CN112175154B

CN112175154B - Particle size controllable silicon-fluorine polymer nano particle and preparation method and application thereof

Info

Publication number: CN112175154B
Application number: CN202011072813.3A
Authority: CN
Inventors: 赵玮; 谭浩; 刘天庆; 贾中凡
Original assignee: Hangzhou Wanguan Technology Co ltd
Current assignee: Hangzhou Wanguan Technology Co ltd
Priority date: 2020-10-09
Filing date: 2020-10-09
Publication date: 2022-04-29
Anticipated expiration: 2040-10-09
Also published as: CN112175154A

Abstract

The invention provides a fluorine-silicon polymer nano particle with controllable particle size, wherein the fluorine-silicon polymer has a structure shown as the following formula (I):

the invention can efficiently, stably and cheaply obtain the silicon-fluorine polymer nano particles with different particle diameters by simple operation, such as regulating and controlling the reaction time. The obtained silicon fluorine polymer also has hydroxyl, carboxyl and other groups, and can be conveniently crosslinked and cured with other materials, such as substances containing isocyanate groups, so as to obtain a super-smooth coating. The organic silicon chain segment in the silicon-fluorine polymer increases the smoothness of the coating, reduces the adhesive force of liquid on the coating and reduces the sliding angle. Not only has beneficial hydrophobic property, but also has beneficial oleophobic property. Further, the obtained super-smooth coating can achieve the effects of self-repairing and wear resistance through heating under the condition that the coating is damaged under the action of external force, and the durability of the coating is effectively improved.

Description

Particle size controllable silicon-fluorine polymer nano particle and preparation method and application thereof

Technical Field

The invention relates to the field of nano materials, in particular to a silicon-fluorine polymer nano particle.

Background

The preparation of the surface with special infiltration function is a research hotspot in the field of interface science. Since the lotus leaf effect was discovered in the last 70 th century, the research on the bionic super-hydrophobic surface for bringing excellent characteristics of drag reduction, pollution prevention, self-cleaning and the like to an object is continuously concerned and developed, and the bionic super-hydrophobic surface also serves as a bionic vivid example to build a bridge between nature and technology. However, the practical application of superhydrophobic coatings in current production life has so far been problematic in many ways, such as that most superhydrophobic materials still have poor durability, low mechanical strength, their fragile and porous surface texture and weak adhesion, which can be easily removed even by a light finger sweep. A few types of super-hydrophobic materials reported at present show relatively good mechanical durability by using sandpaper abrasion and adhesive tape stripping as tests. However, all the reported materials have the defects of single material system, high price, difficult industrial production and the like.

Super-smoothness is another result with special infiltration effect in nature, and the principle that the 2011 university of haver Aizenberg topic group simulates nepenthes to prey insects on a smooth surface is the first time to propose the concept of Slippery liquid-infused porous surface (SLIPS). The essence of the method is that a porous structure is filled with low-surface-energy liquid, and a gas film in a porous solid is replaced by a liquid film to form a more stable solid/liquid composite film layer, so that the problems of poor stability and the like of the solid/gas surface of a super-hydrophobic structure are solved. Due to the low surface energy of the lubricating liquid poured into the porous structure, the environmental liquid has a large contact angle and a small sliding angle on the surface of the solid/liquid composite structure, and is difficult to adhere or invade to the surface, so the surface is also called as a super smooth surface. The super-smooth surface shows unique performances of self-cleaning, self-repairing, stain resistance and the like, quickly becomes a research hotspot since development, and shows wide application prospects in the fields of corrosion prevention, anti-icing and anti-fog, antibiosis and anti-fouling, oil-water separation and the like. However, there is still a great challenge in how to prepare a super-smooth surface with stable properties. On the one hand, the design and preparation standards of the ultra-smooth surface are not explicitly reported, for example, the optimal range of the roughness of the substrate, the number of applicable lubricating oil, the reliability of the ultra-smooth surface and the like are not explicitly provided. On the other hand, although the lubricating oil used in the preparation process is chemically inert, molecular diffusion is always carried out, and the lubricating oil is in contact with an environmental medium for a long time and is finally ineffective. Damage and failure to the ultra-smooth surface in the circulating processes of high temperature, water flow impact, freezing and unfreezing are not solved, so how to prepare the ultra-smooth surface with strong environmental adaptability, reliable service and high performance needs to be overcome by the efforts of scientific researchers.

Besides substances with low surface active energy, a micro-nano structure can be constructed on the surface of the material, and the surface hydrophobicity is improved by changing the surface roughness, wherein the micro-nano structure is a research direction for constructing hydrophobic materials and surfaces at present. Various micro-nano structures are prepared by a chemical method or pulse laser or ultrafast pulse laser, a plurality of patents and literature reports exist for realizing hydrophobicity, but the construction of a micro-nano multilevel microstructure has the disadvantages of complex preparation process, high cost, low efficiency, poor repeatability, higher requirements on test conditions and the size and the shape of a hydrophobic substance, complex operation and no contribution to industrial production.

The fluorosilicone polymer has the advantages of both organic silicon and organic fluorine, has the characteristics of beneficial lubricating property, film forming property and low surface energy, relates to partial application in the field of super-smooth materials at present, and is mainly compounded with the fluorosilicone polymer and some inorganic nano particles, such as nano SiO₂Nano TiO 2₂The method can form a uniform and smooth coating on the surface of the glass, and the introduction of the nano inorganic material obviously improves the hydrophobicity of the coating. In addition, the prior art is that nano SiO modified by acryloxysiloxane is prepared by emulsion polymerization method₂For the core, the fluoroacrylate polymer is the polymer of the shell. However, most of the nanoparticle materials obtained by the above methods are inorganic nanoparticles as a framework material, which are not ideal as a nanoparticle material for a super-smooth coating because of their poor mechanical strength and corrosion resistance and uncontrollable particle size.

CN102093697A discloses a super-hydrophobic film on a bionic lotus leaf surface, which comprises a base film made of a low surface energy material and a micro/nano structure formed on the base film, wherein the micro/nano structure comprises the base film, micron-sized particles uniformly distributed on the base film and nano-sized papillae growing on the micron-sized particles, the self-cleaning film has a hydrophobic self-cleaning effect after film formation, and the nano particles are modified inorganic nano particles, so that the corrosion resistance and the stability are insufficient. The durability of the obtained hydrophobic material, such as abrasion resistance, corrosion resistance, solvent scouring resistance and low temperature resistance, is generally weak, and even if a coating with better hydrophobic/oleophobic performance is obtained, the super-smooth performance of the hydrophobic/oleophobic performance cannot last under the external action (sharp article scratch, coarse article friction, solvent dipping or scouring, ultraviolet radiation and freeze-thaw resistance cycle). In addition, the defects of weak adhesion and low durability between the coating material and the substrate are important reasons for preventing the application of the new material in various fields and the technical transformation. Therefore, the weather resistance, the affinity to the substrate and the mechanical strength of the coating layer are all key factors for restricting the ultra-smooth coating.

Disclosure of Invention

Aiming at overcoming the technical problems of uncontrollable particle size and morphology, unstable product quality and the like of the silicon-fluorine polymer nano material in the prior art. The invention provides a silicon-fluorine polymer nano particle with controllable particle size and a preparation method thereof. The block copolymer with a high molecular structure comprising a polysiloxane chain segment, a polyacrylic acid and derivative chain segment thereof and a polystyrene chain segment is obtained by controlling the type and the amount of each monomer in the block polymer through RAFT reaction. The polymer obtained is a core-shell structure by utilizing the aggregation-induced self-assembly of the styrene chain segment in the polymerization process, and the nano particles with uniform particle size and narrow dispersity are formed. By controlling the reaction conditions, such as the reaction time, the silicon-fluorine polymer nano-particles with different particle sizes can be obtained.

