Antifouling and wear-resistant additive, and preparation method and application thereof

Abstract

The application discloses a kind of antifouling wear-resistant aids and its preparation method and application, belong to fluorine-containing functional preparation technical field, the antifouling wear-resistant aid is made of the following molar fraction raw materials: single end active perfluoropolyether alcohol PFPE-OH 1-2 parts;Isophorone diisocyanate 1-2 parts;Surface contains hydroxyl nano-silica 1 part;Contain unsaturated bond monoisocyanate 2-5 parts;Hydroxy acrylate 2-25 parts;Comonomer 40-400 parts;Reactive monomer 2-20 parts;The reactive monomer contains unsaturated bond, for side chain grafting.This antifouling wear-resistant aid includes nano-silica hybrid multi-branched polymer containing perfluoropolyether group, and multiple unsaturated sites are contained therein, suitable for UV curing coating system, can significantly improve the antifouling, fingerprint resistance and wear resistance of coating surface.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fluorine-containing functional preparations, in particular to a stain-resistant and wear-resistant additive, a preparation method and application thereof. BACKGROUND

[0002] An ultraviolet (UV) cured coating is a hard coating formed by rapid curing and cross-linking of active monomers in the coating under the irradiation of a photoinitiator under ultraviolet light. The UV cured coating has the advantages of fast curing speed, green environmental protection, low energy consumption, good adhesion, high coating film quality, and good durability, and is thus widely used in the fields of electronics, automobiles, medicine, and packaging. In smart phones, tablet computers, and optical displays, the UV coating is often used as a key display interface material. However, it is prone to adhere to impurities such as fingerprints, sebum, and sweat, which affects the user experience. In addition, wear resistance is also one of the key technical indicators. Therefore, it is necessary to develop a stain-resistant and wear-resistant additive to improve the stain resistance and wear resistance of the UV cured coating.

[0003] The method for improving the stain resistance of the coating is generally to add a low surface tension substance (such as a functional additive containing fluorine or silicon) to reduce the surface energy of the coating, or to directly improve the stain resistance by changing the microstructure of the coating surface. Obviously, the method of adding a low surface tension substance to improve the stain resistance of the coating is more efficient and easier to implement. Perfluoropolyether stain-resistant agents have been widely used in recent years, but due to their high fluorine content, they have poor compatibility with other components in the coating, which leads to component separation and thus deteriorates the surface properties. The use of long-chain fluoralkyl side chains can significantly improve the surface stain resistance, but the coating surface has poor smoothness, which affects the user experience of the product. The double-end perfluoropolyether can solve the problems of compatibility and smoothness, but the raw materials are not easy to obtain, making it difficult to achieve widespread use.

[0004] The patent document with the publication number CN118440292A discloses an acrylic compound containing a perfluoropolyether group, which has a central structural unit of two arylene skeletons connected by a carbodiimide group, wherein the perfluoropolyether group is bonded to one end via a urethane bond and a multifunctional (methyl) acryloyl group is bonded to the other end via a urethane bond; the acrylic compound is soluble in commonly used solvents and can impart good initial contact angle and wear resistance to the coating. The reaction mechanism of the present application is the reaction of alcohol hydroxyl group with polyisocyanate to form urethane, and the multi-end bonding of perfluoropolyether chain segment is inevitable, which will lead to difficult control of the structure.

[0005] The patent document with publication number CN115612031A discloses a thermosetting antifouling additive, which is a high molecular polymer with carbon-carbon as the main chain, containing perfluoropolyether groups and hydroxyl groups in the side chain, with fluorine content not exceeding 40.0%, hydroxyl value not less than 17.5 mg KOH / g, and molecular weight of perfluoropolyether group not less than 800 g / mol. The additive is soluble in non-halogen ester ketone alcohol benzene solvents, and has excellent compatibility with hydroxyl acrylate resin and thermosetting coatings. The antifouling additive has good effect when applied in thermosetting coating systems, but when added to UV curing systems, the wear resistance is greatly reduced due to the lack of fixed anchor points, affecting the surface state of the coating.

