CN102321415A - Fluorine-silicon acrylic resin nano composite anti-icing coating and preparation method thereof - Google Patents
Fluorine-silicon acrylic resin nano composite anti-icing coating and preparation method thereof Download PDFInfo
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- CN102321415A CN102321415A CN201110228544A CN201110228544A CN102321415A CN 102321415 A CN102321415 A CN 102321415A CN 201110228544 A CN201110228544 A CN 201110228544A CN 201110228544 A CN201110228544 A CN 201110228544A CN 102321415 A CN102321415 A CN 102321415A
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Abstract
The invention discloses a super hydrophobic anti-icing coating and a preparation method thereof, and is realized by preparing a fluorine contained acrylic resin and combining the fluorine contained acrylic resin with organosilicon resin and nano particles. In a scheme of the invention, the fluorine contained acrylic resin has small surface energy and strong hydrophobicity. The organosilicon resin utilizes effect of -CH3 on a surface thereof and small polarity to substantially reduce contact angle hysteresis. The fluorine contained acrylic resin can crosslink and solidify with the nano particles and active groups in the organosilicon resin to form a composite network. The invention can overcome defects of complex technology, high costs and unsuitability for large scale usage of an ordinary method for preparing a super hydrophobic coating; and the prepared coating can realize super hydrophobic anti-icing effect through a regular spraying method.
Description
Technical field
The invention belongs to topcoating technical field in the chemical, relate to a kind of anti-icing coating, more particularly, relate to a kind of fluorine silicon vinylformic acid compound resin and preparation method thereof.
Background technology
Icing is to be combined and formed by very complicated synoptic process and microphysical processes, and base types such as glaze icing, mixing river in Jiangsu Province which flows into the Huangpu River of Shanghai icing, ice fog river in Jiangsu Province which flows into the Huangpu River of Shanghai icing, bloom, accumulated snow are arranged according to formation condition and hazard rating classification.Mixing the river in Jiangsu Province which flows into the Huangpu River of Shanghai is a compound icing process, at first is glaze, is rime then, is a kind of alternately form of ice, and the speed of growth is very fast, the harm especially severe.
In the face of the harm that icing such as aircraft, lead cause, anti-icing Study on Technology begins to arise from the fifties in last century, is divided into initiatively deicing technology and passive anti-icing technology generally.Initiatively the deicing technology is mainly utilized physical method, presses down ice agent class material through heating unit, mechanical deicing and sprinkling terepthaloyl moietie, salt solution etc., belongs to the processing after freezing, and under uncontrollable condition, can't play a role.Passive anti-icing technology mainly is to have the functional coating that slowly-releasing presses down the ice agent, has phase transformation and low surface energy through structure; Reduce the icing probability in surface adhesion force, surface of ice and the microtexture of internal stress effect destruction ice etc., the technology that through external force such as gravity, wind-force etc. the ice nature is come off at last.Passive anti-icing technical costs is lower, longer duration, and use range is extensive.
Utilizing hydrophobic nature is one of passive method with hating ice property coating to reach anti-icing purpose; Cover at material surface and to be coated with coating with hydrophobicity performance; Can effectively reduce ice and the long-pending sticking power that covers body surface; Can prevent the formation of stagnant ice more effectively, can be again such as can landing under the external force effect of wind, reduce and the ice trouble accident occurs.Present passive anti-icing technology concentrates on and can press down the ice agent by slowly-releasing; Reach colloidal sol-gel (sol-gel) coating (Ayres J, Simendinger WH, the Balik CM. " Characterization of titanium alkoxide sol-gel systems designed for anti-icing coatings:II.Mass loss kinetics " that reduce freezing point and then lower the probability that freezes; Journal of Coatings Technology; 2007,4 (4), 473-481); Have low surface energy and maybe can destroy organosilicon phase transformation coating (Bhamidipati MV, Randolph MA. " Methods and compositions for inhibiting surface icing " the .US 7514017B2 that ices interface microstructure through phase transformation; Byrd NR, Park V, Soden DG, et al. " Tough and stongly-adherent anti-icing coatings " .US 7910683B2); Utilize fluorine resin and nanoparticle compound; Destroy super-hydrophobic coat (Farhadi S, Farzanehl M, the Kulinich SA. " Anti-icing performance of superhydrophobic surfaces " of ice structure through the stress concentration that adheres to and utilize freezing process ice and interface nano material to form that reduces water; Applied Surface Science; 2011,257,6264-6269).