The technical problem to be solved by the invention is to use the obtained silicon-fluorine polymer nano particles as nano filler and other materials to construct a durable super-smooth material with excellent hydrophobic and oleophobic properties.

The first purpose of the present invention is to provide fluorosilicone polymer nanoparticles with controllable particle size, wherein the fluorosilicone polymer has a structure represented by the following formula (I):

wherein R is₁，R₂Independently H, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxyl, R₃Is a fluoroalkyl group of 1 to 16 carbon atoms, R₄Is alkyl substituted by hydroxyl, Ar is aryl with 6 to 20 carbon atoms, A is-R₅-OCO-R₆-, wherein R₅，R₆Independently selected from (Si (CH)₃)₂)_tAlkylene having 1 to 4 carbon atoms, (Si (CH)₃)₂)_tAlkylene oxide of 1 to 4 carbon atoms, R₅，R₆Optionally substituted by hydroxy, halogen, t is 0 or 1; n is selected from the integer of 50-80, m is selected from the integer of 5-20, p is selected from the integer of 10-50, q is selected from the integer of 10-50, and s is selected from the integer of 100-1000.

In one embodiment of the invention, R₅，R₆One is an alkylene group having 1 to 4 carbon atoms, and the other is- (Si (CH)₃)₂) Alkylene having 1 to 4 carbon atoms.

The fluorosilicone polymer nano particle provided by the invention is a block copolymer obtained by RAFT reaction of polysiloxane blocked by active functional groups, RAFT reagent capable of reacting with the active functional groups of the polysiloxane terminal groups, acrylic acid, fluoroalkyl acrylate, hydroxyalkyl acrylate and styrene, and has a core-shell structure, wherein the core is a polystyrene chain segment, and the shell is a block copolymer chain segment of the polysiloxane, fluoroalkyl acrylate, acrylic acid and hydroxyalkyl acrylate.

Further, the alkyl group having 1 to 4 carbon atoms is selected from methyl, ethyl, propyl, butyl; C1-C4 alkoxy is selected from methoxy, ethoxy, propoxy, butoxy; the C1-4 alkyl is selected from methylene, ethylene, propylene, butylene; C1-C16 fluoroalkyl selected from- (CH)₂)_a-CF₃,-(CF₂)_aCF₃,-(CF₂)_aCHF₂,-(CH₂)_b(CHF)_c-CF₃，-(CH₂)_b-(CHF)_c-CHF₂Wherein a, b, c are independently selected from integers from 0 to 16, provided that the number of carbon atoms in the entire fluoroalkyl group is an integer from 1 to 16; r₄Is selected from- (CH)₂)_dOH，-(CH₂)_e(CHOH)_fCH₂(OH)，-(CHOH)_f(CH₂)_eCH₂OH，-(CH₂)_e(CHOH)_fCH₃，-(CHOH)_f(CH₂)_eCH₃Whereind is an integer from 1 to 6, e and f are integers from 0 to 5, provided that e + f is an integer from 1 to 5; ar is phenyl or naphthyl.

Preferably, R₁，R₂Is methyl, R₃is-CH₂CF₃,-CF₂CF₃，-CF₂CF₂CF₃，-CH₂CF₂CHF₂R4 is selected from-CH₂CH₂OH，-CHOHCH₂OH，-CH₂CH₂CH₂OH，-CH₂CH₂CH₂CH₂OH, Ar is selected from phenyl, A is- (CH)₂)₂-O-(CH₂)₂-O-CO-CH(CH₃)-，-(CH₂)₂-O-(CH₂)₂-O-CO-CH₂-，-Si(CH₃)₂-(CH₂)₃-O-(CH₂)₂-O-CO-CH(CH₃)-，-O-CO-CH(CH₃)-，-O-CO-CH₂-。

Preferably, the particle size of the fluorosilicone polymer nanoparticles is controllable within the range of 30-500nm, preferably within the range of 100-300 nm.

The second purpose of the invention is to provide a preparation method of the fluorosilicone polymer nano-particles, which comprises the following steps:

(S1) reacting the hydroxyl terminated polysiloxane with a RAFT agent having a carboxyl group to obtain a chain transfer agent containing a polysiloxane segment;

(S2) the polymerized monomer is fluoroalkyl acrylate, acrylic acid and hydroxyalkyl acrylate, the RAFT reagent is the chain transfer agent containing polysiloxane chain segment obtained in the step (S1), and the polymerization reaction is carried out under the action of an initiator 1 to obtain the macromolecular chain transfer agent containing silicon fluoride;

(S3) continuously reacting styrene with the macromolecular silicon-fluorine-containing chain transfer agent obtained in the step (S2) under the action of an initiator 2 to obtain a fluorine-silicon polymer, and dispersing the fluorine-silicon polymer in a fluorine solvent to obtain the spherical nano dispersion liquid of the silicon-fluorine-containing polymer.

The preparation of the fluorine-silicon polymer nano particles is realized by adopting heterogeneous polymerization reaction in an RAFT (reversible addition-fragmentation chain transfer) controllable free radical polymerization method and adopting a polymerization induction self-assembly principle. The main component of the fluorine-silicon-containing polymer is a core-shell structure consisting of a block copolymer of styrene and acrylic ester, wherein the styrene is used as a core, and the fluorine-silicon macromolecular chain segment is used as a shell. The introduction of the fluorine-containing acrylate monomer can reduce the surface energy of the material and play a role in super-hydrophobicity; the addition of the organic silicon can further improve the lubricity of the super-hydrophobic surface and reduce the friction force of liquid drops on the surface of the coating; the styrene and acrylate copolymer is used as a polymer skeleton material to reinforce the mechanical property of the material and improve the friction resistance. The fluorine-silicon polymer nano particles obtained by the invention are spherical in shape and controllable in particle size, and can be conveniently matched with other materials to prepare micro-nano structures.

The method for regulating the particle size of the fluorosilicone polymer nanoparticles is one or a combination of the following methods: a) adjusting the amount of styrene and/or chain transfer agent; b) regulating and controlling the reaction time; c) regulating and controlling the reaction temperature; d) regulating and controlling the type and the dosage of the initiator. Preference is given to process a) and/or process b). The reaction temperature and the initiator can be regulated to regulate the particle size of the fluorosilicone polymer nanoparticles, but the linear relation and the temperature of the particle size and the dosage of the initiator are not the same as those of the method a) and the method b) and the linear relation is good. The obtained particle size range is wide. It is therefore understood by those skilled in the art that methods c) and d), although not preferred embodiments of the present invention, are still encompassed by the scope of the present invention.

Further, in the method for preparing fluorosilicone polymer nanoparticles, the RAFT chain transfer agent having a carboxyl group in step (S1) is at least one of 2- (butylthiocarbonylthio) propanoic acid, 2- (phenylthiocarbonylthio) propanoic acid, 4-cyano-4- [ [ (dodecylthio) thiolmethyl ] thio ] pentanoic acid, 4-cyano-4-ethyltrithiopentanoic acid and 2- (ethyltrithiocarbonate) -2-methylpropanoic acid.