[0006] The patent document with publication number CN105482680A discloses a UV-curable hyperbranched perfluoropolyether polyurethane acrylate coating, which contains a hyperbranched perfluoropolyether polyurethane acrylate oligomer. The hyperbranched perfluoropolyether polyurethane acrylate oligomer is obtained by reacting perfluoropolyether acid chloride with hyperbranched polyester to obtain a hyperbranched fluorine-containing polyester, and then reacting with polyisocyanate and (methyl) acrylate. The corresponding reaction also has the probability of generating a double-end fluorine-containing hyperbranched polyester, and the reactivity of acid chloride with hydroxyl group is very high, and the reaction is not easy to control. On the one hand, the hyperbranched perfluoropolyether polyurethane acrylate oligomer may have a high fluorine content, which affects the compatibility with the UV coating system, on the other hand, there may be a problem of insufficient crosslinking with active monomers in the UV coating system, affecting the wear resistance of the coating.

[0007] Therefore, there is a need to develop a new type of single-end perfluoropolyether-based antifouling and wear-resistant additive for UV curing coating systems. SUMMARY

[0008] In order to solve the problems of poor controllability of preparation process, difficulty in obtaining raw materials, poor wear resistance and compatibility of the antifouling and wear-resistant additive in the prior art, the present application provides an antifouling and wear-resistant additive, which comprises a nano-silica hybrid multi-branched polymer containing perfluoropolyether groups, and has a plurality of unsaturated sites therein, and is suitable for UV curing coating systems, and can significantly improve the antifouling, anti-fingerprint properties and wear resistance of the coating surface.

[0009] The specific technical solutions adopted are as follows:

[0010] An antifouling and wear-resistant additive, in terms of mole fraction, is made of the following raw materials:

[0011]

[0012]

[0013] The relative density of the nano-silica containing hydroxyl groups is 2.3-3.5 g / cm3 The reactive monomer contains unsaturated bonds, including a vinyl monomer or an acrylate, for side chain grafting.

[0014] Preferably, the anti-fouling and wear-resistant additive is made of the following raw materials in molar fractions:

[0015]

[0016] Specifically, the mono-active perfluoropolyether alcohol PFPE-OH can be selected from K-type, Y-type, Z-type or D-type mono-active perfluoropolyether alcohol.

[0017] Preferably, the mono-active perfluoropolyether alcohol PFPE-OH has a weight average molecular weight of 500-5000 g / mol. Too high molecular weight can affect the solubility of the product anti-fouling and wear-resistant additive in UV coatings and solvents, and cause defects such as coating leveling difference, haze, whitening, etc. Too low molecular weight has a greater impact on anti-fouling properties.

[0018] Preferably, the average particle size of the nano-silica with hydroxyl groups on the surface is 15-35 nm. Too large particle size increases the probability of multiple fluorine chain bonding and poor compatibility due to too many active sites. Too small particle size makes it difficult to form the anti-fouling and wear-resistant additive due to too few active sites.

[0019] The mono-isocyanate containing unsaturated bonds includes isocyanate acrylate, vinyl isocyanate or allyl isocyanate.

[0020] The hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0021] The comonomer is selected from at least one of methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, vinyl acetate, and styrene.

[0022] The reactive active monomer is selected from one or more of isocyanate acrylate, vinyl isocyanate or allyl isocyanate.

[0023] The anti-fouling and wear-resistant additive has strong universality, can be dissolved in conventional solvents and various UV light-cured coating systems, and can also be used in other types of coating systems, such as heat-cured coating systems. The introduction of the anti-fouling and wear-resistant additive into the coating system, especially into the UV light-cured coating system, can significantly improve the anti-fouling and anti-fingerprint properties and wear resistance of the coating surface.

