ester of PMAPOSS-b- polymethylacrylic acid ten：5%；
Vinyl polysiloxane (a/b=15, molecular weight 15000)：50%；
Sulfydryl polysiloxanes (p/q=15, molecular weight 4500)：39%；
Light trigger：6%；
Film mode：Drop coating；
By the trifluoro monooctyl ester block copolymer of PMAPOSS-b- polymethylacrylic acid ten, 0.06g light that 0.05g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of chloroform, is subsequently adding 0.50g ethene
Based polysiloxane, 0.39g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 40%.By drop coating side
Formula is coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 2.5mW/cm2) solidify under irradiation
15min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 104.5 ± 1.0 °, and it is 17.0 ± 1.0 ° that water contact angle is delayed, and ice shear strength is
160.0±8.5kPa。
Embodiment 7：
(1) end group is the preparation of the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17 of sulfydryl
Weigh 0.80g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.02g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 20:5:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 30% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 20h under the conditions of 80 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
The fluorine last of the ten Heavenly stems ester of 0.54g methacrylic acids 17,0.48g PMAPOSS and 2.70mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 20:2:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 10h at 80 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17.
By 30 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and the fluorine last of the ten Heavenly stems ester of 0.40g PMAPOSS-b- polymethylacrylic acid 17
Block copolymer is according to mol ratio 30:1:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17 that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(35000) m/n=0.7, molecular weight is to the fluorine last of the ten Heavenly stems ester of PMAPOSS-b- polymethylacrylic acid 17：10%；
Vinyl polysiloxane (a/b=10, molecular weight 10000)：45%；
Sulfydryl polysiloxanes (p/q=10, molecular weight 3000)：43%；
Light trigger：2%；
Film mode：Spin coating；
By the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17,0.02g light that 0.10g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of tetrahydrofuran, is subsequently adding 0.45g ethene
Based polysiloxane, 0.43g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 30%.By spin coating side
Again 3000r/min rotations 10s is coated in aluminum flake surface to formula 600r/min rotation 5s, surface drying under room temperature, then in ultraviolet light (wavelength
365nm, power 8mW/cm2) solidify 15min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containings ester block copolymer and answer
Close organic silicon coating.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 116.0 ± 1.0 °, and it is 9.2 ± 1.5 ° that water contact angle is delayed, and ice shear strength is
130.6±12.0kPa。
Embodiment 8：
(1) end group is the preparation of the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17 of sulfydryl
Weigh 0.60g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.008g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 15:2:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 50% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 10h under the conditions of 70 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
The fluorine last of the ten Heavenly stems ester of 0.54g methacrylic acids 17,0.48g PMAPOSS and 2.70mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 20:2:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 10h at 80 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17.
By 30 μ l hydrazine hydrates, 8 μ l dimethylphenylphosphines and the fluorine last of the ten Heavenly stems ester of 0.40g PMAPOSS-b- polymethylacrylic acid 17
Block copolymer is according to mol ratio 30:2:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17 that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(20000) m/n=0.5, molecular weight is to the fluorine last of the ten Heavenly stems ester of PMAPOSS-b- polymethylacrylic acid 17：5%；
Vinyl polysiloxane (a/b=20, molecular weight 20000)：50%；
Sulfydryl polysiloxanes (p/q=10, molecular weight 3000)：42%；
Light trigger：3%；
Film mode：Spin coating；
By the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17,0.03g light that 0.05g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of tetrahydrofuran, is subsequently adding 0.50g ethene
Based polysiloxane, 0.42g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 30%.By spin coating side
Formula is coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 2.5mW/cm2) solidify under irradiation
15min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 116.0 ± 1.5 °, and it is 8.0 ± 1.0 ° that water contact angle is delayed, and ice shear strength is
104.0±9.0kPa。
Embodiment 9：
(1) end group is the preparation of the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17 of sulfydryl
Weigh 0.80g MAPOSS monomers, chain-transferring agent 4- cyano group -4- (thio benzoyl) valeric acid (CPADB) 0.02g and
Initiator azodiisobutyronitrile (AIBN) 1.63mg, according to mol ratio 20:5:1 is completely dissolved in toluene solvant, is configured to matter
Amount fraction is 30% solution, and then air in emptying bottle, and nitrogen is protected.Magnetic agitation reaction 20h under the conditions of 80 DEG C of oil baths；
Product is added drop-wise in a large amount of methyl alcohol and is precipitated by reaction after terminating, and removes unreacted monomer and solvent, and room temperature in vacuo is dried
24h, obtains PMAPOSS copolymers.
The fluorine last of the ten Heavenly stems ester of 0.54g methacrylic acids 17,0.48g PMAPOSS and 2.70mg azodiisobutyronitriles (AIBN) are pressed
According to mol ratio 20:2:1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 40%, in being added to Schlenk bottles, so
Air in heel row white vase, and nitrogen protection.Schlenk pipes are put in constant temperature oil bath and react 10h at 80 DEG C.After reaction terminates
Product is added drop-wise in a large amount of methyl alcohol and is precipitated, remove unreacted monomer and solvent, room temperature in vacuo is dried 24h, obtains
The fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17.
