Durable low-surface-energy polymer modifier capable of freezing on surface of matrix and preparation method of durable low-surface-energy polymer modifier

Abstract

The invention discloses a durable low-surface-energy polymer modifier capable of freezing on the surface of a matrix and a preparation method thereof, the main chain of the durable low-surface-energy polymer modifier comprises a polydentate hydrogen bond monomer structure, and the end group of the polymer chain is a fluorinated structure. The durable low-surface-energy polymer modifier disclosed by the invention is co-mixed with matrix resin through a conventional processing and mixing means in a standard production process, and is migrated to the surface of a material in processing, heat treatment and use processes, so that the durable low-surface-energy polymer modifier can achieve multiple effects of water resistance, pollution resistance, dust prevention, anticoagulation, antithrombosis, antibiosis, self-cleaning and the like; the multidentate hydrogen bond monomer structure in the modifier structure realizes freezing of the modifier on the surface of matrix resin, so that the risk of elution and loss of the modifier is effectively reduced, the possibility of migration, washing or dissolution in blood is reduced, and the low surface energy durability effect of the matrix surface is enhanced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of surface modified materials, and particularly relates to a durable low surface energy polymer modifier which can be frozen on the surface of a substrate. BACKGROUND

[0002] In recent years, low surface energy coatings are widely used in drag reduction and noise reduction, self-cleaning, antifouling, corrosion protection and other aspects due to their low surface energy, hydrophobicity, and difficulty in being adhered on the surface, and are highly concerned in the fields of optical electronic equipment, automobiles and medical treatment.

[0003] Low surface energy coatings are generally divided into two categories: one is super-hydrophobic coating with micro-nano structure surface, which is a kind of biomimetic material inspired by the microstructure of lotus leaf surface, and the contact angle is greater than 150°, so water droplets can easily roll on the surface. The other is a flat and smooth hydrophobic surface with low contact angle, which is usually composed of fluorine-containing long chains, fluorinated acrylate and silicone polymers. Because they are not limited by rough surfaces, they have higher optical transparency under the premise of meeting the hydrophobic condition, have a wider range of applications, and their mechanical stability has also been greatly improved compared with super-hydrophobic surfaces. However, the durability of the coating still needs to be improved, because in actual application situations, the use environment is complex, and the coating is subject to physical or chemical damage such as wear, impact and corrosion at any time, and the traditional low surface energy coating cannot resist these damages, and once damaged, it is irreversible, which greatly affects the performance and service life of the coating. How to obtain a durable low surface energy surface with long-term use value and resistance to elution and scratching is a difficult problem in this field that has been solved for a long time.

[0004] In the field of implantable medical materials, the surface / interface behavior of implantable medical materials and blood, cells and tissues is the key to determining the biocompatibility of the materials. A large number of studies have shown that the physicochemical properties of the material surface, such as surface topography and roughness, chemical functional groups, energy state, and hydrophilic / hydrophobicity, charge type and distribution, etc. will affect the adhesion, migration, proliferation and differentiation of the adherents on its surface in vitro biological behavior. The interaction between the material surface and the adherents will have an important influence on the effectiveness and safety of the implant after being implanted into the body. Therefore, by modifying the surface properties of medical materials, an attempt is made to find a material surface that can reduce its surface energy, inhibit platelet adhesion and thrombus formation, and avoid being eluted as much as possible.

[0005] Fluorinated polymers (e.g., perfluoropolyethers) have useful properties including low refractive index, stain resistance, lubricity, and strong hydrophobicity. As a result, fluorinated polymers have been incorporated into various protective coatings to impart one or more of low refractive index, cleanability, durability, and scratch resistance to the protective coatings.

[0006] Fluorinated polymers introduced in the form of coatings, paints, and paint films tend to diffuse to the surface of the coating, but due to their own structure and the presence of compatibility and bonding problems, they become less and less over time due to repeated cleaning or wear of the protective coating surface. People have introduced fluorinated polyethers with reactive groups into the coating to solve the diffusion problem, but many of these methods are laborious and have universality problems. There is an ongoing need for a material and method that can introduce fluorinated polymers into the material matrix so that the fluorinated polymers do not become less and less over time.