Summary of the invention
The objective of the invention is to prepare a kind of super-hydrophobic ice-covering-proof coating; Overcome shortcomings such as technical sophistication in the general preparation super-hydrophobic coat method, with high costs, unsuitable big area use simultaneously, the coating of being developed uses conventional spraying method promptly can reach the effect of super-hydrophobic ice-covering-proof.
The object of the invention is achieved through following technical proposals, promptly through preparing a kind of fluoroacrylic resin and realizing with the compound of silicone resin and nanoparticle.
At first prepare fluoroacrylic resin, according to the radical polymerization principle, have fluoroacrylic resin through the solution polymerization process preparation, used monomer comprises fluorinated acrylate monomer, active cross-linking monomer and the skeleton monomer that makes up soft chain segment and hard segment.At first solvent is warming up to 60～80 ℃; After feeding nitrogen 0.5～2h; With fluorinated acrylate monomer, active cross-linking monomer and make up the skeleton monomer of soft chain segment and hard segment, the initiator that accounts for initiator total amount 60～80wt% mixes; In solvent, evenly drip aforementioned mixed solution then, the dropping time is 2～3h.Drip to be incubated after mixed solution finishes and continue reaction 1～2h.0.5 add the remaining initiator that accounts for initiator total amount 20～40wt% in the～2h again, continue reaction 2～3h.After being cooled to room temperature, using normal hexane to purify and obtain fluoroacrylic resin.Said fluoropolymer has film coated surface can be lower than 20mN/m, and the normal-temperature water contact angle is greater than 105 ° performance.
Wherein said skeleton monomer is propenoate skeleton monomer or methacrylic ester skeleton monomer; Said propenoate skeleton monomer is methyl acrylate, ethyl propenoate, propyl acrylate or Bing Xisuandingzhi, and said methacrylic ester skeleton monomer is TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, methylacrylic acid pentyl ester, N-Hexyl methacrylate or Octyl methacrylate.
Said active cross-linking monomer is acrylate cross linked monomer or methacrylic ester cross-linking monomer, and said acrylate cross linked monomer is glycidyl acrylate, vinylformic acid, propenoic acid beta-hydroxy ethyl ester or propenoic acid beta-hydroxy propyl ester; Said methacrylic ester cross-linking monomer is SY-Monomer G, methylacrylic acid, Jia Jibingxisuanβ-Qiang Yizhi or methylacrylic acid β-hydroxypropyl acrylate.
Said fluoro-acrylate monomer is methylacrylic acid hexafluoro butyl ester, methylacrylic acid ten difluoro fat in heptan, methylacrylic acid ten trifluoro monooctyl esters, methylacrylic acid 15 fluorine esters in the ninth of the ten Heavenly Stems or methylacrylic acid 17 fluorine esters in the last of the ten Heavenly stems.
Said initiator is the initiator of thermal initiation radical polymerization, like Diisopropyl azodicarboxylate, ABVN.
Said solvent is the cooperation of organic solvents such as toluene, acetone, ETHYLE ACETATE, N-BUTYL ACETATE or its arbitrary proportion.
In above-mentioned reaction system, said fluoroacrylic resin is processed through solution polymerization process according to the raw material of following weight part:
Preferred following proportioning raw materials
Secondly; Nanoparticle is carried out modification; Employed nanoparticle is the mixing of a kind of among nano silicon, nano titanium oxide, nano zirconium dioxide, nano zine oxide, nano tin dioxide, the nano oxidized lithium or two kinds and two or more arbitrary proportions; Toluene or YLENE are heated to reflux temperature, add the nanoparticle dispersion liquid of ultra-sonic dispersion.Add quality subsequently and be hydrophobic organic siloxane modified dose of 0.2～2 times of nanoparticle, about 2～8h refluxes.Clean the excess treating agent with soxhlet's extractor at last.Specifically, the particle diameter of said nanoparticle is 10～500nm, and optimum grain-diameter is 30～80nm.Described nanometer particle-modified dose mainly is the silane modifier R that contains hydrophobic chain
1 4-mSiR
m, R
2 3Si-O-Si-R
3 3And R
4[(SiR
5 2) O] nR
6R wherein
1, R
4, R
5And R
6Be methacryloxypropyl, alkyl, fluoroalkyl, R, R
2And R
3 3Be methoxyl group, oxyethyl group or chlorine atom; M is 1; 2 or 3; N is 2～10000, and for example a kind of in γ-methacryloxypropyl trimethoxy silane, hexadecyl Trimethoxy silane, 17 fluorine decyl triethoxyl silanes, dimethyldichlorosilane(DMCS) or the octadecyltriethoxy silane carries out modification, so that it can be uniformly dispersed in organic solvents such as toluene.