[0024] The application further provides a preparation method of the anti-fouling and wear-resistant additive, comprising the following steps:

[0025] (1) reacting a single-end active perfluoropolyether alcohol PFPE-OH and isophorone diisocyanate to obtain a single-end perfluoropolyether carbamate;

[0026] (2) reacting the single-end perfluoropolyether carbamate and nano-silica with a surface containing hydroxyl groups to obtain a hybrid fluorine-containing nano-silica intermediate;

[0027] (3) reacting the hybrid fluorine-containing nano-silica intermediate and a single isocyanate containing an unsaturated bond to introduce the unsaturated bond into the hybrid fluorine-containing nano-silica intermediate;

[0028] (4) reacting the hybrid fluorine-containing nano-silica intermediate with an unsaturated bond obtained in step (3) and a hydroxy acrylate, a comonomer monomer to obtain a polymer intermediate;

[0029] (5) reacting the polymer intermediate and a reactive active monomer to graft the reactive active monomer to the side chain of the polymer intermediate to obtain the anti-fouling and wear-resistant additive.

[0030] Taking isophorone diisocyanate, isocyanate acrylate ethyl ester, hydroxy acrylate ethyl ester and methyl methacrylate as examples, the reaction equation of the application is shown in the following formula:

[0031]

[0032]

[0033] Preferably, the preparation method of the anti-fouling and wear-resistant additive specifically comprises the following steps:

[0034] S01 weighing single-end active perfluoropolyether alcohol PFPE-OH and isophorone diisocyanate according to a proportion, dissolving the two in 1-2 times weight of heptafluorocyclopentane, adding 300-500 ppm of a catalyst dibutyl tin dilaurate according to the weight of the reactants, and reacting under inert gas protection at 35-50 DEG C for 3-6 h to obtain a single-end perfluoropolyether carbamate solution;

[0035] S02 weighing nano-silica with a surface containing hydroxyl groups according to a proportion, dispersing the nano-silica in the solution obtained in S01, and continuing to react under inert gas protection for 3-10 h to obtain a hybrid fluorine-containing nano-silica intermediate solution;

[0036] S03 to the solution obtained in S02, drop the corresponding amount of unsaturated bond containing monoisocyanate (such as isocyanate acrylate ethyl), continue to react under inert gas protection for 3-6h, the unsaturated bond into the hybrid fluorine-containing nanosilica intermediate, reduced pressure distillation to obtain a viscous with unsaturated bond hybrid fluorine-containing nanosilica intermediate;

[0037] S04 proportionally weighed acrylic acid hydroxy ester, comonomer and 1-3 times the weight of ethyl acetate solvent mixture, inert gas protection to 60-85℃, add 0.5-3% of the total monomer content of azobisisobutyronitrile, while slowly drop the unsaturated bond-containing hybrid fluorine-containing nanosilica intermediate obtained in S03 0.5-2h, and then continue to react for 2-4h, then cooling, to obtain a polymer intermediate solution;

[0038] S05 to the polymer intermediate solution obtained in S04, drop the reactive monomer, while adding 200-400ppm of catalyst dibutyltin dilaurate, inert gas protection to 35-50℃ for 3-6h, then separate to obtain anti-fouling and wear-resistant additives, and then add isopropyl alcohol to adjust the active ingredient to 20% for standby.

[0039] Specifically, in step (1), since the activity of isocyanate group on the branched chain of isophorone diisocyanate is 3 times that of the isocyanate group on the aliphatic ring, it can be controlled to react only with the isocyanate group on the branched chain and not to participate in the reaction of the isocyanate group on the aliphatic ring during the reaction with perfluoropolyether alcohol, thereby greatly reducing the technical difficulty and making it controllable to become a single-chain type anti-fouling and wear-resistant additive.