The initiator 1 and the initiator 2 are not particularly limited, and may be any radical initiator conventionally used in RAFT reactions, such as azobisisobutyronitrile, 4,4' -azobis (4-cyanovaleric acid), 2,2' -azabicyclo (2-imidazoline) dihydrochloride, 2,2' -azobisisobutylamidine dihydrochloride, 2,2' -azobis (2-methylpropionitrile), 1,1 ' -azobiscyanocyclohexane, and potassium persulfate. Preferably, initiator 1 is 2,2 '-azabicyclo (2-imidazoline) dihydrochloride, and initiator 2 is at least one of 1, 1' -azonitrile cyclohexane.

In the step (S1), the carboxyl activating agent is at least one of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride (EDCI), 4-Dimethylaminopyridine (DMAP), 1, 3-Dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS), and is preferably a combination of EDCI and DMAP in a molar amount of 8-10: 1.

In step (S1), the molar weight ratio of the monohydroxy-terminated polysiloxane, the RAFT chain transfer agent having a carboxyl group, and the carboxyl group activator is 2 to 3: 2-3: 2-4.

In the step (S1), the monohydroxy terminated polysiloxane and the RAFT chain transfer agent with carboxyl are added at low temperature, and then the carboxyl activating agent is added to react at room temperature; the low temperature is-20 to-5 ℃, and the reaction is carried out for 15 to 30 hours at the room temperature and at the temperature of 20 to 30 ℃.

In step (S2), the molar ratio of fluoroalkyl acrylate, acrylic acid, hydroxyalkyl acrylate, and chain transfer agent containing a polysiloxane segment is 3-4:6-8: 0.4-0.6. The amount of initiator 1 used is 0.05 to 1%, preferably 0.07 to 0.08% of the molar amount of the total of the monomers (fluoroalkyl acrylate, acrylic acid, hydroxyalkyl acrylate).

The reaction condition of the step (S2) is that inert gas is firstly introduced to fully remove oxygen, and the reaction is carried out for 2 to 2.5 hours at the temperature of between 50 and 70 ℃. The solvent is a compound of water and oxacycloalkane according to the mass ratio of 6-8: 2-4. The oxacycloalkane is selected from tetrahydrofuran, oxetane, 1, 3-dioxolane, 1, 4-dioxane.

In the step (S3), the amount of the macromolecular chain transfer agent containing silicofluoride is 0.15 to 0.25 per thousand, preferably 0.18 to 0.22 per thousand of the molar amount of the styrene; the amount of the initiator 2 is 0.01 to 0.05 per thousand, preferably 0.02 to 0.03 per thousand of the molar amount of the styrene.

The reaction condition of the step (S3) is that inert gas is firstly introduced to fully remove oxygen, and the reaction is carried out for 2 to 6 hours at the temperature of between 80 and 90 ℃. The solvent is at least one selected from isopropanol, ethyl acetate, n-butanol, tetrahydrofuran, diethyl ether, isopropyl ether, chloroform and dichloromethane.

The step (S3) is a suspension precipitation polymerization, and styrene is a good solvent for both the monomer participating in the polymerization and the polymer. The particle size of the obtained fluorine-silicon polymer nano particles can be conveniently controlled by regulating and controlling the reaction time.

The third purpose of the invention is to provide the application of the fluorine-silicon polymer nano particles as raw materials in preparing the ultra-smooth coating.

The fluorine-silicon polymer nano particles provided by the invention have a certain amount of hydroxyl groups on high molecular weight, and can be crosslinked and cured with substances with isocyanate groups to obtain an ultra-smooth coating.

The substance having an isocyanate group may be a polyisocyanate curing agent commonly used in the art, such as toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, 4',4 "-triphenylmethane triisocyanate, 2' -dimethyl-3, 3',5,5' -triphenylmethane tetraisocyanate.

The material carrying isocyanate groups may also be an isocyanate-terminated polymer, typically prepared by reacting a diol with an isocyanate, such as a polyisocyanate curing agent as disclosed in patent CN103387648A, or a fluorocarbon branched diisocyanate as disclosed in patent CN110078678A,

in a preferred embodiment of the present invention, the material having isocyanate groups is a fluorinated polyurethane having a structure represented by the following formula (II):

wherein R is_aIs alkylene of 2-6 carbon atoms, R_bFor the cyanate ester-removing moiety of diisocyanates R_cis-O- (CH)₂)_c-R_fWherein c is an integer of 0 to 4, R_fIs a fluoroalkyl group having 4 to 12 carbon atoms,

represents polyether segment and/or polyester segment, the molecular weight of the polyether or polyester segment is 200-400, x is an integer of 0-5, and y is an integer of 1-5.

Further, the alkylene group having 2 to 6 carbon atoms is ethylene, propylene, butylene, pentylene, hexylene, and the fluoroalkyl group having 4 to 12 carbon atoms is selected from the group consisting of- (CF)_2)p-CF₃，-(CF_2)p-CHF₂，-(CF_2)q-(CHF_)w-CF₃-(CF_2)q，-(CHF_)w-CHF₂Wherein p is an integer of 3 to 11, q is an integer of 3 to 11, and w is an integer of 0 to 8, provided that w + q is an integer of 3 to 11.

Further, said R_bIs selected from

Wherein represents the site of attachment of an isocyanate group; r_cIs selected from-O-CH₂-(CF₂)₃-CF₃，-O-CH₂-(CF₂)₄-CF₃，O-CH₂-(CF₂)₅-CF₃，-O-CH₂-(CF₂)₆-CF₃，-O-CH₂-(CF₂)₇-CF₃。

The fluorinated polyurethane is obtained by a preparation method comprising the following steps: and (2) curing and crosslinking the fluorine-containing dihydric alcohol, polyether dihydric alcohol and/or polyester dihydric alcohol and dihydric alcohol with diisocyanate to obtain the fluorinated polyurethane terminated by isocyanate groups. The reaction condition is that the reaction is carried out for 3 to 8 hours at the temperature of between 60 and 80 ℃, and the solvent is at least one of butyl acetate, acetone and butanone.

The fluorine-containing dihydric alcohol is 2,2,3, 3-tetrafluoro-1, 4-butanediol, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol, hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-butanediol, 1H,9H, 9H-perfluoro-1, 9-nonanediol, 2,3, 4,4,5, 5-octafluoro-1, 6-hexanediol, 1H,10H, 10H-perfluoro-1, 10-decanediol or 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, more preferably, the fluorine-containing dihydric alcohol is epichlorohydrin and aliphatic fluorinated monohydric alcohol which are subjected to affinity substitution reaction under alkaline conditions to obtain epoxidized fluorinated ether, then under the action of perchloric acid, the ring opening of the epoxy group is carried out to obtain the dihydric alcohol. The structure of the aliphatic fluorinated monohydric alcohol is R_f-(CH₂)_c-OH, wherein R_fAnd c is as defined above for the fluorinated polyurethane of formula (II).

The structural formula of the polyether diol and the polyester diol is shown in the specification

Wherein

Represents a polyether or polyester segment, the polyether diol is selected from polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene glycol-propylene glycol (PTMG), polytetrahydrofuran-propylene oxide copolyol; the polyester polyol is selected from polyethylene glycol adipate diol, polyethylene glycol adipate-diethylene glycol, polyethylene glycol adipate diol, polypropylene glycol adipate diol, polybutylene glycol adipate diol, polyethylene glycol succinate diol and polyethylene glycol terephthalate diol.

The dihydric alcohol is selected from ethylene glycol, propylene glycol, butanediol, hexanediol and cyclohexanediol.

The diisocyanate is selected from diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI).