The 3rd; Fluoroacrylic resin, modified Nano particle, silicone resin, solidifying agent, solvent evenly can be obtained anti-icing paint; Selecting solvent for use is the cooperation of organic solvents such as toluene, acetone, ETHYLE ACETATE or its arbitrary proportion; The solidifying agent of selecting for use is the solidifying agent that hexamethylene diisocyanate trimer (HDI), diphenylmethanediisocyanate tripolymer (MDI), PDI etc. contain the vulcabond performed polymer, and the solidifying agent of for example selecting for use is the product N3390 of Bayer A.G.The silicone resin of selecting for use can be dissolved in organic solvent (for example toluene) and can mix with vinyl resin simultaneously, and structure is as shown in the formula shown in (1):
R wherein
1, R
2, R
3, R
4Be methyl, ethyl, phenyl; R
5, R
6Be hydroxyl, methoxyl group, oxyethyl group; M is 10～100, and n is 20～1000, and viscosity is 20～200000cP.The silicone resin that can select for use specifically is Dow corning company series product 840.
In the technical scheme of the present invention, according to following weight part that raw materials mix is even, promptly get coating of the present invention,
The said components preferable range is following
It is following that said components is more preferably scope
Technical scheme of the present invention makes up the surface of super-drainage structure; This shows must satisfy two conditions: micro-nano secondary structure and resin with low surface energy; Need to prove that surfaceness is very huge to the surface adhesion force influence; The resistance of surperficial smooth interface generation relative displacement more is more little; But certain roughness can make the contact area of water droplet reduce and then reduce the interface that freezes, and so the air chamber sticking power that also can cause stress concentration to reduce to ice to the ice at interface at freezing process in addition is certain roughness adhering to of helping reducing to ice.
Among the present invention program, the surface energy of fluoroacrylic resin is very little, and hydrophobicity is strong.Silicone resin utilizes surface-CH
3Effect and less polarity can significantly reduce the contact angle hysteresis phenomenon.Fluoroacrylic resin can with the active group crosslinking curing in nanoparticle and the silicone resin, form composite network.
Utilize coating of the present invention under 0.4～1MPa air pressure, to spray and to obtain compound anti-icing coating.Anti-icing performance testing method of the present invention is following: freezing 3h under-20 ℃ of environment prepares supercooled water with pure water.The aluminium sheet that is coated with anti-icing coating (is of a size of 12cm * 5cm), has a down dip 30 °-10 ℃ of conditions and place 2h.On the blank aluminium sheet that subsequently supercooled water is poured into the inclination different angles and the experiment aluminium sheet, shake is not after have ice and come off gently after freezing, and the weight of on the aluminium sheet sample, freezing is being covered in weighing, and with the aluminium sheet of the anti-icing coating of spraying not on the amount of freezing compare.Above step is tried to achieve MV after repeating five times, and experimental result shows utilizes coating of the present invention can reduce ice cover more than 80%.The present invention overcomes shortcomings such as technical sophistication in the general preparation super-hydrophobic coat method, with high costs, unsuitable big area use, and the coating of being developed uses conventional spraying method promptly can reach the effect of super-hydrophobic ice-covering-proof.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.The contact angle tester that utilizes is the JC2000D4 type contact angle tester of Shanghai Zhongchen digital technology equipment Co., Ltd.
Embodiment one:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.In 3h, drip the mixed solution of 4g TEB 3K, 8g NSC 20956,2.81g Bing Xisuandingzhi, 3g SY-Monomer G, 4g methylacrylic acid ten difluoro heptyl esters, 0.21g Diisopropyl azodicarboxylate subsequently; Behind the isothermal reaction 0.5h, in 0.5h, continue to drip the mixed solution of 0.1g Diisopropyl azodicarboxylate and 10g toluene.Continue reaction 2h.Reaction finishes the back with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 18mN/m, with the normal temperature contact angle of water be 112 °, the contact angle under-10 ℃ is 105 °.
