CN105131835A - 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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- CN105131835A CN105131835A CN201510472230.2A CN201510472230A CN105131835A CN 105131835 A CN105131835 A CN 105131835A CN 201510472230 A CN201510472230 A CN 201510472230A CN 105131835 A CN105131835 A CN 105131835A
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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-containing ester block copolymer composite organic coating and Synthesis and applications, belong to hydrophobic anti-icing and applied technical field.
Background technology
In fields such as aerospace, power communication, communications and transportation, the surperficial icing of matrix brings significant damage and financial loss to the mankind and society.Although traditional physics deicing method (as mechanical deicing, heating deicing) and chemical deicing method (spray salt solution, add freezing agent) etc. extensively use, there are the problems such as efficiency is low, contaminate environment.Build the method for freezing functional coating at matrix surface, cost is low, consume energy little, easy to implement, there is great using value.
Fluorine material relies on its extremely low surface energy, lower specific inductivity, and significantly can reduce the performances such as the interaction force between coating and ice, is widely used in the preparation of ice-covering-proof coating.Sojoudi etc. adopt the method for chemical vapour deposition to form bilayer at silicon chip or surface of steel plate, lower floor is polydivinylbenezene, upper strata is polyacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, the ice addisive strength of silicon chip and surface of steel plate coating is respectively 185.3kPa and 158.5kPa, ice addisive strength significantly reduces (SojoudiH, McKinleyGH, GleasonKK.Linker-freegraftingoffluorinatedpolymericcross-linkednetworkbilayersfordurablereductionoficeadhesion.Ma terialsHorizons, 2015, 2 (1), 91-99).Chinese patent (speed, Li Yan, Hu Mingjie by Huang, Zhao Yuming, Liu Xinghai, Li little Lin, yellow high honour, Luo Yunbai. a kind of ice-covering-proof coating and preparation method thereof .CN102205680B, 2014) disclose a kind of ice-covering-proof compound coating, comprise three layers altogether, internal layer is modifying epoxy resin by organosilicon layer, middle layer is polyelectrolyte salt deposit, and skin is fluorinated silicone modified acrylate layer.
Polyhedral oligomeric silsesquioxane (POSS) is the compound that a class has nano molecular size and hybrid inorganic-organic structure.This with the framework formed without switch for core, peripheral the special construction that surrounds by organic substituent, give physical properties and the chemical reactivity of its uniqueness.Polyethyl methacrylate and 17 fluorine decyl POSS (F-POSS) are that 80:20 is blended with mass ratio by Meuler etc., and be spun on surface of steel plate, its surperficial ice addisive strength is 165kPa, contact angle hysteresis is 5.6 °, show as good ice-covering-proof property (MeulerAJ, SmithJD, VaranasiKK, MabryJM, McKinleyGH, CohenRE.Relationshipsbetweenwaterwettabilityandiceadhesi on.ACSAppliedMaterialInterfaces, 2010,2 (11): 3100-3110).The present inventor early stage with functionalization POSS for linking agent, with fluoroalkylpolysiloxane and vinyl polysiloxane for matrix, construct the fluorine silicon resin coating with surface micro-nano structure, ice sticking power obviously declines (Yuan Xiaoyan, Luo Cheng Hao, Tao Chao, Zhu Kongying, Zhao Yunhui, Li Xiaohui. the preparation method of a kind of POSS cross-linking modified fluorine silicon coating and hydrophobic anti-icing application .CN104277713A, 2015).