By 30 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and the fluorine last of the ten Heavenly stems ester of 0.40g PMAPOSS-b- polymethylacrylic acid 17
Block copolymer is according to mol ratio 30:1:1 is dissolved in tetrahydrofuran, is configured to the solution that mass fraction is 10%, is added to
In there-necked flask.Reaction 3h is stirred at room temperature.Crude product is poured in methyl alcohol and is precipitated by reaction after terminating, and is then placed in vacuum baking
Case is dried 24h, obtains the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17 that end group is sulfydryl, its structural formula
For
(2) preparation of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating
(20000) m/n=0.5, molecular weight is to the fluorine last of the ten Heavenly stems ester of PMAPOSS-b- polymethylacrylic acid 17：30%；
Vinyl polysiloxane (a/b=20, molecular weight 20000)：34%；
Sulfydryl polysiloxanes (p/q=10, molecular weight 3000)：30%；
Light trigger：6%；
Film mode：Spraying；
By the fluorine last of the ten Heavenly stems ester block copolymer of PMAPOSS-b- polymethylacrylic acid 17,0.06g light that 0.30g end groups are sulfydryl
Initiator (DMPA) is completely dissolved in benzotrifluoride and (1w/1w) in the mixed solvent of tetrahydrofuran, is subsequently adding 0.34g ethene
Based polysiloxane, 0.30g sulfydryl polysiloxanes continuously adds solvent and is made into the mixed solution that concentration is 30%.By spraying side
Formula is coated in aluminum flake surface, surface drying under room temperature, then in ultraviolet light (wavelength 365nm, power 5mW/cm2) solidify under irradiation
30min, obtains ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coatings.
(3) water contact angle, contact angle hysteresis and ice shear strength test
Jing testing coatings water contact angle is 116.0 ± 0.5 °, and it is 8.0 ± 1.0 ° that water contact angle is delayed, and ice shear strength is
160.5±7.5kPa。
A kind of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic that the present invention is disclosed and proposed
Coating and preparation and application, those skilled in the art can pass through to use for reference the link realizations such as present disclosure, appropriate change condition route,
Although the method for the present invention and technology of preparing are described by preferred embodiment, person skilled substantially can be not
Depart from and in present invention, spirit and scope methods and techniques described herein route is modified or is reconfigured, come real
Now final technology of preparing.Specifically, all similar replacements and change for a person skilled in the art
It is it will be apparent that they are considered as being included in spirit of the invention, scope and content.
Claims (8)
1. a kind of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating；Characterized in that, each group
Divide and mass percentage content is：
End group is the poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl：1～30%；
Vinyl polysiloxane：30～50%；
Sulfydryl polysiloxanes：30～50%；
Light trigger：1～6%；
The end group is that the structural formula of the poly- fluoroalkyl block copolymers of PMAPOSS-b- of sulfydryl is：
Wherein m/n=0.1～2；Molecular weight is 6000～35000g/mol；RfFor-CH2CF(CF3)CFHCF(CF3)2、-CH2CH2
(CF2)5CF3Or-CH2CH2(CF2)7CF3。
2. coating as claimed in claim 1, is characterized in that described sulfydryl polysiloxane structure formula is：
Wherein p/q=10～20；Molecular weight is 3000～6000g/mol.
3. coating as claimed in claim 1, is characterized in that described vinyl polysiloxane structural formula is：
Wherein, a/b=10～20, molecular weight is 10000～20000g/mol.
4. coating as claimed in claim 1, is characterized in that described light trigger is 2,2- dimethoxy -2- phenyl benzene second
Ketone.
5. a kind of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating system as claimed in claim 1
Preparation Method, is characterized in that：By the poly- fluoroalkyl block copolymers of PMAPOSS-b-, the poly- silica of sulfydryl that end group is sulfydryl
Alkane, vinyl polysiloxane and light trigger are dissolved in by mass percentage in solvent, be configured to mass concentration for 10%～
50% solution, is coated in substrate surface, surface drying under room temperature, and 10～30min is then solidified under ultraviolet light irradiation, obtains ultraviolet
Photocuring POSS fluorine-containing ester block copolymer composite organic coatings.
6. method as claimed in claim 5, is characterized in that the poly- fluoroalkyls of PMAPOSS-b- that end group is sulfydryl are embedding
Section copolymer preparation method be：The poly- fluoroalkyl block of hydrazine hydrate, dimethylphenylphosphine and PMAPOSS-b- is total to
Polymers is according to mol ratio (10～30):(1～10):1 is dissolved in tetrahydrofuran, be made into mass fraction be 10%～50% it is molten
Quick 1～5h of strong agitation under liquid, and room temperature；Reacted product adds excessive methanol extraction；Then room temperature in vacuo is dried
24h, obtains the poly- fluoroalkyl block copolymers of PMAPOSS-b- that end group is sulfydryl.
7. method as claimed in claim 6, is characterized in that the system of the poly- fluoroalkyl block copolymers of PMAPOSS-b-
Preparation Method is：By fluorinated acrylate, PMAPOSS and azodiisobutyronitrile (AIBN) according to mol ratio (20～100):(2～
10):1 is dissolved in benzotrifluoride, is configured to the solution that mass fraction is 10～50%, in being added to Schlenk bottles, then removes
Oxygen；6～20h of reaction at 65～80 DEG C is put in constant temperature oil bath；Product adds excessive methanol precipitation after reaction；Then will produce
Thing is put in vacuum drying oven and is dried 24 hours, obtains the poly- fluoroalkyl block copolymers of PMAPOSS-b-；Fluorine-containing propene
Acid esters is dodecafluoroheptyl methacrylate, the trifluoro monooctyl ester of methacrylic acid ten, the fluorine last of the ten Heavenly stems ester one of which of methacrylic acid 17.
8. a kind of ultraviolet light polymerization POSS fluorine-containings ester block copolymer composite organic coating as claimed in claim 1
As the application of ice-covering-proof material.
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| 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 |
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