2, adding 150ml toluene and 5g particle diameter are the silicon-dioxide of 20nm in beaker, use cell pulverization machine 600W ultra-sonic dispersion 3min.Drip 2g γ-methacryloxypropyl trimethoxy silane subsequently, mix, backflow 8h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 25CP with 1g synthetic fluoroacrylic resin, 0.8g viscosity, structure suc as formula the silicone resin structure of (2) suc as formula shown in (2):
Embodiment two:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.In 3h, drip the mixed solution of 4g TEB 3K, 8g NSC 20956,2.81g Bing Xisuandingzhi, 3g SY-Monomer G, 4g methylacrylic acid ten trifluoro monooctyl esters, 0.21g Diisopropyl azodicarboxylate subsequently; Behind the isothermal reaction 0.5h, in 0.5h, continue to drip the mixed solution of 0.1g Diisopropyl azodicarboxylate and 10g toluene.Continue reaction 2h.Reaction finishes the back with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 16mN/m, and the normal temperature contact angle of water is 115 °, and the contact angle under-10 ℃ is 108.
2, in beaker, add the silicon-dioxide of 150ml toluene and 5g particle diameter 50nm, use cell pulverization machine ultra-sonic dispersion 3min under 600W.Drip 2g hexadecyl Trimethoxy silane subsequently, mix, backflow 8h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 20CP with 3g institute synthetic fluoroacrylic resin, 1g viscosity; Structure is 15～30 suc as formula silicone resin
m of (3); N is that 20～40 (3) 1g improved silicas, 4g toluene, 6g acetone mix; Under the air pressure of 0.6MPa, spray with spray gun, the coat-thickness that obtains is 50 μ m.The normal temperature contact angle of filming with water is 155 °, and roll angle is less than 5 °; Water contact angle under-10 ℃ is 145 °, and roll angle is less than 12 °.The anti-icing performance test finds that experimental group reduces ice cover 80%.
Embodiment three:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.The mixed solution of Dropwise 5 g TEB 3K, 6g NSC 20956,4g Bing Xisuandingzhi, 3g Rocryl 400,4g methylacrylic acid ten trifluoro monooctyl esters, 0.21g Diisopropyl azodicarboxylate in 3h subsequently; Behind the isothermal reaction 0.5h, add the mixed solution of 0.1g Diisopropyl azodicarboxylate and 10g toluene in the 0.5h.Continue to finish reaction behind the reaction 2h, with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 17mN/m, and the normal temperature contact angle of water is 114 °, and the contact angle under-10 ℃ is 103 °.
2, the silicon-dioxide that in beaker, adds 150ml toluene and 5g particle diameter 15～20nm uses the cell pulverization machine at 600W ultra-sonic dispersion 3min.Drip 2g 17 fluorine decyl triethoxyl silanes subsequently, mix backflow 8h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 70CP with 2g institute synthetic fluorine-containing synthetic resins, 1.5g viscosity, structure is suc as formula the silicone resin of (4)
m is 50～80; N is modified manometer silicon dioxide, the 0.6g solidifying agent of 90～160 (4) 0.6g; 3g toluene, 4g ETHYLE ACETATE mix; Spraying under the air pressure of 0.6MPa, the coat-thickness that obtains is 50 μ m.The normal temperature contact angle of the water of filming is 155 °, and roll angle is less than 4 °; Water contact angle under-10 ℃ is 143 °, and roll angle is less than 12 °.The anti-icing performance test finds that experimental group reduces ice cover 80%.
Embodiment four:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.In 3h, drip the mixed solution of 6g TEB 3K, 4g NSC 20956,5g Bing Xisuandingzhi, 3g Rocryl 400,4g methylacrylic acid 15 fluorine esters in the ninth of the ten Heavenly Stems, 0.3g Diisopropyl azodicarboxylate subsequently; Behind the isothermal reaction 1h, in 1h, continue to drip the mixed solution of 0.1g Diisopropyl azodicarboxylate and 10g toluene.Continue to finish reaction behind the reaction 2h, with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 14mN/m, with the normal temperature contact angle of water be 118 °, the water contact angle under-10 ℃ is 107 °.