UV-light (UV) curing technology be utilize the energy of UV-light cause low molecule performed polymer in coating or oligomer and as reactive thinner monomer molecule between chain polymerization and crosslinking reaction.Compared to conventional curing technology, UV curing technology has solidification rapidly, and solidification quality is high, and running cost is low, and required storage area is little, the advantages such as clean and effective.Such as, Chinese patent (section Jingjing. a kind of hydrophobic ultraviolet-cured paint .CN103666207A, 2014) disclose a kind of mode adopting photocuring, utilize silane-modified resin, make become paint film have hydrophobic method.Sulfydryl-alkene click-reaction, because of features such as solidification productive rate are high, oxygen inhibition effect is little, becomes a kind of UV curing method received much concern.Goswami etc. utilize sulfydryl-alkene reaction two ends to be contained the polysiloxane of vinyl and sulfydryl polysiloxane carries out photocured cross-linked.The silicone elastomer generated has lower viscous loss, there is snappiness (GoswamiK, SkovAL, DaugaardAE.UV-cured, platinum-free, softpoly (dimethylsiloxane) networks.ChemistryEuropeanJournal, 2014,20 (30), 9230-9233).In addition, it is blended that side chain is contained the polysiloxane of vinyl, sulfydryl polysiloxane and aerosil by Xue etc., and adopt the method for ultraviolet light polymerization to be cross-linked to form silicon rubber.Result shows, the silicon rubber generated has good mechanical property and thermostability (XueL, ZhangY, ZuoY, DiaoS, ZhangJ, Feng, S.PreparationandcharacterizationofnovelUV-curingsilicone rubberviathiol-enereaction.MaterialsLetters, 2013,106,425-427).
At present, eight summits are that the POSS that fluoridizes of organic fluoride-containing group applies in ice-covering-proof, Chinese patent (Yuan Xiaoyan, Li Bo, Zhao Yunhui, Li Xiaohui. crosslinkable gathers fluoroalkyl-b-polysiloxane and preparation method .CN103709344A, and 2014) also disclose a kind of method containing the fluorine silica acrylic acid ester block copolymer of POSS block with reversible addion-fragmentation chain transfer (RAFT) polymerization synthesis, and apply the preparation with hydrophobic ice-phobic coating.But using POSS fluorinated acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock as active additive, all contain the case that the polysiloxane of vinyl and sulfydryl polysiloxane obtain ice-covering-proof coating as the main body of photocuring using molecular chain two ends and side chain and have no relevant report.Polymethyl acyloxy isobutyl-oligomeric silsesquioxane (the PMAPOSS)-b-that this patent is sulfydryl with RAFT polymerization process synthesis end group gathers fluoroalkyl segmented copolymer.Then with vinyl polysiloxane, sulfydryl polysiloxane for crosslinked main component, obtain coating by the method for ultraviolet light polymerization.Associated viscera rarely has report so far.
Summary of the invention
Object of the present invention aims to provide a kind of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating and Synthesis and applications.Described coatingsurface has micro phase separation structure, and has certain roughness, and its preparation method process is simple, and raw material is easy to get, and reaction conditions is gentle, controlled, can be used for hydrophobic, ice-covering-proof material.
The present invention is realized by the following technical programs, a kind of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating, it is characterized in that, by mass percentage (each constituent mass per-cent sum is 100%), each component and mass content are:
End group is that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer: 1 ~ 30%;
Vinyl polysiloxane: 30 ~ 50%;
Sulfydryl polysiloxane: 30 ~ 50%;
Light trigger: 1 ~ 6%;
Described end group is the molecular formula that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer:
Wherein m/n=0.1 ~ 2; Molecular weight is 6000 ~ 35000g/mol.
R
ffor-CH
2cF (CF
3) CFHCF (CF
3)
2,-CH
2cH
2(CF
2)
5cF
3or-CH
2cH
2(CF
2)
7cF
3;
Described sulfydryl polysiloxane, is characterized in that, sulfydryl polysiloxane molecule formula is:
Wherein p/q=10 ~ 20; Molecular weight is 3000 ~ 6000g/mol.
Described vinyl polysiloxane, is characterized 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-dimethoxy-2-phenyl acetophenone (DMPA).