[0007] CN 100549064C discloses an acryloyl-containing perfluoropolyether made from a reactive fluorinated polyether and a polyvalent (meth)acryloyl compound by Michael addition reaction, and uses the polymerizable fluorinated polyether to form a composite product by introducing the perfluoropolyether into the coating component by a coating reaction, which cannot truly achieve long-acting passive modification of the bulk, and due to the limitations of Michael addition reaction and the influence of the structure of the compound itself, its application is narrow, and the reactivity and compatibility with paint curing systems such as polyurethane, alkyd resin, or epoxy resin are poor. In addition, the perfluoropolyether has poor solubility with other hydrocarbon components in the paint, and will float to the surface of the paint film during film formation, reducing the surface energy of the paint film, and ultimately affecting its oil, water, and dust resistance.

[0008] The Wincure series of patents (CN 110167995B, US8071683B2, US8178620B2, CN 110891620B, CN110891621B, CN 112135882A) discloses a fluorine-containing surface-modified macromolecule, and the series of patents characterizes the influence of the modified molecule on the thermal performance and contact angle of the product, and conducts DEHP leaching analysis, BCA analysis of protein deposition, analysis of deposition in blood, and application exploration of bacterial adhesion on polyurethane (PU) sticks, but the series of patents does not disclose the influence of the addition of the modified molecule on the performance of the matrix and the durability effect of the product, and the improvement effect on the contact angle is not very significant.

[0009] How to further improve the hydrophobic effect of organic fluorine system, increase the applicability of the matrix, and obtain a low surface energy modifier with excellent low surface energy modification effect, strong practicality, wide applicability, and long-acting durability has been a difficult problem to be solved. Using a multi-tooth hydrogen bond monomer structure to improve the durability of the organic fluorine modifier and obtaining a durable low surface energy polymer modifier that can be frozen on the surface of the matrix, the related technology and method have not been reported and disclosed. SUMMARY

[0010] The present application aims at the problem of obtaining a durable low surface energy surface with long-term use value by using a modifier, which cannot be solved in the prior art, which is resistant to washing and scratching, and also ensures good bonding with the substrate and does not affect the strength of the substrate, which is solved by adopting the following technical scheme:

[0011] The present application provides a durable low surface energy polymer modifier which can freeze on the surface of a substrate, characterized in that it contains a multi-dentate hydrogen bond monomer structure capable of forming a tri-dentate or more hydrogen bond structure on its main chain, and its polymer chain end group is a fluorinated structure; it is prepared from at least the following weight parts of raw materials:

[0012]

[0013] The multi-dentate hydrogen bond reactant can form a multi-dentate hydrogen bond monomer structure after polymerization reaction with the isocyanate group;

[0014] The multi-dentate hydrogen bond monomer structure contains at least one of the following structures:

[0015]

[0016] wherein R is selected from hydroxyl, amino, alkyl; X is independently selected from nitrogen atom, carbon atom; i is the number of connecting units, when X is selected from nitrogen atom, i=0 or 1, when X is selected from carbon atom, i=1 or 2;

[0017] The fluorinated structure is selected from the following structures:

[0018]

[0019] wherein x is independently an integer from 1 to 2, when x is 1, the carbon atom is also connected to a hydrogen atom; y is the number of repeating units, which is an integer from 3 to 9.

[0020] In the present application, the durable low surface energy polymer modifier which can freeze on the surface of a substrate preferably has the following structure:

[0021]

[0022] wherein P, I, A, F t , m, n, r are defined as follows:

[0023] P is independently at least one unit formed by polymerization of aliphatic polymer diol or aliphatic polymer diamine, wherein the number average molecular weight of the aliphatic polymer diol or aliphatic polymer diamine is selected from 400-2000 Da;

[0024] I each independently is a unit formed after polymerization of at least one aliphatic diisocyanate;

[0025] A each independently is a unit formed after polymerization of at least one multidentate hydrogen bond former;

[0026] F t each independently is a unit formed after polymerization of at least one monohydroxy fluoroalcohol compound;

[0027] m, n, r are the number of repeating units, each independently is an integer from 1 to 5, and m + n + r < 10.