[0040] In step (2), the nanosilica with hydroxyl groups on the surface has multiple hydroxyl reaction sites, which can react with the isocyanate group on the aliphatic ring of the single-end type perfluoropolyether carbamate generated in the first step. Due to the steric hindrance of its structure and the large difference in solubility with fluorine-containing molecules, by adding excess nanosilica, it can be relatively simple to control the connection of a single fluorine-containing chain segment to a single silica microsphere. The excess nanosilica can continue to react backward to ultimately generate a nanosilica hybrid polymer molecule containing no fluorine and multiple organic chains, or can be used as a multi-pronged active monomer to improve the crosslinking density and wear resistance and aging resistance.

[0041] Further, the polymer segment formed by the hydroxyl acrylate and the reactive monomer can form a stem-like structure around the hybrid fluorine-containing nanosilica intermediate, thereby forming a multi-branched structure with a perfluoropolyether segment at one end and an organic polymer segment at the other end, which can not only be dissolved in a non-fluorine-containing solvent, but also has excellent compatibility with the active monomer in the UV coating system. Moreover, the multi-branched structure has good flowability and strong mobility, and can quickly move upward with the fluorine-containing segment during the film forming process, which helps to improve the anti-fouling and wear-resistant properties. Moreover, the polymer segment contains multiple hydroxyl groups (produced by the hydroxyl-containing acrylate monomer), which can provide reaction groups for the next unsaturation.

[0042] The application further provides application of the anti-fouling and wear-resistant additive in preparation of a coating.

[0043] Preferably, the coating is a UV light-cured coating, and the anti-fouling and wear-resistant additive is added in an amount of 0.5-5 wt% based on the weight of the UV light-cured coating, preferably 0.1-3 wt%.

[0044] When the anti-fouling and wear-resistant additive is added to the UV coating to form a film, the entire structure is driven upward toward the air due to the extremely low surface tension effect, and is located at the outermost layer, thereby showing excellent smoothness and anti-fouling property. Moreover, the anti-fouling and wear-resistant additive has a flexible chain structure, and can stretch under external force during the initial wear-resistant process, thereby having a synergistic effect on wear resistance.

[0045] Compared with the prior art, the application has the following beneficial effects:

[0046] (1) The anti-fouling and wear-resistant additive provided by the application has good compatibility with the coating system. The anti-fouling and wear-resistant additive includes a nanosilica hybrid multi-branched polymer containing a perfluoropolyether group. The multi-branched structure significantly improves the compatibility, and the anti-fouling and wear-resistant additive can also provide multiple crosslinking sites, thereby improving the anti-fouling durability of the coating system (especially the UV light-cured coating).

[0047] (2) The anti-fouling and wear-resistant additive provided by the application has good surface anti-fouling effect. The anti-fouling and wear-resistant additive is a multi-branched dendritic fluorine-containing hybrid structure. During film forming, the perfluoropolyether segment moves upward toward the air due to the self-layering effect of the fluorine-containing segment, the hybrid nanosilica is located at the next layer to form a nanoscale microconvex structure, and the polymer branch containing multiple unsaturated bonds which can be crosslinked with the monomer in the coating or dissolved in the solvent is located downward, and is fixed in the coating layer in a rootstock-like crosslinking manner, thereby fixing the surface conformation, and the prepared coating layer has good and stable surface anti-fouling property.

[0048] (3) The anti-fouling and wear-resistant additive provided by the application can significantly improve the wear resistance of the coating. The introduction of nano-silicon dioxide helps to improve the wear resistance and aging resistance of the UV coating, and the crosslinking density is increased by synergizing with multiple branched chain crosslinking curing sites, thereby reducing physical damage and friction during use.