It is as follows that above-mentioned end group is that the PMAPOSS-b-of sulfydryl gathers the preparation method of fluoroalkyl segmented copolymer:
(1) preparation of PMAPOSS can adopt (DengY, BernardJ, AlcouffeP, GalyJ, DaiL, G é rard, J.F.Nanostructuredhybridpolymernetworksfrominsituself-as semblyofRAFT-synthesizedPOSS-basedblockcopolymers.Journa lofPolymerSciencePartA:PolymerChemistry, 2011,49 (20): 4343-4352) following method preparation:
Take methacryloxy isobutyl-oligomeric silsesquioxane (MAPOSS) monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) and initiator Diisopropyl azodicarboxylate (AIBN); according to mol ratio (10 ~ 30): (2 ~ 10): 1 is fully dissolved in toluene solvant; be mixed with the solution of 20% ~ 50%; then air in emptying bottle, and nitrogen protection.60 DEG C ~ 80 DEG C oil bath condition lower magnetic force stirring reaction 5h ~ 24h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
(2) PMAPOSS-b-gathers the preparation of fluoroalkyl segmented copolymer:
By fluorinated acrylate (one in dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems), PMAPOSS and Diisopropyl azodicarboxylate (AIBN) according to mol ratio (20 ~ 100): (2 ~ 10): 1 is dissolved in phenylfluoroform; be configured to the solution that massfraction is 10% ~ 50%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath and react 6 ~ 24h at 65 DEG C ~ 80 DEG C.After reaction terminates, product is added drop-wise in a large amount of methyl alcohol and precipitates, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo.
(3) end group is the preparation that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer:
Hydrazine hydrate, 3,5-dimethylphenyl phosphorus and PMAPOSS-b-are gathered fluoroalkyl segmented copolymer according to mol ratio (10 ~ 30): (1 ~ 10): 1 is dissolved in tetrahydrofuran (THF), be made into the solution that massfraction is 10% ~ 50%, and quick violent stirring 1 ~ 5h under room temperature.Reacted product adds excessive methanol extraction.Then the dry 24h of room temperature in vacuo, obtaining end group is that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer.
(4) preparation method of above-mentioned ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating is as follows:
Be that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer, sulfydryl polysiloxane, vinyl polysiloxane and light trigger and is dissolved in solvent by above-mentioned mass percent by end group, be configured to the solution that mass concentration is 10% ~ 50%, be coated in substrate surface, surface drying under room temperature, then at UV-light (wavelength 365nm, power 2 ~ 10mW/cm
2) solidification 10 ~ 30min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
Above-mentioned ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating, solvent for use is the one in phenylfluoroform, methylene dichloride, trichloromethane and tetrahydrofuran (THF); Coating method can adopt a painting, utilize the spin coating of spin coating instrument, spraying or dip-coating etc.
(5) test of water contact angle, contact angle hysteresis and ice shearing resistance
Utilize the wettability numerical value such as the contact angle of contact angle tester testing coating, contact angle tester model is JC2000D, utilizes with depletion method mensuration water contact angle delayed;
Thruster method is utilized to carry out ice shearing force testing to coating.Test process is as follows: often organize sample and get five, be positioned in cold bench, the hollow glass cylinder (internal diameter 8mm) hydrophobic treatment crossed is positioned over coated center position, instills 450 μ L ultrapure waters.Arrange temperature control program be cooled to-15 DEG C with the speed of 10 DEG C/min and keep this temperature 3h.Utilize pull and push dynamometer test from contact cylinder to pushed away from the power coatingsurface maximum value to cylinder.Pull and push dynamometer model is ZP-500N, and thruster speed is 1 ~ 10cm/min, and five samples are averaged.