The molar ratio of the dihydric alcohol is 1-1.2:1-1.2:1-1.2, and the molar ratio of all the dihydric alcohol (the sum of the fluorine-containing dihydric alcohol, the polyether dihydric alcohol and the polyester dihydric alcohol) to the diisocyanate is 1: 1-1.2.

In a more preferred technical scheme, the fluorosilicone polymer nanoparticles provided by the invention are combined with isocyanate group-terminated polyurethane and an adhesion enhancer. The adhesion enhancer is silane coupling agent with amino, such as at least one of 3-aminopropyl trimethoxy silane, aminopropyl methyl diethoxy silane, gamma-diethylenetriamine propyl methyl dimethoxy silane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and the amino methyl trimethoxy silane.

Further, the mass ratio of the fluorine-silicon polymer nano particles, the isocyanate group-terminated polyurethane and the adhesion enhancer is 10-20: 20-40: 1-5.

Furthermore, when the fluorosilicone polymer nanoparticles, the isocyanate-terminated polyurethane and the adhesion enhancer are used to prepare the super-smooth coating, a solvent is required, and the type and amount of the solvent are well known in the art, such as a fluoroalkane solvent, an ester solvent and a ketone solvent.

The fluorinated polyurethane is formed by copolymerization and crosslinking of long-chain polyol, fluorine-containing polyol and isocyanate. The super-smooth hydrophobic coating prepared by matching the fluorinated polyurethane and the nano-scale fluorine-silicon polymer nano-particles has the advantages of hydrophobicity, oleophobicity, wear resistance, corrosion resistance and high adhesive force, and overcomes the defects of easy shedding, poor mechanical property, high cost and the like of the existing super-hydrophobic nano-material coating. The addition of the nano-scale fluorine-containing polymer particles not only provides a micro-nano structure necessary for the surface of the super-hydrophobic coating for the coating; meanwhile, the organic silicon chain segment part provides lubricity for the surface of the coating, so that the rolling angle of liquid contacted with the surface is greatly reduced, and the material has great potential application prospects in the fields of antifouling, icing prevention and self-cleaning. One end of the added adhesion force intensifier is siloxane group which can react with hydroxyl on the surface of the base material, and the amino group on the other end reacts with isocyanate group of fluorinated polyurethane or carboxyl on silicon fluorine polymerization, so that the adhesion force between the super-smooth material and the base material is enhanced.

The coating process of the ultra-smooth coating prepared by the invention is various and simple and feasible, can be spraying, brushing, dipping, roller coating and the like, and is suitable for the surfaces of various substrates. More particularly, after the surface of a part of fluorine-silicon polymer nano particles bonded by non-chemical bonds in the coating is abraded, the fluorine-silicon polymer nano particles can migrate to the surface of the coating through microphase separation under a heating condition, so that a low-surface-energy micro-nano structure is formed again to achieve the self-repairing and durable effect of the coating, and the problem that the existing super-hydrophobic coating is not long in durability is solved.

The invention also provides a preparation method of the super-smooth coating, which comprises the following steps: uniformly mixing fluorinated polyurethane dissolved in a lipid solvent, fluorosilicone polymer nano particle dispersion dispersed in a fluorinated alkane solvent and the fluorinated alkane solvent, and adding an adhesion force enhancer under the stirring condition to obtain the super-smooth coating. The invention also provides application of the super-smooth coating to water and oil resistance of the surface of a substrate. Specifically, the super-smooth coating is coated on the surface of a clean base material, and the super-smooth coating is obtained on the surface of the base material after drying and curing. The method of applying the superhydrophobic coating of the present invention is shown in fig. 1.

Such substrates include, but are not limited to, fabrics, glass, cables, concrete, wood, cardboard, cement, metals, ceramics; means for such coating include, but are not limited to, spraying, brushing, rolling, dipping. The amount of coating applied is not particularly limited, and the dry film thickness of the paint film is generally 10 to 20 μm.

The curing is drying and curing for 4-6h at room temperature, and curing for 20-30h at 60-70 ℃ in a vacuum drying oven.

The invention can efficiently, stably and cheaply obtain the silicon-fluorine polymer nano particles with different particle diameters by simple operation, such as regulating and controlling the reaction time. The obtained silicon fluorine polymer also has hydroxyl and carboxyl groups, and can be conveniently crosslinked and cured with other materials, such as substances containing isocyanate groups, to obtain a super-smooth coating. The organic silicon chain segment in the silicon-fluorine polymer increases the smoothness of the coating, reduces the adhesive force of liquid on the coating and reduces the sliding angle. Not only has beneficial hydrophobic properties, but also has beneficial oleophobic properties. Part of the fluorine-silicon nano particles are bonded with the polymer resin through non-chemical bonds, so that after the surface of the coating is abraded, the micro-phase separation of the fluorine-silicon nano particles and the polymer resin is accelerated through heating treatment, the fluorine-silicon nano particles and the polymer resin are rapidly migrated to the surface of the coating to form a low-surface-energy micro-nano structure again, the self-repairing and abrasion-resistant effects are achieved, and the durability of the coating is effectively improved.

Drawings

FIG. 1 is a schematic illustration of the application of the ultra-smooth coating of the present invention.

FIG. 2 is a transmission electron micrograph of the fluorosilicone polymer nanoparticles obtained in preparation example 1.

FIG. 3 is a TEM image of the fluorosilicone polymer nanoparticles obtained in preparation example 3.

FIG. 4 is a TEM image of the fluorosilicone polymer nanoparticles obtained in preparation example 4.

FIG. 5 is a TEM image of the fluorosilicone polymer nanoparticles obtained in preparation example 5.

FIG. 6 is a TEM image of the fluorosilicone polymer nanoparticles obtained in preparation example 10.

FIG. 7 is a TEM image of fluorosilicone polymer nanoparticles prepared in preparation example 11.

FIG. 8 is a TEM image of fluorosilicone polymer nanoparticles prepared in preparation example 12.

FIG. 9 is a scanning electron micrograph of the surface of the ultra-smooth coating obtained in example 1.

FIG. 10 is a surface contact angle measurement of the ultra-smooth coating obtained in example 1.

Fig. 11 is an illustration of the smoothness of the super-smooth coating obtained in example 1 with respect to oil, anti-oil adhesion and self-cleaning function.

FIG. 12 is a graph showing the performance of the ultra-smooth coating obtained in example 1 after being erased by oil-based marker and water-based marker.

Detailed Description

The superhydrophobic coatings of the present invention are further illustrated and described in the following specific examples, in which the materials are all commercially available reagents unless otherwise specified.

Polyether diol (PTMG) was purchased from Pasteur and had a molecular weight of 1000.

Monohydroxy-terminated polydimethylsiloxane was purchased from Sigma. The structural formula is

A total of 4 specifications, each having a molecular weight of 3410g/mol, n being about 43; the molecular weight is 4080g/mol, and n is about 52; the molecular weight is 4670g/mol, and n is about 60; the molecular weights were 5720g/mol, respectively, and n was about 74.