[0028] In the present application, the low surface energy polymer modifier which can be frozen on the surface of the substrate, the weight average molecular weight Mw is preferably 4000-10000, the content of fluorine element is preferably 2-10%.

[0029] In the present application, the aliphatic polymer diol, aliphatic polymer diamine is respectively selected from the following structure:

[0030]

[0031] wherein, M each independently is aliphatic carbon chain, aliphatic carbon hetero chain, siloxane chain, k is an integer greater than or equal to 1.

[0032] In the embodiment of the present application, the aliphatic polymer diol includes but is not limited to polyether diol, polyester diol, polyurethane diol, polylactic acid diol, polysiloxane diol, polycarbonate diol, polyolefin diol, polyacrylate diol, polymethacrylate diol and copolymer of the above segment structure and mixture containing the above structure.

[0033] Further, the aliphatic polymer diol includes but is not limited to polytetrahydrofuran diol, polyethylene oxide diol, polypropylene oxide diol, polypropylene oxide-ethylene oxide diol, polytrimethylene ether diol, polyethylene glycol adipate diol, polypropylene glycol adipate diol, polybutylene glycol adipate diol, polyhexylene glycol adipate diol, polyneopentyl glycol adipate, polydiethylene glycol adipate diol, polycaprolactone diol, polycarbonate diol, polyhexamethylene carbonate diol, polypropylene carbonate diol, polylactic acid diol, polyacrylate diol, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated epoxidized polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated polyisoprene, hydroxyl-terminated hydrogenated polyisoprene, polysiloxane diol, hydroxyl-terminated hydrocarbon polysiloxane diol, or a combination of one or more thereof.

[0034] In embodiments of the present application, the aliphatic polymeric diamine includes, but is not limited to, polyethylene oxide diamine, polypropylene oxide diamine, polytetrahydrofuran diamine, hydrocarbon amino-terminated polysiloxane diamine.

[0035] In embodiments of the present application, the aliphatic diisocyanate includes, but is not limited to, butane 1,4-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), octane 1,8-diisocyanate, dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), 1,4-cyclohexane dimethyl diisocyanate (HXDI), trimethyl-1,6-hexamethylene diisocyanate (TMDI), methylcyclohexane diisocyanate (HTDI), norbornane diisocyanate (NBDI), lysine diisocyanate (LDI), and mixtures thereof.

[0036] In the present application, the multi-dentate hydrogen bond reactant contains two reactive groups, and contains at least one of the following structures:

[0037]

[0038] wherein R is selected from the group consisting of hydroxyl, amino, alkyl; each X is independently selected from the group consisting of nitrogen atom, carbon atom; i is the number of linking units, i = 0 or 1 when X is selected from the group consisting of nitrogen atom, i = 1 or 2 when X is selected from the group consisting of carbon atom.

[0039] In the present application, the reactive group is selected from the group consisting of hydroxyl, amino, mercapto, hydrazine, hydrazide.

[0040] In embodiments of the present application, the multi-dentate hydrogen bond reactant includes, but is not limited to, the following structures:

[0041] Carbohydrazide Oxalyl dihydrazide Maleic acid dihydrazide Succinic acid dihydrazide Adipic acid dihydrazide Azelaic acid dihydrazide Sebacic acid dihydrazide Dodecanedioic acid dihydrazide Phthalic acid dihydrazide Isophthalic acid dihydrazide Terephthalic acid dihydrazide 6-Aminonicotinoyl hydrazide Pyrimidinone derivative

[0042] Pyridine derivative Five-membered nitrogen heterocyclic compounds

[0043]

[0044] In the present application, the monohydroxy fluorinated alcohol compound has the following structure:

[0045]

[0046] wherein L is an organic linking group, each x is independently the number of fluorine atoms attached to a carbon atom, which is an integer from 1 to 2, wherein when x is 1, the carbon atom is also attached to a hydrogen atom; and y is the number of repeating units, which is an integer from 3 to 9.