A kind of ultraviolet light polymerization POSS fluoroalkyl segmented copolymer composite organic coating disclosed by the invention and Synthesis and applications.End group is that polymethyl acyloxy isobutyl-oligomeric silsesquioxane (the PMAPOSS)-b-of sulfydryl gathers the realization of fluoroalkyl segmented copolymer employing reversible addion-fragmentation chain transfer (RAFT) polymerization process.With vinyl polysiloxane, sulfydryl polysiloxane for crosslinked main ingredient, obtain coating by the method for ultraviolet light polymerization.Unique cage structure of POSS, the surface energy that fluoroalkyl is less, make PMAPOSS-b-gather fluoroalkyl segmented copolymer easily to move to coatingsurface, be conducive to forming micro phase separation structure on surface, give the certain roughness of coatingsurface and pattern, strengthen surface hydrophobicity and the sticking power of reduction ice.Silicone backbone is submissive, and surface energy is low, film forming ability is strong.Therefore, the light solidifying coating solidification of employing prepared by the method is rapid, energy consumption is low, and the transparency is good, and has lower surface energy, good hydrophobicity and lower ice shearing resistance, can be applicable to hydrophobic, ice-phobic coating field.
The invention has the advantages that: (1) polymethyl acyloxy isobutyl-oligomeric silsesquioxane (PMAPOSS)-b-gathers fluoroalkyl segmented copolymer and is easy to surface transport, and micro phase separation structure can be formed on surface due to thermodynamics uncompatibility between two blocks.(2) organosilicon is that the coating of main ingredient has low temperature elasticity, low surface energy, makes coating have good hydrophobicity.(3) the light solidifying coating solidification prepared by is simple efficient, environmental protection and economy, and film performance is excellent, has actual application value.
Accompanying drawing explanation
The contact angle schematic diagram of Fig. 1 embodiment 5 photocuring POSS fluorinated acrylate block copolymer coating, water contact angle reaches 105.5 ± 0.5 °.
The contact angle schematic diagram of Fig. 2 embodiment 8 photocuring POSS fluorinated acrylate block copolymer coating, water contact angle reaches 116.0 ± 1.5 °.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific examples.
Embodiment 1:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer of sulfydryl
Take 0.40gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.008g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 10:2:1; be mixed with the solution that massfraction is 20%; then air in emptying bottle, and nitrogen protection.70 DEG C of oil bath condition lower magnetic force stirring reaction 10h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
0.80g dodecafluoroheptyl methacrylate, 0.40gPMAPOSS and 2.2mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 40:2:1; be configured to the solution that massfraction is 50%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 65 DEG C, reacts 6h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer.
10 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer are dissolved in tetrahydrofuran (THF) according to mol ratio 30:1:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 5h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester (m/n=0.1, molecular weight is 15000): 1%;
Vinyl polysiloxane (a/b=10, molecular weight 10000): 47%;
Sulfydryl polysiloxane (p/q=15, molecular weight 4500): 50%;
Light trigger: 2%;
Film mode: spin coating;
Be that PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer, the 0.01g light trigger (DMPA) of sulfydryl is fully dissolved in phenylfluoroform by 0.01g end group, then 0.47g vinyl polysiloxane is added, 0.50g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 30%.By spin coating mode 600r/min revolve 5s again 3000r/min revolve 10s and be coated in aluminium flake surface, surface drying under room temperature, then at UV-light (wavelength 365nm, power 2.5mW/cm
2) solidify 10min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 103.0 ± 1.0 ° after tested, and water contact angle is delayed is 19.5 ± 0.5 °, and ice shearing resistance is 170.5 ± 8.5kPa.
Embodiment 2:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer of sulfydryl
Take 0.40gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.02g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 10:5:1; be mixed with the solution that massfraction is 30%; then air in emptying bottle, and nitrogen protection.60 DEG C of oil bath condition lower magnetic force stirring reaction 20h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
By 1.00g dodecafluoroheptyl methacrylate; 0.80gPMAPOSS and 2.20mg Diisopropyl azodicarboxylate (AIBN) is dissolved in phenylfluoroform according to mol ratio 50:4:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 10h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer.