[0049] (4) The anti-fouling and wear-resistant additive of the application is easy to obtain, and the preparation method has small process control difficulty. The application uses single-end active perfluoropolyether alcohol PFPE-OH and isophorone diisocyanate to react, and then is hybridized with nano-silicon dioxide containing hydroxyl groups on the surface. The difference in activity of isocyanate groups can realize precise control of the bonding of single-chain perfluoropolyether, avoid the disorder of process control and the generation of multiple fluorine chains, and achieve excellent selectivity and the effect of single-molecule fluorine single-chain of the anti-fouling and wear-resistant additive of the application, which is more suitable for industrial production. DETAILED DESCRIPTION

[0050] In order to make the purpose, features and advantages of the application more obvious and easy to understand, the following will be described in detail through specific embodiments. In the following description, many specific details are set forth in order to provide a thorough understanding of the application. However, the application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the concept of the application, so the application is not limited by the specific examples disclosed below. The technical features of each embodiment of the application can be combined accordingly without mutual conflict.

[0051] The operation methods not specified in the following examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturers. The contents not described in detail in the specification belong to the prior art known to those skilled in the art.

[0052] Examples 1-6, Comparative Examples 1-4

[0053] Specifically, the raw materials for preparing the examples and comparative examples of the anti-fouling and wear-resistant additive are shown in Table 1; the preparation method of the anti-fouling and wear-resistant additive comprises the following steps: S01. The monofunctional perfluoropolyether alcohol PFPE-OH and isophorone diisocyanate are weighed according to the proportions in the table, dissolved in heptafluoro-cyclopentane, 500 ppm of a catalyst dibutyltin dilaurate is added, under inert gas protection, the temperature is raised to 50°C, and the reaction is carried out for 5 hours to obtain a monofunctional perfluoropolyether carbamate solution; S02. The nano-silicon dioxide with hydroxyl groups on the surface is weighed according to the proportions, dispersed in the solution obtained in S01, and the reaction is continued under inert gas protection for 5 hours to obtain a hybrid fluorine-containing nano-silicon dioxide intermediate solution; S03. The corresponding amount of a monoisocyanate containing an unsaturated bond is added dropwise to the solution obtained in S02, and the reaction is continued under inert gas protection for 4 hours to introduce the unsaturated bond into the hybrid fluorine-containing nano-silicon dioxide intermediate, and the viscous hybrid fluorine-containing nano-silicon dioxide intermediate with an unsaturated bond is obtained by distillation under reduced pressure; S04. The hydroxy acrylate, comonomer and ethyl acetate solvent are mixed according to the proportions, the temperature is raised to 60°C under inert gas protection, 2% of azobisisobutyronitrile based on the total monomer content is added, and the hybrid fluorine-containing nano-silicon dioxide intermediate with an unsaturated bond obtained in S03 is slowly added dropwise for 1 hour, and then the reaction is continued for 3 hours before cooling to obtain a polymer intermediate solution; S05. The reactive monomer is added dropwise to the polymer intermediate solution obtained in S04, and 300 ppm of a catalyst dibutyltin dilaurate can be added, the temperature is raised to 50°C under inert gas protection, and the reaction is carried out for 6 hours to obtain the anti-fouling and wear-resistant additive, isopropyl alcohol is added to adjust the active ingredient to 20%, and the anti-fouling and wear-resistant additive solution is obtained.

[0054] Table 1 Composition of raw materials for preparing examples and comparative examples (in moles)

[0055]

[0056] Performance test

[0057] (1) UV coating configuration and coating preparation

[0058] Table 2 Typical configuration table of UV coating

[0059]

[0060] (2) The film forming process of the anti-fouling and wear-resistant coating is as follows: the prepared UV coating is sprayed onto a PC plate, the wet film thickness is 15-25 um, then it is dried at 65°C for 5 minutes, and then it is irradiated and cured by a 60W high-pressure mercury lamp, the irradiation energy is 2.5 J / cm 2 , the irradiation time is 10-15s, and the PC coating sample plate after curing is detected for coating performance.