[0047] In the detailed description of the present application, the monohydroxy fluorinated alcohol compound includes, but is not limited to, hexafluorobutanol (CAS: 382-31-0), 2,2,3,3,4,4,4-heptafluorobutanol (CAS: 375-01-9), 2,2,3,3,4,4,5,5-octafluoropentanol (CAS: 355-80-6), heptafluoro hexanol (CAS: 679-02-7), 1H, 1H, 2H, 2H-perfluorohexanol (CAS: 2043-47-2), undecafluoro-n-hexanol (CAS: 423-46-1), 1H, 1H, 2H, 2H-perfluorooctanol (CAS: 647-42-7), 1H, 1H, 8H-perfluorooctanol (CAS: 10331-08-5), 1H, 1H-heptadecafluorononanol (CAS: 423-56-3), 1H, 1H, 2H, 2H-perfluorodecanol (CAS: 678-39-7), 1H, 1H-perfluorodecanol (CAS: 307-37-9), preferably hexafluorobutanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol, 1H, 1H, 2H, 2H-perfluorohexanol, 1H, 1H, 2H, 2H-perfluorooctanol, 1H, 1H, 2H, 2H-perfluorodecanol.

[0048] The present application also provides a preparation method of a durable low surface energy polymer modifier that can be frozen on the surface of a substrate, characterized by the following steps:

[0049] S1: heat the aliphatic polymer diol or aliphatic polymer diamine to 80-120°C, vacuumize and remove water for 2-4h;

[0050] S2: heat the aliphatic polymer diol or aliphatic polymer diamine with a fixed molar amount of aliphatic diisocyanate to 60-110°C under nitrogen, and stir for 2-6h until the -NCO content in the system reaches stability, to obtain a prepolymer;

[0051] S3, adding the polydentate hydrogen bond reactant to the prepolymer of S2, controlling the reaction temperature at 40-80℃, and continuing to heat and stir the reaction for 2-8h under nitrogen, and then adding the monohydroxy fluoroalcohol compound to continue the reaction for 2-12h to end the reaction;

[0052] S4, washing and purifying the crude product obtained in S3, and drying in a vacuum oven at room temperature and 60-120℃ in sequence.

[0053] Further, the molar ratio of the four of the aliphatic polymer diol or aliphatic polymer diamine, aliphatic diisocyanate, polydentate hydrogen bond reactant, and monohydroxy fluoroalcohol compound is 1:1.3-4.5:0.2-3.5:0.3-1.1.

[0054] In one specific embodiment of the present application, a polyurethane catalyst is added to the system to promote the reaction; the polyurethane catalyst mainly includes tertiary amine catalysts (including quaternary ammonium salts thereof) and organic metal compounds. The tertiary amine catalysts can be further divided into aliphatic amine, aromatic amine, and alcohol amine and ammonium salt compounds. The organic metal compounds include carboxylate, metal alkyl compound, etc., and the metal elements contained mainly include tin, potassium, lead, mercury, zinc, titanium, bismuth, etc., and the most commonly used are organotin compounds, potassium carboxylate catalysts, organic heavy metal catalysts, zinc carboxylate, and bismuth carboxylate catalysts.

[0055] Further, the addition amount of the polyurethane catalyst is 0.02-0.5wt% of the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0056] In one specific embodiment of the present application, a non-aqueous aprotic solvent is added in steps S2 and S3, the non-aqueous aprotic solvent acts as a heat transfer medium, which can reduce the viscosity of the system, facilitate the dissipation of polymerization heat, thus more easily control the reaction temperature, reduce the risk of local overheating, also facilitate the control of the molecular weight of the polymer, obtain a polymer with uniform structure and molecular weight distribution, and also facilitate the diffusion of monomers and reaction products in the solvent.

[0057] Further, the addition amount of the non-aqueous aprotic solvent is 1-10 times of the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0058] The present application also provides a durable low surface energy material, which comprises 80-100 parts by weight of a base resin, 2-10 parts by weight of the durable low surface energy polymer modifier capable of being frozen on the surface of the base resin as described in the present application, 0-10 parts by weight of an additive, and 0-30 parts by weight of a filler.

[0059] Further, the base resin includes, but is not limited to, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylic resin, unsaturated polyester, polyurethane, polyamide, polycarbonate, thermoplastic polyester, thermoplastic elastomer, polysulfone, polyether sulfone, polyaryl sulfone, polyaryl ether ketone, silicone resin.