3 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer are dissolved in tetrahydrofuran (THF) according to mol ratio 10:1:1, are configured to the solution that massfraction is 30%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester (m/n=1, molecular weight is 14000): 5%;
Vinyl polysiloxane (a/b=15, molecular weight 15000): 45%;
Sulfydryl polysiloxane (p/q=15, molecular weight 4500): 49%;
Light trigger: 1%;
Film mode: spin coating;
Be that PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer, the 0.02g light trigger (DMPA) of sulfydryl is fully dissolved in tetrahydrofuran solvent by 0.05g end group, then 0.45g vinyl polysiloxane is added, 0.48g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 20%.By spin coating mode 600r/min revolve 5s again 3000r/min revolve 10s and be coated in aluminium flake surface, surface drying under room temperature, then at UV-light (wavelength 365nm, power 2.5mW/cm
2) solidify 10min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 104.7 ± 1.5 ° after tested, and water contact angle is delayed is 17.0 ± 1.0 °, and ice shearing resistance is 165.0 ± 10.0kPa.
Embodiment 3:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer of sulfydryl
Take 0.80gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.04g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 20:10:1; be mixed with the solution that massfraction is 50%; then air in emptying bottle, and nitrogen protection.70 DEG C of oil bath condition lower magnetic force stirring reaction 20h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
2.00g dodecafluoroheptyl methacrylate, 2.00gPMAPOSS and 2.21mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 100:10:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 6h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer.
30 μ l hydrazine hydrates, 40 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer are dissolved in tetrahydrofuran (THF) according to mol ratio 30:10:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.After reaction terminates crude product is poured in methyl alcohol and precipitates, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer that end group is sulfydryl, its structure be for
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester (m/n=0.3, molecular weight is 6000): 30%;
Vinyl polysiloxane (a/b=10, molecular weight 10000): 35%;
Sulfydryl polysiloxane (p/q=10, molecular weight 3000): 30%;
Light trigger: 5%;
Film mode: dip-coating;
Be that PMAPOSS-b-polymethyl acrylic acid ten difluoro heptyl ester segmented copolymer, the 0.05g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and tetrahydrofuran (THF) by 0.30g end group, then 0.35g vinyl polysiloxane is added, 0.30g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 50%.Aluminium flake surface is coated in, surface drying under room temperature, then at UV-light (wavelength 365nm, power 5mW/cm by dip coating manner
2) solidify 20min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 105.0 ± 1.2 ° after tested, and water contact angle is delayed is 15.0 ± 1.0 °, and ice shearing resistance is 155.0 ± 15.0kPa.
Embodiment 4:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer of sulfydryl
Take 0.80gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.04g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 20:10:1; be mixed with the solution that massfraction is 50%; then air in emptying bottle, and nitrogen protection.70 DEG C of oil bath condition lower magnetic force stirring reaction 20h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
0.43g methacrylic acid ten trifluoro monooctyl ester, 0.40gPMAPOSS and 2.21mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 20:2:1; be configured to the solution that massfraction is 30%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 65 DEG C, reacts 24h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer.
30 μ l hydrazine hydrates, 40 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer are dissolved in tetrahydrofuran (THF) according to mol ratio 30:10:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester (m/n=1, molecular weight is 14000): 20%;
Vinyl polysiloxane (a/b=15, molecular weight 15000): 30%;
Sulfydryl polysiloxane (p/q=20, molecular weight 6000): 47%;
Light trigger: 3%;
Film mode: spraying;
Be that PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer, the 0.03g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and methylene dichloride by 0.20g end group, then 0.30g vinyl polysiloxane is added, 0.47g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 30%.Aluminium flake surface is coated in, surface drying under room temperature, then at UV-light (wavelength 365nm, power 6mW/cm by spraying method
2) solidify 20min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 106.0 ± 1.2 ° after tested, and water contact angle is delayed is 16.2 ± 1.3 °, and ice shearing resistance is 145.0 ± 12.0kPa.
Embodiment 5:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer of sulfydryl
Take 0.40gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.008g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 10:2:1; be mixed with the solution that massfraction is 20%; then air in emptying bottle, and nitrogen protection.70 DEG C of oil bath condition lower magnetic force stirring reaction 10h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
1.08g methacrylic acid ten trifluoro monooctyl ester, 0.80gPMAPOSS and 2.2mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 50:4:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 10h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer.