Preparation example 1

The fluorine-silicon polymer nano particles are prepared by adopting heterogeneous suspension polymerization reaction in an RAFT (reversible addition-fragmentation chain transfer) controllable free radical polymerization method and adopting a polymerization-induced self-assembly principle. The specific operation is as follows: n- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride (EDCI, 0.43g,2.24mmol) was dissolved in 5mL of dichloromethane and added dropwise to a solution (10mL) of monohydroxy-terminated polydimethylsilane (7.48g,1.6mmol, number of repeating units of dimethylsilane about 60), RAFT chain transfer agent 2- (butylthiocarbonylthio) propanoic acid (PABTC, 0.57g,2.39mmol) and 4-dimethylaminopyridine (DMAP, 0.029g,0.24mmol) in dichloromethane at-20 deg.C, and after the addition was complete, stirring was carried out at room temperature for 20 hours. After the reaction was complete, the organic layer was washed 2 times with saturated aqueous NaCl solution and dried to obtain silane-containing RAFT chain transfer agent. Adding fluorine-containing monomer trifluoroethyl acrylate (1.2g, 7.8mmol), hydroxyethyl acrylate (1.7g, 15mmol), acrylic acid (1.1g, 15mmol), initiator 2,2' -azabicyclo (2-imidazoline) dihydrochloride VA-044(10mg, 0.032mmol), the prepared organosilane chain transfer agent (7.80g, 1.6mmol), mixed solvent water/1, 4-dioxane (80: 20/m: m, 40g) into a 100mL round-bottom flask, sealing and placing in a magnetic stirrer at 60 ℃ for stirring for 2 hours after nitrogen is introduced for 20 minutes, cooling the obtained mixed solution after the reaction is finished, distilling off the redundant solvent, and finally obtaining the fluorosilicone macromolecular chain transfer agent for preparing the fluorosilicone polymer nanoparticles. Dissolving the fluorosilicone macromolecular chain transfer agent (0.54g, 0.05mmol), styrene monomer (25g, 0.24mol) and initiator 1, 1' -azonitrile cyclohexane (1.23mg, 0.005mmol) in isopropanol (25g, 48.8 wt%, styrene: isopropanol: 1/m: m), introducing nitrogen for 10 minutes, placing in a magnetic stirrer at 90 ℃ for stirring for 3 hours, after the reaction is finished, placing in an ice-water bath for terminating polymerization, reducing pressure, extracting the monomer and solvent which do not participate in the reaction, dispersing in a fluorine solvent-225, and stirring at room temperature for 24 hours to obtain the spherical fluorine-containing polymer nano dispersion liquid with solid content of 50%.

Fig. 2 is a transmission electron micrograph of the fluorosilicone polymer nanoparticles obtained in preparation 1, which shows that the polymer microspheres have a narrow particle size distribution, and the average particle size of the polymer microspheres is about 180 nm.

Preparation example 2

N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride (EDCI, 0.288g,1.50mmol) was dissolved in 5mL of dichloromethane and added dropwise to a solution (10mL) of monohydroxy-terminated polydimethylsilane (PDMS, 4.37g,1.07mmol, number of repeating units of dimethylsilane about 52), RAFT chain transfer agent 2- (butylthiocarbonylthio) propanoic acid (PABTC, 0.381g,1.60mmol) and 4-dimethylaminopyridine (DMAP, 0.019g,0.16mmol) in dichloromethane at-20 deg.C, and after the addition was complete, the mixture was stirred at room temperature for 20 hours. After the reaction was complete, the organic layer was washed 2 times with saturated aqueous NaCl solution and dried to obtain silane-containing RAFT chain transfer agent. Adding fluorine-containing monomer trifluoroethyl acrylate (1.2g, 7.8mmol), hydroxyethyl acrylate (1.7g, 15mmol), acrylic acid (1.1g, 15mmol), initiator 2,2' -azabicyclo (2-imidazoline) dihydrochloride VA-044(10mg, 0.032mmol), the prepared organosilane chain transfer agent (4.53g, 1.07mmol), mixed solvent water/1, 4-dioxane (80: 20/m: m, 40g) into a 100mL round-bottom flask, sealing and placing in a magnetic stirrer at 60 ℃ for stirring for 2 hours after nitrogen is introduced for 20 minutes, cooling the obtained mixed solution after the reaction is finished, distilling off the redundant solvent, and finally obtaining the fluorosilicone macromolecular chain transfer agent for preparing the fluorosilicone polymer nanoparticles. Dissolving the fluorosilicone macromolecular chain transfer agent (0.50g, 0.05mmol), styrene monomer (25g, 0.24mol) and initiator 1, 1' -azonitrile cyclohexane (1.23mg, 0.005mmol) in isopropanol (25g, 48.8 wt%, styrene: isopropanol: 1/m: m), introducing nitrogen for 10 minutes, placing in a magnetic stirrer at 90 ℃ for stirring for 3 hours, after the reaction is finished, decompressing and extracting the monomer and solvent which do not participate in the reaction, dispersing in fluorine solvent AK-225, and stirring at room temperature for 24 hours to obtain the spherical fluorine-containing polymer nano dispersion liquid, wherein the solid content is 40%, and the average particle size of the polymer microspheres is 200 nm.

Preparation example 3

The other conditions and operations are the same as those in preparation example 1, except that the fluorosilicone macromolecular chain transfer agent and the styrene monomer are polymerized under the action of the initiator, and the mixture is placed in a magnetic stirrer at 90 ℃ to be stirred for 0.5 hour. The electron micrograph of the obtained fluorosilicone polymer nanoparticles is shown in FIG. 3, and the average particle size is about 15 nm.

Preparation example 4

The other conditions and operations were the same as in preparation example 1 except that the amount of styrene monomer used was 10g, and the mixture was stirred in a magnetic stirrer at 90 ℃ for 3 hours. The electron micrograph of the obtained fluorosilicone polymer nanoparticles is shown in FIG. 4, and the average particle size is 30 nm. The resulting polymer nanoparticles are significantly smaller in particle size, probably due to the reduced amount of styrene, which is not only a monomer for polymerization but also a good solvent for the polymer. The method adopts suspension precipitation polymerization, so that the styrene dosage is too small, the polymer is precipitated without complete reaction, and the chain growth cannot be continued. Therefore, the length of the polystyrene segment, or the number of repeating units, in the resulting polymer is low, and the particle size is small. And the polymer microspheres have wider particle size distribution due to different chain segments of the polystyrene.

Preparation example 5

The other conditions and operations are the same as those in preparation example 1, except that the fluorosilicone macromolecular chain transfer agent and the styrene monomer are polymerized under the action of the initiator, and the mixture is placed in a magnetic stirrer at 90 ℃ to be stirred for 1 hour. The electron micrograph of the obtained fluorosilicone polymer nanoparticles is shown in FIG. 5, and the average particle size is 50 nm.

Preparation example 6

The other conditions and operation were the same as in preparation example 1, except that the monohydroxy-terminated polydimethylsilane had a molecular weight of 3410g/mol and the number of recurring dimethylsilane units was approximately 43; the molar amount of monohydroxy-terminated polydimethylsilane used was constant and remained at 1.6 mmol.

Preparation example 7

The other conditions and operations are the same as those in preparation example 1, except that when preparing the fluorosilicone polymer nanoparticles, the molecular weight of the monohydroxy terminated polydimethylsilane is 5720g/mol, and the number of the dimethylsilane repeating units is about 74; the molar amount of monohydroxy-terminated polydimethylsilane used was constant and remained at 1.6 mmol.

Preparation example 8

The other conditions and operations were the same as in preparation example 1 except that the amounts of the monomers used were changed to fluorine-containing monomers trifluoroethyl acrylate 7.8mmol, hydroxyethyl acrylate 7.8mmol, and acrylic acid 7.8 mmol.

Preparation example 9

The other conditions and operation were the same as in preparation example 1 except that the amount of the organosilane chain transfer agent used was 10.27g, 2.2 mmol.