2, the titanium oxide that in beaker, adds 150ml toluene and 5g particle diameter 50nm uses the cell pulverization machine at 600W ultra-sonic dispersion 3min.Drip 2g 17 fluorine decyl triethoxyl silanes subsequently, mix backflow 5h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 45CP with the resulting fluoroacrylic resin of 2.5g, 1.8g viscosity, structure is suc as formula (5) silicone resin
Embodiment five:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.In 3h, drip the mixed solution of 6g TEB 3K, 4g NSC 20956,5g Bing Xisuandingzhi, 3g Rocryl 400,4g methylacrylic acid 17 fluorine esters in the last of the ten Heavenly stems, 0.3g Diisopropyl azodicarboxylate subsequently; Behind the isothermal reaction 1h, in 1h, continue to drip the mixed solution of 0.1g Diisopropyl azodicarboxylate and 10g toluene.Continue reaction 2h and finish reaction, with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 15mN/m, with the normal temperature contact angle of water be 116 °, the water contact angle under-10 ℃ is 109 °.
2, add the ZIRCONIUM DIOXIDE 99.5 of 150ml toluene and 6g particle diameter 40nm in the beaker, utilize cell pulverization machine 600W ultra-sonic dispersion 3min.Drip the 3g dimethyldichlorosilane(DMCS) subsequently, mix, backflow 5h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 55CP with the resulting fluoroacrylic resin of 3g, 1.8g viscosity, structure is suc as formula the silicone resin of (6)
Embodiment six:
1, in four-hole bottle, adds 60g toluene, feed nitrogen, be warming up to 80 ℃.The mixed solution of Dropwise 5 g TEB 3K, 8g NSC 20956,7g Bing Xisuandingzhi, 4g Rocryl 400,8g methylacrylic acid hexafluoro butyl ester, 0.4g Diisopropyl azodicarboxylate in the 3h subsequently; Behind the isothermal reaction 1h, add the mixed solution of 0.15g Diisopropyl azodicarboxylate and 15g toluene in the 1h.Continue reaction 2h, with the normal hexane resin of purifying, vacuum-drying.The surface energy of this resin is 18mN/m, and the normal temperature contact angle of water is 113 °.Contact angle under-10 ℃ is 103 °.
2, in beaker, add the nano zine oxide of 150ml toluene and 6g particle diameter 60nm, utilize cell pulverization machine 600W ultra-sonic dispersion 3min.Drip the 3g dimethyldichlorosilane(DMCS) subsequently, mix, backflow 5h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be silicone resin, the modified nano zinc oxide of 1.5g, the 1.8g solidifying agent of 55CP structural formula with the resulting fluoroacrylic resin of 5g, 3g viscosity like (6); 15g toluene, 2g ETHYLE ACETATE mix; Under the air pressure of 0.6MPa, spray, the coat-thickness that obtains is 50 μ m.The normal temperature contact angle of the water of filming is 152 °, and roll angle is less than 6 °; Contact angle under-10 ℃ is 146 °, and roll angle is less than 11 °.The anti-icing performance test finds that experimental group reduces ice cover 83%.
Embodiment seven:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.The mixed solution of Dropwise 5 g TEB 3K, 8g NSC 20956,7g Bing Xisuandingzhi, 4g SY-Monomer G, 8g methylacrylic acid 17 fluorine esters in the last of the ten Heavenly stems, 0.4g Diisopropyl azodicarboxylate in the 3h subsequently; Behind the isothermal reaction 1h, add the mixed solution of 0.15g Diisopropyl azodicarboxylate and 15g toluene in the 1h.Continue reaction 2h, with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 20mN/m, and the normal temperature contact angle of water is 110 °.Contact angle under-10 ℃ is 104 °.
2, add the nano tin dioxide of 150ml toluene and 6g particle diameter 60nm in the beaker, utilize cell pulverization machine 600w ultra-sonic dispersion 3min.Drip the 3g dimethyldichlorosilane(DMCS) subsequently, mix, backflow 5h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 45CP with the resulting fluoroacrylic resin of 5g, 1.8g viscosity; Structure is suc as formula the silicone resin of (5), the modified Nano White tin oxide of 1.5g, and 12g toluene, 6g ETHYLE ACETATE mix; Spraying under the air pressure of 0.6MPa, the coat-thickness that obtains is 50 μ m.The normal temperature contact angle of the water of filming is 156 °, and roll angle is less than 5 °; Contact angle under-10 ℃ is 149 °, and roll angle is less than 10 °.The anti-icing performance test finds that experimental group reduces ice cover 80%.