30 μ l hydrazine hydrates, 20 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer are dissolved in tetrahydrofuran (THF) according to mol ratio 30:5:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester (m/n=1, molecular weight is 14000): 30%;
Vinyl polysiloxane (a/b=15, molecular weight 15000): 40%;
Sulfydryl polysiloxane (p/q=20, molecular weight 6000): 28%;
Light trigger: 2%;
Film mode: spin coating;
Be that PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer, the 0.02g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and tetrahydrofuran (THF) by 0.30g end group, then 0.40g vinyl polysiloxane is added, 0.28g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 30%.By spin coating mode 600r/min revolve 5s again 3000r/min revolve 10s and be coated in aluminium flake surface, then at UV-light (wavelength 365nm, power 5mW/cm
2) solidify 30min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 105.5 ± 0.5 ° after tested, and water contact angle is delayed is 13.2 ± 0.5 °, and ice shearing resistance is 130.5 ± 10.2kPa.
Embodiment 6:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer of sulfydryl
Take 1.20gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.02g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 30:5:1; be mixed with the solution that massfraction is 30%; then air in emptying bottle, and nitrogen protection.60 DEG C of oil bath condition lower magnetic force stirring reaction 20h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
0.86g methacrylic acid ten trifluoro monooctyl ester, 0.80gPMAPOSS and 2.21mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 40:4:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 70 DEG C, reacts 12h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer.
30 μ l hydrazine hydrates, 20 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer are dissolved in tetrahydrofuran (THF) according to mol ratio 30:5:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester (m/n=2, molecular weight is 23000): 5%;
Vinyl polysiloxane (a/b=15, molecular weight 15000): 50%;
Sulfydryl polysiloxane (p/q=15, molecular weight 4500): 39%;
Light trigger: 6%;
Film mode: drip and be coated with;
Be that PMAPOSS-b-polymethyl acrylic acid ten trifluoro monooctyl ester segmented copolymer, the 0.06g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and trichloromethane by 0.05g end group, then 0.50g vinyl polysiloxane is added, 0.39g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 40%.Aluminium flake surface is coated in, surface drying under room temperature, then at UV-light (wavelength 365nm, power 2.5mW/cm by dripping painting mode
2) solidify 15min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 104.5 ± 1.0 ° after tested, and water contact angle is delayed is 17.0 ± 1.0 °, and ice shearing resistance is 160.0 ± 8.5kPa.
Embodiment 7:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems of sulfydryl
Take 0.80gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.02g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 20:5:1; be mixed with the solution that massfraction is 30%; then air in emptying bottle, and nitrogen protection.80 DEG C of oil bath condition lower magnetic force stirring reaction 20h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
0.54g methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, 0.48gPMAPOSS and 2.70mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 20:2:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 80 DEG C, reacts 10h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems.
30 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems are dissolved in tetrahydrofuran (THF) according to mol ratio 30:1:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems (m/n=0.7, molecular weight is 35000): 10%;
Vinyl polysiloxane (a/b=10, molecular weight 10000): 45%;
Sulfydryl polysiloxane (p/q=10, molecular weight 3000): 43%;
Light trigger: 2%;
Film mode: spin coating;
Be that PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems, the 0.02g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and tetrahydrofuran (THF) by 0.10g end group, then 0.45g vinyl polysiloxane is added, 0.43g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 30%.By spin coating mode 600r/min revolve 5s again 3000r/min revolve 10s and be coated in aluminium flake surface, surface drying under room temperature, then at UV-light (wavelength 365nm, power 8mW/cm
2) solidify 15min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 116.0 ± 1.0 ° after tested, and water contact angle is delayed is 9.2 ± 1.5 °, and ice shearing resistance is 130.6 ± 12.0kPa.