Preparation example 10

The other conditions and operation were the same as in preparation example 1 except that DMAP was not added, the amount of EDCI added was changed to 2.5mmol, and the photograph of an electron microscope is shown in FIG. 6. It can be seen that when a single carboxyl activator is used, rather than the DMAP and EDCI compounded carboxyl activator of preparation example 1, the average particle size of the resulting nanoparticles does not change significantly, but the particle size distribution is broadened.

Preparation example 11

The other conditions and operations are the same as those in preparation example 1, except that the fluorosilicone macromolecular chain transfer agent and the styrene monomer are polymerized under the action of the initiator, and the mixture is placed in a magnetic stirrer at 90 ℃ to be stirred for 5 hours. The electron micrograph of the obtained fluorosilicone polymer nanoparticles is shown in FIG. 7, and the average particle size is 300 nm. The longer the time of styrene polymerization, the longer the chain length of the polystyrene segment in the copolymer, and the larger the particle size of the polymer nanoparticles.

Preparation example 12

The other conditions and operations are the same as those in preparation example 1, except that the fluorosilicone macromolecular chain transfer agent and the styrene monomer are polymerized under the action of the initiator, and the mixture is placed in a magnetic stirrer at 90 ℃ to be stirred for 2 hours. The electron micrograph of the obtained fluorosilicone polymer nanoparticles is shown in FIG. 8, and the average particle diameter is 100 nm. The results show that the time of styrene participating in polymerization is shortened, the chain length of the polystyrene chain segment in the copolymer is shortened, and the particle size of the polymer nanoparticles is further reduced.

Example 1

1) Preparation of fluorine-containing dihydric alcohol

The specific operation is as follows: 2,3, 4,5, 6,7, 8-pentadecafluorooctan-1-ol (PDFOL) (4.898g,0.012mol) and epichlorohydrin (7.54mL,0.096mol) were dissolved in 80mL of 1, 4-dioxane (80mL), and powdered sodium hydroxide (0.528g,0.132mol) was added to the stirred mixed solution, followed by heating at 70 ℃ for 8 hours. After the reaction, the precipitate was removed by filtration, and the filtrate was concentrated by a rotary evaporator to obtain an intermediate 3- (2,2,3,3,4,5,5,6,6,7,7,8,8, 8-pentadecafluorooctyloxymethyl) -oxirane (PDFOMO). The crude PDFOMO was purified by silica gel column chromatography using n-hexane/ethyl acetate (50:1) to give 2.7g of PDFOMO (59%). PDFOMO (2.7g,0.0592mol) was dissolved in 60mL THF, and 30mL perchloric acid (8%) was added. After the mixture was stirred at room temperature for 12 hours, perchloric acid was neutralized with sodium carbonate. The solvent was removed by rotary evaporation, the resulting residue was washed with 50mL of diethyl ether to remove the salts, and the solvent diethyl ether was removed by rotary evaporation. The crude PFOPPOL was purified by silica gel column chromatography with n-hexane/ethyl acetate (4:3) to give 2.25g of PFOPPOL. The synthetic route is as follows:

2) preparation of Fluorinated Polyurethane (FPU)

Synthesizing fluorine-containing polyurethane (FPU) by using a solution polymerization method, wherein the fluorine-containing polyurethane (FPU) is prepared from isophorone diisocyanate (IPDI), polyether glycol (PTMG), fluorine-containing glycol (PFOPDOL) and 1, 4-Butanediol (BDO) chain extenders. The specific operation steps are as follows: IPDI (0.045mol, 10g) was added dropwise to PTMG (0.01mol, 10g) at 60 ℃ followed by gradually raising the temperature to 80 ℃ and reacting for 2 hours. And adding a small amount of butyl acetate in the reaction to adjust the viscosity of the system. BDO (0.012mol, 1.08g) and PFOPDOL (0.013mol, 6.16g) were added to the above mixed solution, and the reaction was continued for 4 hours to obtain an FPU prepolymer. After cooling to room temperature, butyl acetate was added to make the solid content 40%.

The synthetic route is as follows:

3) preparation of fluorosilicone polymer nanoparticles

Same as in preparation example 1

4) Preparation of super-smooth coating on surface of base material

The specific operation is as follows: the surface of the glass substrate is sequentially cleaned by ethanol and acetone to remove oil stains, and the glass substrate is dried in a vacuum drying oven at 70 ℃ for 12 hours. Uniformly mixing 40G of the FPU prepolymer butyl acetate solution prepared above, 20G of fluorosilicone polymer nanoparticle dispersion liquid and 39G of AK-225G solvent, slowly dropwise adding 1G of adhesion enhancer KH-550 under stirring, and continuously stirring for 30 minutes. And (3) uniformly spraying the mixed solution on the surface of the treated base material by using a high-volume low-pressure spray gun at room temperature, drying and curing for 4 hours at room temperature, and then putting the base material into a vacuum drying oven for curing for 24 hours at 70 ℃ to obtain the fluorosilicone polymer nanoparticle modified fluorinated polyurethane super-smooth coating. The affinity of the fluorine-containing polyurethane and the substrate enhanced by the adhesion enhancer is schematically shown below:

fig. 6 is a scanning electron microscope photograph of the surface of the ultra-smooth coating obtained in the present embodiment, and it can be seen that the coating is uniform and dense and has a certain micro-nano structure. FIG. 7 is a surface contact angle test of the super-smooth coating obtained in this example, and it can be seen that the contact angle with water is 131 deg., and the super-smooth coating has good hydrophobic property.

The used oil was dropped on the surface of the coating obtained in example 1, stood upright, and a photograph was taken of the oil droplets from the beginning to 50 seconds, as shown in fig. 8. The waste engine oil does not have adhesiveness on the surface of the coating, the waste engine oil slips from the surface of the coating after a short time, and the low adhesiveness of the waste engine oil shows that the coating has good smoothness, anti-oil-stain adhesiveness and a self-cleaning function.

The coating of the embodiment is written by an oil-based marking pen and a water-based marking pen respectively, and the handwriting can be completely erased by a common paper towel, as shown in fig. 9, the handwriting of the oil-based marking pen on the coating can be seen, and the handwriting on the coating can be completely erased after the common paper towel is wiped. The low adhesion to the marked handwriting shows that the coating has good scrawling resistance and has good application prospect in the fields of municipal construction and coating and the like.

Example 2

1) Preparation of fluorine-containing dihydric alcohol

The specific operation is as follows: 2,3, 4,5, 6,7, 8-pentadecafluorooctan-1-ol (PDFOL) (4.898g,0.012mol) and epichlorohydrin (7.54mL,0.096mol) were dissolved in 80mL of 1, 4-dioxane (80mL), and powdered sodium hydroxide (0.528g,0.132mol) was added to the stirred mixed solution, followed by heating at 70 ℃ for 8 hours. After the reaction, the precipitate was removed by filtration, and the filtrate was concentrated by a rotary evaporator to obtain an intermediate 3- (2,2,3,3,4,5,5,6,6,7,7,8,8, 8-pentadecafluorooctyloxymethyl) -oxirane (PDFOMO). The crude PDFOMO was purified by silica gel column chromatography using n-hexane/ethyl acetate (50:1) to give 2.7g of PDFOMO (59%). PDFOMO (2.7g,0.0592mol) was dissolved in 60mL THF, and 30mL perchloric acid (8%) was added. After the mixture was stirred at room temperature for 12 hours, perchloric acid was neutralized with sodium carbonate. The solvent was removed by rotary evaporation, the resulting residue was washed with 50mL of diethyl ether to remove the salts, and the solvent diethyl ether was removed by rotary evaporation. The crude PFOPPOL was purified by silica gel column chromatography with n-hexane/ethyl acetate (4:3) to give 2.25g of PFOPPOL.