Embodiment eight:
1, in four-hole bottle, adds 50g toluene, feed nitrogen, be warming up to 80 ℃.The mixed solution of Dropwise 5 g TEB 3K, 8g NSC 20956,7g Bing Xisuandingzhi, 4g SY-Monomer G, 8g methylacrylic acid 15 fluorine esters in the ninth of the ten Heavenly Stems, 0.4g Diisopropyl azodicarboxylate in the 3h subsequently; Behind the isothermal reaction 1h, add the mixed solution of 0.15g Diisopropyl azodicarboxylate and 15g toluene in the 1h.Continue reaction 2h, with the normal hexane resin of purifying, vacuum-drying.The surface energy of resulting fluoroacrylic resin is 19mN/m, and the normal temperature contact angle of water is 111 °; Contact angle under-10 ℃ is 106 °.
2, add the nano oxidized lithium of 150ml toluene and 6g particle diameter 10nm in the beaker, utilize cell pulverization machine 600w ultra-sonic dispersion 3min.Drip the 3g octadecyltriethoxy silane subsequently, mix, backflow 8h.Reflux with soxhlet's extractor at last and clean 8h, dry for use.
3, be 110CP with the resulting fluoroacrylic resin of 6g, 2g viscosity, structure is suc as formula the silicone resin of (7)
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. the nano combined anti-icing paint of fluorine silicon vinyl resin is characterized in that, by fluoroacrylic resin, silicone resin, modified Nano particle, solidifying agent and solvent composition, wherein
2. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 1 is characterized in that said each component proportion optimization is following:
3. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 2 is characterized in that, said each set of dispense ratio is more preferably following:
4. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 1 is characterized in that said fluoropolymer has film coated surface can be lower than 20mN/m, and the normal-temperature water contact angle is greater than 105 ° performance.
5. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 4; It is characterized in that; Said fluoropolymer is through the solution polymerization process preparation, and used monomer comprises fluorinated acrylate monomer, active cross-linking monomer and the skeleton monomer that makes up soft chain segment and hard segment, at first solvent is warming up to 60～80 ℃; After feeding nitrogen 0.5～2h; With fluorinated acrylate monomer, active cross-linking monomer and make up the skeleton monomer of soft chain segment and hard segment, the initiator that accounts for initiator total amount 60～80wt% mixes, and in solvent, evenly drips aforementioned mixed solution then, the dropping time is 2～3h.Drip to be incubated after mixed solution finishes and continue reaction 1～2h, add the remaining initiator that accounts for initiator total amount 20～40wt% in 0.5～2h again, continue to react 2～3h.After being cooled to room temperature, using normal hexane to purify and obtain fluoroacrylic resin, said each proportioning raw materials is following:
Wherein said skeleton monomer is propenoate skeleton monomer or methacrylic ester skeleton monomer; Said propenoate skeleton monomer is methyl acrylate, ethyl propenoate, propyl acrylate or Bing Xisuandingzhi, and said methacrylic ester skeleton monomer is TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, methylacrylic acid pentyl ester, N-Hexyl methacrylate or Octyl methacrylate
Said active cross-linking monomer is acrylate cross linked monomer or methacrylic ester cross-linking monomer, and said acrylate cross linked monomer is glycidyl acrylate, vinylformic acid, propenoic acid beta-hydroxy ethyl ester or propenoic acid beta-hydroxy propyl ester; Said methacrylic ester cross-linking monomer is SY-Monomer G, methylacrylic acid, Jia Jibingxisuanβ-Qiang Yizhi or methylacrylic acid β-hydroxypropyl acrylate
Said fluoro-acrylate monomer is methylacrylic acid hexafluoro butyl ester, methylacrylic acid ten difluoro fat in heptan, methylacrylic acid ten trifluoro monooctyl esters, methylacrylic acid 15 fluorine esters in the ninth of the ten Heavenly Stems or methylacrylic acid 17 fluorine esters in the last of the ten Heavenly stems
Said initiator is the initiator of thermal initiation radical polymerization, like Diisopropyl azodicarboxylate, ABVN
Said solvent is the cooperation of organic solvents such as toluene, acetone, ETHYLE ACETATE, N-BUTYL ACETATE or its arbitrary proportion.
6. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 5 is characterized in that said each proportioning raw materials is preferably following:
7. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 1; It is characterized in that; The nanoparticle that said modified Nano particle uses is the mixing of a kind of among nano silicon, nano titanium oxide, nano zirconium dioxide, nano zine oxide, nano tin dioxide, the nano oxidized lithium or two kinds and two or more arbitrary proportions; Toluene or YLENE are heated to reflux temperature; The nanoparticle dispersion liquid that adds ultra-sonic dispersion adds quality and is hydrophobic organic siloxane modified dose of 0.2～2 times of nanoparticle subsequently, and about 2～8h refluxes.Clean the excess treating agent with soxhlet's extractor at last
The particle diameter of said nanoparticle is 10～500nm, and optimum grain-diameter is 30～80nm; Described nanometer particle-modified dose mainly is the silane modifier R that contains hydrophobic chain
1 4-mSiR
m, R
2 3Si-O-Si-R
3 3And R
4[(SiR
5 2) O] nR
6, R wherein
1, R
4, R
5And R
6Be methacryloxypropyl, alkyl, fluoroalkyl, R, R
2And R
3 3Be methoxyl group, oxyethyl group or chlorine atom; M is 1; 2 or 3; N is 2～10000, and for example a kind of in γ-methacryloxypropyl trimethoxy silane, hexadecyl Trimethoxy silane, 17 fluorine decyl triethoxyl silanes, dimethyldichlorosilane(DMCS) or the octadecyltriethoxy silane carries out modification, so that it can be uniformly dispersed in organic solvents such as toluene.
8. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 1; It is characterized in that said solidifying agent is the solidifying agent that hexamethylene diisocyanate trimer, diphenylmethanediisocyanate tripolymer etc. contain the vulcabond performed polymer.
9. the nano combined anti-icing paint of a kind of fluorine silicon vinyl resin according to claim 1 is characterized in that, said silicone resin can be dissolved in organic solvent and can mix with vinyl resin simultaneously, and structure is as shown in the formula shown in (1):
R wherein
1, R
2, R
3, R
4Be methyl, ethyl, phenyl; R
5, R
6Be hydroxyl, methoxyl group, oxyethyl group; M is 10～100, and n is 20～1000, and viscosity is 20～200000cP.
10. one kind prepares the method for weighing the nano combined anti-icing paint of 1 described fluorine silicon vinyl resin; It is characterized in that; Carry out according to following step: at first carry out hydrophobic modified nanoparticle; Then fluoroacrylic resin, modified Nano particle, silicone resin, solidifying agent, solvent are mixed according to proportioning raw materials and can obtain anti-icing paint, selecting solvent for use is the cooperation of organic solvents such as toluene, acetone, ETHYLE ACETATE or its arbitrary proportion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110228544A CN102321415A (en) | 2011-08-11 | 2011-08-11 | Fluorine-silicon acrylic resin nano composite anti-icing coating and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060932A1 (en) * | 2000-02-15 | 2001-08-23 | J.C. Hempel's Skibsfarve-Fabrik A/S | Antifouling paint composition |
| CN1824699A (en) * | 2006-02-10 | 2006-08-30 | 华东理工大学 | Method of lowering acrylate material surface energy |
| CN101157740A (en) * | 2007-09-29 | 2008-04-09 | 海洋化工研究院 | Fluorin-containing acrylic resin having ultra-low surface energy and preparation method and application in paint thereof |
| US20100314575A1 (en) * | 2009-06-16 | 2010-12-16 | Di Gao | Anti-icing superhydrophobic coatings |
-
2011
- 2011-08-11 CN CN201110228544A patent/CN102321415A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060932A1 (en) * | 2000-02-15 | 2001-08-23 | J.C. Hempel's Skibsfarve-Fabrik A/S | Antifouling paint composition |
| CN1824699A (en) * | 2006-02-10 | 2006-08-30 | 华东理工大学 | Method of lowering acrylate material surface energy |
| CN101157740A (en) * | 2007-09-29 | 2008-04-09 | 海洋化工研究院 | Fluorin-containing acrylic resin having ultra-low surface energy and preparation method and application in paint thereof |
| US20100314575A1 (en) * | 2009-06-16 | 2010-12-16 | Di Gao | Anti-icing superhydrophobic coatings |
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Application publication date: 20120118 |