Embodiment 8:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems of sulfydryl
Take 0.60gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.008g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 15:2:1; be mixed with the solution that massfraction is 50%; then air in emptying bottle, and nitrogen protection.70 DEG C of oil bath condition lower magnetic force stirring reaction 10h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
0.54g methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, 0.48gPMAPOSS and 2.70mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 20:2:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 80 DEG C, reacts 10h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems.
30 μ l hydrazine hydrates, 8 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems are dissolved in tetrahydrofuran (THF) according to mol ratio 30:2:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems (m/n=0.5, molecular weight is 20000): 5%;
Vinyl polysiloxane (a/b=20, molecular weight 20000): 50%;
Sulfydryl polysiloxane (p/q=10, molecular weight 3000): 42%;
Light trigger: 3%;
Film mode: spin coating;
Be that PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems, the 0.03g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and tetrahydrofuran (THF) by 0.05g end group, then 0.50g vinyl polysiloxane is added, 0.42g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 30%.Aluminium flake surface is coated in, surface drying under room temperature, then at UV-light (wavelength 365nm, power 2.5mW/cm by spin coating mode
2) solidify 15min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 116.0 ± 1.5 ° after tested, and water contact angle is delayed is 8.0 ± 1.0 °, and ice shearing resistance is 104.0 ± 9.0kPa.
Embodiment 9:
(1) end group is the preparation of the PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems of sulfydryl
Take 0.80gMAPOSS monomer, chain-transfer agent 4-cyano group-4-(thiobenzoyl) valeric acid (CPADB) 0.02g and initiator Diisopropyl azodicarboxylate (AIBN) 1.63mg; fully be dissolved in toluene solvant according to mol ratio 20:5:1; be mixed with the solution that massfraction is 30%; then air in emptying bottle, and nitrogen protection.80 DEG C of oil bath condition lower magnetic force stirring reaction 20h; Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS multipolymer.
0.54g methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems, 0.48gPMAPOSS and 2.70mg Diisopropyl azodicarboxylate (AIBN) are dissolved in phenylfluoroform according to mol ratio 20:2:1; be configured to the solution that massfraction is 40%; join in Schlenk bottle; then air in emptying bottle, and nitrogen protection.Schlenk pipe is put into constant temperature oil bath at 80 DEG C, reacts 10h.Be added drop-wise in a large amount of methyl alcohol by product after reaction terminates and precipitate, removing unreacted monomer and solvent, the dry 24h of room temperature in vacuo, obtains PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems.
30 μ l hydrazine hydrates, 4 μ l dimethylphenylphosphines and 0.40gPMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems are dissolved in tetrahydrofuran (THF) according to mol ratio 30:1:1, are configured to the solution that massfraction is 10%, join in there-necked flask.At room temperature stirring reaction 3h.Be poured in methyl alcohol by crude product after reaction terminates and precipitate, then put into the dry 24h of vacuum drying oven, obtain the PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems that end group is sulfydryl, its structural formula is
(2) preparation of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating
PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester in the last of the ten Heavenly stems (m/n=0.5, molecular weight is 20000): 30%;
Vinyl polysiloxane (a/b=20, molecular weight 20000): 34%;
Sulfydryl polysiloxane (p/q=10, molecular weight 3000): 30%;
Light trigger: 6%;
Film mode: spraying;
Be that PMAPOSS-b-polymethyl acrylic acid 17 fluorine ester block copolymer in the last of the ten Heavenly stems, the 0.06g light trigger (DMPA) of sulfydryl is fully dissolved in (1w/1w) in the mixed solvent of phenylfluoroform and tetrahydrofuran (THF) by 0.30g end group, then 0.34g vinyl polysiloxane is added, 0.30g sulfydryl polysiloxane, continues to add solvent and is made into the mixing solutions that concentration is 30%.Aluminium flake surface is coated in, surface drying under room temperature, then at UV-light (wavelength 365nm, power 5mW/cm by spraying method
2) solidify 30min under irradiation, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
(3) water contact angle, contact angle hysteresis and ice shearing resistance test
Coating water contact angle is 116.0 ± 0.5 ° after tested, and water contact angle is delayed is 8.0 ± 1.0 °, and ice shearing resistance is 160.5 ± 7.5kPa.