2) Preparation of Fluorinated Polyurethane (FPU)

Synthesizing fluorine-containing polyurethane (FPU) by using a solution polymerization method, wherein the fluorine-containing polyurethane (FPU) is prepared from isophorone diisocyanate (IPDI), polyether glycol (PTMG), fluorine-containing glycol (PFOPDOL) and 1, 4-Butanediol (BDO) chain extenders. The specific operation steps are as follows: IPDI (0.045mol, 10g) was added dropwise to PTMG (0.01mol, 10g) at 60 ℃ followed by gradually raising the temperature to 80 ℃ and reacting for 2 hours. And adding a small amount of butyl acetate in the reaction to adjust the viscosity of the system. BDO (0.008mol, 0.71g) and PFOPDOL (0.017mol, 8.06g) were added to the above mixed solution, and the reaction was continued for 4 hours to obtain an FPU prepolymer. After cooling to room temperature, butyl acetate was added to make the solid content 50%.

3) Preparation of fluorosilicone polymer nanoparticles

Same as preparation example 2

4) Preparation of super-smooth coating on surface of base material

The specific operation is as follows: and cleaning the surface of the tinplate base material by using acetone to remove oil stains and rust stains, and drying in a drying oven in a vacuum drying oven at 70 ℃ for 12 hours. Uniformly mixing 40G of the FPU prepolymer butyl acetate solution prepared above, 10G of fluorosilicone polymer nanoparticle dispersion liquid and 48G of AK-225G solvent, slowly dropwise adding 2G of adhesion enhancer KH-550 under stirring, and continuously stirring for 30 minutes. And (3) uniformly spraying the mixed solution on the surface of the treated base material by using a high-volume low-pressure spray gun at room temperature, drying and curing for 4 hours at room temperature, and then putting the base material into a vacuum drying oven for curing for 24 hours at 70 ℃ to obtain the fluorosilicone polymer nanoparticle modified fluorinated polyurethane super-smooth coating. The contact angle with water was tested to be 125 °.

Examples 3 to 12

The other conditions and operations were the same as those of example 1 except that fluorosilicone polymer nanoparticles were prepared in preparation examples 3 to 12, respectively.

Example 13

The other conditions and operations were the same as those of example 1 except that the amount of the fluorosilicone polymer nanoparticle dispersion used in step (4) was changed to 40 g.

Example 14

The other conditions and operations were the same as those of example 1 except that the amount of the fluorosilicone polymer nanoparticle dispersion used in step (4) was changed to 7 g.

Comparative example 1

The other conditions and operations were the same as in example 1 except that in step (4), no adhesion enhancer KH-550 was added.

Comparative example 2

Porous polytetrafluoroethylene membrane with average pore diameter of 200nm and thickness of 60-80 μm, and dropping lubricating oil with dropper

100 to form an oil film on the surface to obtain a SLIPS coating.

Application example 1

The coatings obtained in the inventive and comparative examples were subjected to the following performance tests, and the results are shown in table 1 below.

1.Testing of coating hydrophobicity: the contact angle is characterized by the contact angle with water, and the contact angle test adopts a FCA2000A2 type contact angle measuring instrument.

2.Testing of the oleophobicity of coatings: hexadecane was dropped on the coating, the coating was placed vertically, the sliding distance of the oil drop was tested for 5s, and the average was taken 5 times. The sliding distance is a linear distance that starts from the circular center of the initial oil drop when it lands and ends at the end of the oil drop that is lower than 5s later.

3.Hardness testThe pencil hardness test is adopted, and the test method refers to GB 6739-86.

4Adhesion testThe method is carried out according to ISO4624-2004, a grid cutting tester is used for coating a sample on a sample plate, after the sample is dried for 16 hours, the sample plate is pulled in parallel by 3-4cm by the grid cutting tester, the gap between cutting knives is 2mm, and a paint film is cut through to a substrate; then, the same method is used to form a plurality of small squares perpendicular to the former. Comparative grading was performed using visual or magnifying glass control standards. The criteria for its classification are described as:

rank of	Description of the invention
		Level 0	The cutting edge is completely smooth without one lattice falling off
Level 1	A little coating layer falls off at the intersection, and the affected area cannot be obviously more than 5 percent
		Stage 2	The coating at the intersection of the cuts or along the edges of the cuts falls off, and the influence area is 5 to 15 percent
Grade 3	The cross cutting area of the coating which is affected by large-area falling along the cutting edge is 15 to 35 percent
		4 stage	The whole lattice falls off along the edge, some lattices partially or completely fall off, and the affected area is 35 to 65 percent

5.Anti-graffiti Performance test: reference is made to the industry standard JG/T304-2011. A20 mm by 20mm mark was drawn on the center of the coating with an oil-based marker, and wiping was repeated 25 times with a wiping pressure of about 1.5 kg. The cleanability evaluation criteria were as follows:

rank of	Description of the invention
		Level 1	Can be removed by dry lint-free cotton cloth
Stage 2	Can be removed by 1% neutral water-based weak cleaning agent
		Grade 3	Can be removed with orange-based detergent
4 stage	Can be removed by anhydrous alcohol
		Can not be removed	The four cleaning materials can not be removed, or the coating after cleaning has obvious light loss, color change or other damages

All test results are shown in table 1 below:

TABLE 1

The data in Table 1 show that the super-smooth coating provided by the invention has excellent super-smooth performance and good performances in the aspects of hydrophobicity and oleophobicity. It can be seen that the change in the coating composition of the present invention has a greater impact on the oleophobic properties, for reasons that may be related to the mechanism of water and oil repellency of the ultra-smooth coating, the hydrophobicity being achieved by its low surface energy, and the ultra-smooth properties being achieved by the extremely low friction between the coating and the oil droplet interface. Because of the existence of the adhesion force intensifier in the coating, the acting force between the coating and the substrate is greatly improved; meanwhile, the hardness of the super-smooth coating reaches 4H, and the problem that the waterproof and oilproof performance is reduced due to the fact that the super-smooth coating is easy to peel off and damage is solved.

Application example 2

In order to test the abrasion resistance and weather resistance of the resulting superhydrophobic coating, the following tests were performed, and the superhydrophobic coating after the test was re-tested for contact angle and rolling angle, and the results are shown in table 2 below.

1. And (3) wear resistance test: the resulting mixture was rubbed repeatedly 200 times with 320 mesh sandpaper under a 500g weight with the edge of the sandpaper as a boundary, and the hydrophobicity (contact angle with water) and oleophobicity (sliding distance of oil droplets 5 s) after the rubbing were measured.

2. And (3) washing resistance test: the coating was rinsed with water for 12h and tested for hydrophobicity and oleophobicity.

3. And (3) freeze-thaw resistance test: a full-automatic low-temperature freeze-thaw tester (JC-ZDR-6, Xin power electromechanical equipment instrument factory) is adopted, and 20 cycles are carried out with a freeze-thaw cycle of-40 ℃/6 h-25 ℃/6h as one cycle.