[0060] Further, the additive includes, but is not limited to, antioxidant, light stabilizer, heat stabilizer, toughening agent, lubricant, release agent, plasticizer, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant.

[0061] Further, the filler includes, but is not limited to, inorganic non-metallic filler, metal filler, organic filler, organic metal compound filler.

[0062] The application further discloses application of the durable low surface energy material in the fields of coating, textiles, electronic products, automobile accessories, and filter membranes.

[0063] The application further discloses application of the durable low surface energy material in the field of medical products.

[0064] Further, the durable low surface energy material is applied to the fields of medical polyurethane products and medical polyamide products, in particular, medical polyurethane products and medical polyamide products in contact with body fluids.

[0065] Compared with the prior art, the application has the following beneficial effects:

[0066] (1) The durable low surface energy polymer modifier which can be frozen on the surface of the substrate in the application, under the processing and heat treatment conditions, the multi-dentate hydrogen bond monomer structure in the modifier polymer chain is in the dissociation state, has good migration ability, can be well dispersed in the substrate, and is gathered from the inside of the substrate to the surface, in the process of cooling to room temperature, the modifier on the surface of the substrate can be bonded through the strong hydrogen bond action between the multi-dentate hydrogen bond monomer structures, increase the locking between each other. The multi-dentate hydrogen bond monomer structure in the modifier polymer in the application forms a three-dentate or more than three-dentate hydrogen bond structure, which can improve the strength and stability of the modifier polymer structure containing multi-dentate hydrogen bond monomer, enhance the interaction between the modifiers, prevent it from migrating out of the substrate, realize the freezing on the surface of the substrate resin, thereby effectively reducing the risk of modifier elution and loss, reducing the possibility of migration, or being washed out, or dissolved into the blood, enhancing the low surface energy durability effect of the substrate surface, the modified sample maintains good hydrophobicity retention effect in the open environment, PBS buffer and blood simulation test liquid, realizes the combination of hydrophobicity and long-term durability; In addition, by using the fluorinated structure at the end group of the polymer chain, the enrichment efficiency and degree of fluorine on the surface of the substrate are improved, the introduction of fluorinated structure at the end group of the modifier not only improves the migration of fluorine segment, but also does not affect the binding ability of the main chain of the modifier and the substrate. The end group fluorine segment has higher activity and migration rate than the main chain fluorine segment and the side chain fluorine segment, so that the fluorine enrichment efficiency on the surface of the substrate is higher. The fluorine atoms at the chain end are finally enriched in the extremely thin surface layer, and the composition and structure of the polymer substrate are basically not affected, so that the polymer can retain the original excellent bulk properties. In contrast, the main chain and side chain fluorinated structure generally have the problems of processing difficulty, high cost, poor combination with the substrate, and easy to fall off. The durable low surface energy polymer modifier which can be frozen on the surface of the substrate in the application realizes the fluorine enrichment of the modifier on the surface of the substrate by combining the multi-dentate hydrogen bond monomer structure and the end group fluorinated structure, and exhibits good low surface energy modification effect, and shows more excellent mechanical properties.

[0067] (2) The application uses flexible aliphatic polymer diol, aliphatic polymer diamine and aliphatic diisocyanate with strong chain movement ability as raw materials, and through a large number of experiments, the suitable and effective raw material components, the raw material molecular weight range and the polymerization degree are explored, so that the modified polymer chain structure has good migration ability under the conditions of processing and heat treatment, and after the modified agent migrates to the surface, the fluorine enrichment on the surface of the matrix is realized through hydrogen bond association, which promotes the freezing of the modified agent on the surface of the matrix. By controlling the polymer chain segment structure and molecular weight of the modified agent, it can be suitable / compatible with various matrix resins, improve the bonding degree of the modified agent and the matrix resin, and the multi-tooth hydrogen bond monomer structure in the polymer chain of the modified agent can also be associated with the hydrogen bond structure in the matrix resin, thereby enhancing the bonding force of the modified agent and the matrix as a whole, and realizing the stability on the surface of the matrix. After adding the modified agent to the matrix resin, the surface energy of the matrix resin can be reduced by more than 80%, the contact angle can be increased by more than 40-50°, and the mechanical strength of the matrix resin can also be improved. These beneficial effects are closely related to the polymer structure of the modified agent.