Open and a kind of ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating that proposes of the present invention and Synthesis and applications, those skilled in the art are by using for reference present disclosure, the links such as appropriate change condition route realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (9)
1. a ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating; It is characterized in that, each component and mass percentage content are:
End group is that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer: 1 ~ 30%;
Vinyl polysiloxane: 30 ~ 50%;
Sulfydryl polysiloxane: 30 ~ 50%;
Light trigger: 1 ~ 6%.
2. coating as claimed in claim 1, is characterized in that described end group is the structural formula that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer and is:
Wherein m/n=0.1 ~ 2; Molecular weight is 6000 ~ 35000g/mol; R
ffor-CH
2cF (CF
3) CFHCF (CF
3)
2,-CH
2cH
2(CF
2)
5cF
3or-CH
2cH
2(CF
2)
7cF
3.
3. coating as claimed in claim 1, is characterized in that described sulfydryl polysiloxane separation structure formula is:
Wherein p/q=10 ~ 20; Molecular weight is 3000 ~ 6000g/mol.
4. 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.
5. coating as claimed in claim 1, is characterized in that described light trigger is 2,2-dimethoxy-2-phenyl acetophenone.
6. claim 1 ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating production, it is characterized in that: be that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer, sulfydryl polysiloxane, vinyl polysiloxane and light trigger and is dissolved in by mass percentage in solvent by end group, be configured to the solution that mass concentration is 10% ~ 50%, be coated in substrate surface, surface drying under room temperature, then under ultraviolet light irradiation, solidify 10 ~ 30min, obtain ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating.
7. method as claimed in claim 6, it is characterized in that end group is the preparation method that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer and is: hydrazine hydrate, 3,5-dimethylphenyl phosphorus and PMAPOSS-b-are gathered fluoroalkyl segmented copolymer according to mol ratio (10 ~ 30): (1 ~ 10): 1 is dissolved in tetrahydrofuran (THF), be made into the solution that massfraction is 10% ~ 50%, and quick violent stirring 1 ~ 5h under room temperature; Reacted product adds excessive methanol extraction; Then the dry 24h of room temperature in vacuo, obtaining end group is that the PMAPOSS-b-of sulfydryl gathers fluoroalkyl segmented copolymer.
8. method as claimed in claim 7, it is characterized in that the preparation method that PMAPOSS-b-gathers fluoroalkyl segmented copolymer is: by fluorinated acrylate (dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid 17 fluorine ester in the last of the ten Heavenly stems is wherein a kind of), PMAPOSS and Diisopropyl azodicarboxylate (AIBN) be according to mol ratio (20 ~ 100): (2 ~ 10): 1 is dissolved in phenylfluoroform, be configured to the solution that massfraction is 10 ~ 50%, join in Schlenk bottle, then remove oxygen.Put into constant temperature oil bath and react 6 ~ 20h at 65 ~ 80 DEG C; Reaction after product adds excessive methanol precipitation; Then product is put into vacuum drying oven dry 24 hours, obtain PMAPOSS-b-and gather fluoroalkyl segmented copolymer.
9. ultraviolet light polymerization POSS fluorine-containing ester block copolymer composite organic coating is used for hydrophobic, ice-covering-proof material.
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| CN114573771A (en) * | 2022-03-03 | 2022-06-03 | 中石化石油工程技术服务有限公司 | Fluorine-containing silicon polymer shale inhibitor for water-based drilling fluid and preparation method thereof |
| CN116162408A (en) * | 2023-04-22 | 2023-05-26 | 山东福瑞斯新材料科技有限公司 | Organosilicon solvent-free waterproof anticorrosive paint and preparation method and application thereof |
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