TABLE 2

As can be seen from the data in Table 2, the ultra-smooth coating of the present invention has excellent wear resistance, washing resistance and freeze-thaw resistance. In all three tests, both hydrophobicity and oleophobicity were well preserved and did not undergo a severe drop. In the preferred embodiment of the present invention, the reduction is very small, especially the oleophobicity, since the coating of the present invention does not contain lubricating oil, but the silicone segment is chemically bonded as part of the polymer nanofiller, and will not easily fall off and precipitate from the coating. Therefore, the ultra-smooth performance is not substantially reduced in the washing resistance test and the freeze-thaw resistance test. Comparative example 2 is a coating of a conventional slippery liquid-impregnated porous surface (SLIPS), in which a lubricant is filled in a porous material, and although excellent hydrophobic and oleophobic properties can be obtained, in friction resistance, washing resistance and freeze-thaw resistance tests, the loss of the lubricant causes the hydrophobic and oleophobic properties of the coating to be reduced, especially the oleophobic properties.

Application example 3

The surface of the coating obtained in the example was scratched with a sharp knife 500 times to make the surface of the coating have a distinct scratch, the contact angle of the scratched coating with water was tested, the coating was baked at 130 ℃ for 10 minutes, and the contact angle of the coating with water was retested after cooling, and the results are shown in table 3 below, where it can be seen that the super-hydrophobic and slippery property was restored after the heating treatment, because the fluorine-containing portion of the coating migrated to the surface again.

TABLE 3

As can be seen from the data in Table 3, the coating obtained by the super-smooth coating provided by the invention also has a self-repairing function, and the fluorine-containing part of the scratched coating can migrate to the surface again only after being simply heated and baked for a short time, so that the hydrophobic property of all or part of the coating is recovered.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A fluorosilicone polymer nanoparticle with controllable particle size, the fluorosilicone polymer having a structure represented by the following formula (I):

wherein R is₁，R₂Independently H, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxyl, R₃Is a fluoroalkyl group of 1 to 16 carbon atoms, R₄Is alkyl substituted by hydroxy, Ar is aryl with 6 to 20 carbon atomsA is-R₅-OCO-R₆-, wherein R₅，R₆Independently selected from- (Si (CH)₃)₂)_tAlkylene having 1 to 4 carbon atoms, - (Si (CH)₃)₂)_tAlkylene oxide of 1 to 4 carbon atoms, R₅，R₆Optionally substituted by hydroxy, halogen, t is 0 or 1; n is selected from an integer of 50-80, m is selected from an integer of 5-20, p is selected from an integer of 10-50, q is selected from an integer of 10-50, and s is selected from an integer of 100-1000;

the fluorosilicone polymer nano particle is a block copolymer obtained by RAFT reaction of polysiloxane with an end capped by an active functional group, RAFT reagent capable of reacting with the active functional group at the end group of the polysiloxane, acrylic acid, fluoroalkyl acrylate, hydroxyalkyl acrylate and styrene, and has a core-shell structure, wherein the core is a polystyrene chain segment, and the shell is a block copolymer chain segment of the polysiloxane, the fluoroalkyl acrylate, the acrylic acid and the hydroxyalkyl acrylate.

2. The fluorosilicone polymer nanoparticles of claim 1, wherein the C1 to C4 alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl; C1-C4 alkoxy is selected from methoxy, ethoxy, propoxy, butoxy; alkylene having 1 to 4 carbon atoms selected from methylene, ethylene, propylene, butylene; C1-C16 fluoroalkyl selected from- (CH)₂)_a-CF₃,-(CF₂)_aCF₃,-(CF₂)_aCHF₂,-(CH₂)_b(CHF)_c-CF₃，-(CH₂)_b-(CHF)_c-CHF₂Wherein a, b, c are independently selected from integers from 0 to 16, provided that the number of carbon atoms in the entire fluoroalkyl group is an integer from 1 to 16; r₄Is selected from- (CH)₂)_dOH，-(CH₂)_e(CHOH)_fCH₂(OH)，-(CHOH)_f(CH₂)_eCH₂OH，-(CH₂)_e(CHOH)_fCH₃，-(CHOH)_f(CH₂)_eCH₃Wherein d is an integer of 1 to 6, and e and f are integers of 0 to 5Provided that e + f is an integer of 1 to 5; ar is phenyl or naphthyl.

3. The fluorosilicone polymer nanoparticle of claim 2, wherein R is₁，R₂Is methyl, R₃is-CH₂CF₃,-CF₂CF₃，-CF₂CF₂CF₃，-CH₂CF₂CHF₂，R₄Is selected from-CH₂CH₂OH，-CHOHCH₂OH，-CH₂CH₂CH₂OH，-CH₂CH₂CH₂CH₂OH, Ar is selected from phenyl, A is- (CH)₂)₂-O-(CH₂)₂-O-CO-CH(CH₃)-，-(CH₂)₂-O-(CH₂)₂-O-CO-CH₂-，-Si(CH₃)₂-(CH₂)₃-O-(CH₂)₂-O-CO-CH(CH₃)-，-O-CO-CH(CH₃)-，-O-CO-CH₂-。

4. The fluorosilicone polymer nanoparticles of claim 1, wherein the particle size of the fluorosilicone polymer nanoparticles is controllable in the range of 30-500 nm.

5. The fluorosilicone polymer nanoparticles of claim 4, wherein the particle size of the fluorosilicone polymer nanoparticles is controllable within the range of 100nm to 300 nm.

6. The method for preparing fluorosilicone polymer nanoparticles with controllable particle size according to any one of claims 1 to 5, comprising the steps of:

7. The preparation method according to claim 6, wherein the particle size of the fluorosilicone polymer nanoparticles is controlled by one or more of the following methods: a) adjusting the amount of styrene and/or chain transfer agent; b) regulating and controlling the reaction time; c) regulating and controlling the reaction temperature; d) regulating and controlling the type and the dosage of the initiator.

8. The method of claim 6, wherein the RAFT chain transfer agent having a carboxyl group in the step (S1) is at least one selected from the group consisting of 2- (butylthiocarbonylthio) propanoic acid, 2- (phenylthiocarbonylthio) propanoic acid, 4-cyano-4- [ [ (dodecylthio) thiolmethyl ] thio ] pentanoic acid, 4-cyano-4-ethyltrithiopentanoic acid and 2- (ethyltrithiocarbonate) -2-methylpropanoic acid; and/or

The initiator 1 and the initiator 2 are selected from azobisisobutyronitrile, 4,4' -azobis (4-cyanovaleric acid), 2,2' -azabicyclo (2-imidazoline) dihydrochloride, 2,2' -azobisisobutylamidine dihydrochloride, 2,2' -azobis (2-methylpropionitrile), 1,1 ' -azobiscyanocyclohexane and potassium persulfate.

9. The process of claim 8 wherein initiator 1 is 2,2 '-azabicyclo (2-imidazoline) dihydrochloride and initiator 2 is 1, 1' -azocyanocyclohexane.

10. The method of claim 6, wherein the step (S1) is performed in the presence of a carboxyl activating agent, the carboxyl activating agent being at least one of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride (EDCI), 4-Dimethylaminopyridine (DMAP), 1, 3-Dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS);

in step (S1), the molar weight ratio of the hydroxyl terminated polysiloxane, the RAFT chain transfer agent with carboxyl groups and the carboxyl activating agent is 2 to 3: 2-3: 2-4.

11. The method of claim 10, wherein the carboxyl activating agent is a combination of EDCI and DMAP in a molar ratio of 8-10: 1.

12. The method of claim 6, wherein the reaction conditions in the step (S3) are that inert gas is introduced to remove oxygen sufficiently, and the reaction is carried out at 80-90 ℃ for 2-6 h.

13. Use of the fluorosilicone polymer nanoparticles of any one of claims 1 to 5 or the fluorosilicone polymer nanoparticles prepared by the preparation method of any one of claims 6 to 12 as a raw material for formulating a super-smooth coating.