[0061] (3) Test method and test standard

[0062] ①Solubility test: the anti-fouling and wear-resistant additive prepared by the examples or comparative examples was added into 8 parts by mass of solvent at 2 parts by mass, dispersed for more than 20 minutes to ensure sufficient dissolution, and then placed for more than 24 hours. Whether there was delamination or precipitation was observed. No delamination, precipitation and transparency indicated solubility, represented by "◎"; no precipitation and delamination but not completely transparent, represented by "○"; otherwise, the solubility was poor, represented by "×".

[0063] ②Anti-fouling test: water contact angle measurement. The UV coating sample prepared was tested for contact angle using a Shanghai Zhongchen JC2000 D1 dynamic contact angle measuring instrument, and the test method was GB / T24368. Deionized water was used as the test liquid, and the test should be carried out at a temperature of (25±2) °C. One sample was tested three times for one test liquid, and the average value was taken. Water contact angle greater than 115° was represented by A, 110-115° by B, and ≤110° by C.

[0064] ③Wear resistance test 1: the obtained UV coating was subjected to steel wool wear resistance test, according to RIM WI-QMR-06-002 standard test, on Taber 5700 linear wear tester (Taber industry), using 0000# steel wool and under the condition of 1000g weight, contact area 2cm*2cm, the surface of the coating was rubbed, the cycle speed was 50 times / min, the rubbing length was 5.0cm, and the rubbing times were 2000 times. The water contact angle of the coating surface after rubbing was ≥105°, represented by OK, ≥100° represented by √, <100° represented by ×, and <90° represented by ××.

[0065] ④Wear resistance test 2: the obtained UV coating was subjected to steel wool wear resistance test, according to RIM WI-QMR-06-002 standard test, on Taber 5700 linear wear tester (Taber industry), using polyester fiber WIP-1009LE dust-free cloth three-layer folding, contact area 1cm*1cm, weight 500g, cycle speed 50 times / min, rubbing length 5.0cm, rubbing times 3000 times. The water contact angle of the coating surface after rubbing was ≥105°, represented by OK, ≥100° represented by √, and <100° represented by ×.

[0066] The test results of the anti-fouling and wear-resistant additive and the prepared coating according to the examples and comparative examples of the present application are shown in the following table:

[0067] Table 3 Solubility test results

[0068]

[0069] Table 4 Coating performance test results

[0070] Example Stain resistance Abrasion resistance 1 Abrasion resistance 2 Example 1 A OK OK Example 2 B √ √ Example 3 A OK OK Example 4 A OK OK Example 5 A OK OK Example 6 A OK OK Comparative Example 1 B × × Comparative Example 2 A ×× ×× Comparative Example 3 B × × Comparative Example 4 C X X

[0071] From the performance test of the comparative examples, it can be seen that in Comparative Example 1, the fluorine-containing segment of the nanosilica connects multiple isocyanatoethyl acrylate to form a root-like anchoring structure directly connected with the nanosilica, without branched polymer segments, resulting in poor compatibility with conventional solvents and poor compatibility with the UV coating system, easy to precipitate in advance, causing the coating to be opaque and the surface stain resistance of the coating to be uneven; Comparative Example 2 does not have the last step of isocyanatoethyl acrylate, and there is no crosslinking point with the UV coating active monomer in the stain and wear resistant additive, and it is difficult to anchor on the surface, so the surface stain resistance is higher and the wear resistance is poor. In Comparative Example 3, there is no nanosilica hybrid, so a structure with one end being a perfluoropolyether and the other end being an organic polymer chain is formed. The compatibility of this structure in ordinary solvents is not good, and it is easy to precipitate in advance. Without the synergistic effect of the micro-convex structure of the nanosilica, the water contact angle is not ideal, and the wear resistance is also unsatisfactory. Comparative Example 4 does not add a fluorine-containing segment of perfluoropolyether, so a multi-branched dendritic non-fluorine structure is formed, which can be used as an active monomer in UV coating, but due to the absence of fluorine elements, the water contact angle and wear resistance are both poor.