[0068] (3) The durable low surface energy polymer modifier in the application can be blended into the matrix resin through conventional processing and mixing means in the standard production process, and migrates to the surface of the material during processing and heat treatment, which can play the effects of waterproofing, anti-fouling, dustproofing, anti-clotting, anti-thrombosis, antibacterial, self-cleaning and the like. Unlike the traditional coating which realizes surface hydrophobicity by being coated on the surface of the matrix, the low surface energy modifier in the application is embedded in the matrix resin, which belongs to long-acting passive modification, and does not have the risk of wear and tear and falling off as the traditional coating, thereby avoiding various accidents (especially medical accidents). At the same time, the multi-tooth hydrogen bond monomer structure in the structure of the modified agent enables the matrix surface to have a durable modification effect, thereby significantly improving the durability of the product and greatly prolonging the service life of the product. In addition, due to the passive property of the modified agent, it can be applied to products of various shapes and structures (including complex structures and small size structures), and is not limited by the appearance and shape of the product, and can be uniformly distributed on the surfaces of the product.

[0069] The above beneficial effects fully show that the durable low surface energy polymer modifier which can freeze on the surface of the matrix has excellent performance and wide applicability. These features and advantages of the application will become apparent from the following specific embodiment description and examples. BRIEF DESCRIPTION OF DRAWINGS

[0070] Figure 1 The infrared spectrum of the modified agent 7 obtained in Example 7 of the application.

[0071] Figure 2 The infrared spectrum of the modified agent 8 obtained in Example 8 of the application.

[0072] Figure 3 The surface EDS fluorine element mapping spectrum of the sample obtained in the application example 2.3 is shown in the following figure.

[0073] Figure 4 The SEM images of the surface morphology of the samples obtained in the application examples and the comparative examples are shown in the following figure; wherein, A is the SEM image of the surface morphology of the sample obtained in the application comparative example 2, and B is the SEM image of the surface morphology of the sample obtained in the application example 2.3.

[0074] Figure 5 The tensile strength comparison graphs of the samples obtained in the application examples and the comparative examples are shown in the following figure; wherein, A is the tensile strength comparison graph of the samples obtained in the application comparative example 1 and the application example 1.2; B is the tensile strength comparison graph of the samples obtained in the application comparative example 2 and the application example 2.3; C is the tensile strength comparison graph of the samples obtained in the application comparative example 3 and the application example 3.3; D is the tensile strength comparison graph of the samples obtained in the application comparative example 5 and the application example 5.2; E is the tensile strength comparison graph of the samples obtained in the application comparative example 6 and the application example 6.1; F is the tensile strength comparison graph of the samples obtained in the application comparative example 7 and the application example 7.1.

[0075] Figure 6 The tear strength comparison graphs of the samples obtained in the application examples and the comparative examples are shown in the following figure; wherein, A is the tear strength comparison graph of the samples obtained in the application comparative example 1 and the application example 1.2; B is the tear strength comparison graph of the samples obtained in the application comparative example 2 and the application example 2.3; C is the tear strength comparison graph of the samples obtained in the application comparative example 3 and the application example 3.3; D is the tear strength comparison graph of the samples obtained in the application comparative example 6 and the application example 6.1; E is the tear strength comparison graph of the samples obtained in the application comparative example 7 and the application example 7.1.

[0076] Figure 7 The water contact angle test graphs of the samples obtained in the application examples and the comparative examples are shown in the following figure; wherein, A is the water contact angle test graph of the sample obtained in the application comparative example 1, B is the water contact angle test graph of the sample obtained in the application example 1.2, C is the water contact angle test graph of the sample obtained in the application comparative example 3, D is the water contact angle test graph of the sample obtained in the application example 3.3, E is the water contact angle test graph of the sample obtained in the application comparative example 4, and F is the water contact angle test graph of the sample obtained in the application example 4.2.