[0072] In summary, the stain and wear resistant additive provided by the present application is a nanosilica hybrid multi-branched polymer containing a perfluoropolyether group, and the hybrid polymer contains multiple unsaturated sites, which is suitable for UV curing coating systems and significantly improves the stain and fingerprint resistance and wear resistance of the coating surface. The coating system of the stain and wear resistant additive of the present application has strong universality and can be dissolved in conventional solvents and various UV coating systems.

[0073] The above examples have described the technical solutions of the present application in detail, and it should be understood that the above examples are only specific embodiments of the present application and are not intended to limit the present application. Any modification, supplement or similar replacement within the principle range of the present application should be included in the protection scope of the present application.

Claims

1. An antifouling and wear resistant aid, characterized in that, The antifouling and wear-resistant additive is made from the following raw materials in molar amounts: 1-2 parts of single-end active perfluoropolyether alcohol PFPE-OH; 1-2 parts of isophorone diisocyanate; One part of nano-silica with hydroxyl groups on its surface; 2-5 parts of monoisocyanate containing unsaturated bonds; 2-25 parts of hydroxy acrylate; 40-400 parts of comonomer; 2-20 parts of reactive monomer; The relative density of the nano-silica with hydroxyl groups on the surface is 2.3-3.5 g / cm 3 The reactive monomer contains an unsaturated bond for side chain grafting. The monoisocyanate containing unsaturated bonds is selected from ethyl isocyanate acrylate, vinyl isocyanate, or allyl isocyanate; The comonomer is selected from at least one of methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, vinyl acetate, and styrene. The reactive monomer is selected from at least one of ethyl isocyanate, vinyl isocyanate, or allyl isocyanate; The preparation method of the aforementioned antifouling and wear-resistant additive includes the following steps: (1) A single-ended perfluoropolyether alcohol PFPE-OH and isophorone diisocyanate were reacted to obtain a single-ended perfluoropolyether carbamate. (2) A hybrid fluorinated nano-silica intermediate is obtained by reacting single-ended perfluoropolyether urethane with nano-silica containing hydroxyl groups on its surface; (3) By reacting hybrid fluorine-containing nano silica intermediates with monoisocyanates containing unsaturated bonds, unsaturated bonds are introduced into the hybrid fluorine-containing nano silica intermediates; (4) The hybrid fluorinated nano silica intermediate with unsaturated bonds obtained in step (3) reacts with hydroxyl acrylate and comonomer to obtain a polymer intermediate; (5) The reactive monomer is grafted onto the side chain of the polymer intermediate by reacting the polymer intermediate with the reactive monomer to obtain the antifouling and wear-resistant additive.

2. The anti-staining wear-aid of claim 1, wherein, Made from the following molar amounts of raw materials: One part of single-end active perfluoropolyether alcohol PFPE-OH; 1 part of isophorone diisocyanate; One part of nano-silica with hydroxyl groups on its surface; 3-4 parts of monoisocyanate containing unsaturated bonds; 4-20 parts of hydroxy acrylate; 100-300 parts of comonomer; 3-20 parts of reactive monomer.

3. The anti-staining wear-aid of claim 1, wherein The single-end active perfluoropolyether alcohol PFPE-OH is selected from K-type, Y-type, Z-type or D-type single-end active perfluoropolyether alcohols, with a weight-average molecular weight of 500-5000 g / mol.

4. The antifouling and wear-resistant additive according to claim 1, characterized in that, The average particle size of nano-silica containing hydroxyl groups on its surface is 15-35 nm.

5. The antifouling and wear-resistant additive according to claim 1, characterized in that, The hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

6. The application of the antifouling and wear-resistant additive according to any one of claims 1-5 in the preparation of coatings.

7. The application of the antifouling and wear-resistant additive according to claim 6 in the preparation of coatings, characterized in that, The coating is a UV-curable coating, and the amount of antifouling and wear-resistant additive added is 0.5-5 wt% based on the weight of the UV-curable coating.

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