[0077] Figure 8The water contact angle test figures of the samples obtained in the application comparative examples and application examples are shown in the figure; wherein, A is the water contact angle test figure of the sample obtained in the application comparative example 5, B is the water contact angle test figure of the sample obtained in the application example 5.2, C is the water contact angle test figure of the sample obtained in the application comparative example 6, D is the water contact angle test figure of the sample obtained in the application example 6.1, E is the water contact angle test figure of the sample obtained in the application comparative example 7, and F is the water contact angle test figure of the sample obtained in the application example 7.1.

[0078] Figure 9 The water contact angle test figures of the samples obtained in the application comparative examples and application examples are shown in the figure; wherein, A is the water contact angle test figure of the sample obtained in the application comparative example 2, B is the water contact angle test figure of the sample obtained in the application example 2.3, C is the water contact angle test figure of the sample obtained in the application comparative example 8, D is the water contact angle test figure of the sample obtained in the application comparative example 9, E is the water contact angle test figure of the sample obtained in the application comparative example 10, F is the water contact angle test figure of the sample obtained in the application comparative example 11, and G is the water contact angle test figure of the sample obtained in the application comparative example 12. DETAILED DESCRIPTION

[0079] In the present application, the term "main chain" refers to the chain having the most number of chain members in the polymer structure.

[0080] In the present application, the term "end group" refers to the chemical group located at the end of the chain skeleton in the polymer structure and connected with the main chain of the polymer.

[0081] In the present application, the term "aliphatic" refers to the chain hydrocarbon and the cyclic hydrocarbon and its derivatives other than the aromatic compound, which can be the saturated compound connected by the single bond or the unsaturated compound containing the double bond and / or the triple bond, and can contain the elements of oxygen, nitrogen, sulfur, chlorine, etc. in addition to the elements of carbon and hydrogen.

[0082] In the present application, the term "aliphatic carbon chain" refers to the aliphatic chain structure containing only carbon atoms in the main chain skeleton, which can be the saturated chain or the unsaturated chain, and includes but is not limited to any one of the following groups, the unsaturated form of any one of the groups, the substituted form of any one of the groups, the hetero-substituted form of any one of the groups, and the combination thereof: polyolefin chain, such as polyethylene chain, polypropylene chain, polyisobutylene chain, polyvinyl chloride chain, polyvinylidene chloride chain, polyvinyl fluoride chain, polytetrafluoroethylene chain, polytrifluorochloroethylene chain, polyvinyl acetate chain, polyvinyl alkyl ether chain, polybutadiene chain, polyisoprene chain, polychloroprene chain, polynorbornene chain, etc.; polyacrylic chain, such as polyacrylic acid chain, polyacrylamide chain, polymethyl acrylate chain, polymethyl methacrylate chain, etc.; polyacrylonitrile chain, such as polyacrylonitrile chain, etc.

[0083] In the present invention, the term "aliphatic carbon hetero chain" refers to an aliphatic chain structure having both carbon atoms and any one or more hetero atoms in the backbone skeleton, which can be a saturated chain or an unsaturated chain, and includes but is not limited to any one of the following groups, the unsaturated form of any one, the substituted form of any one, the hetero-hybridized form of any one, and combinations thereof: polyether-based chains such as polyethylene oxide chains, polypropylene oxide chains, polytetrahydrofuran chains, epoxy resin chains, and the like; polyester-based chains such as polycaprolactone chains, polyvalerolactone chains, polylactide chains, unsaturated polyester chains, alkyd resin chains, polycarbonate chains, and the like; polyamine-based chains such as polyamide chains, polyimide chains, polyurethane chains, polyurea chains, polythiourethane chains, and the like.

[0084] In the present invention, the term "siloxane chain" refers to a chain structure having both silicon atoms and oxygen atoms in the backbone skeleton, and also includes hydrocarbon-based siloxane chain structures in the backbone skeleton, and includes but is not limited to any one of the following groups, the substituted form of any one, the hetero-hybridized form of any one, and combinations thereof: polydimethylsiloxane chains, polymethylphenylsiloxane chains, polymethylhydrosiloxane chains, polyether-modified siloxane chains, amino-hydrocarbon-modified siloxane chains, epoxy-modified siloxane chains, fluorine-hydrocarbon-modified siloxane chains, methyl-alkyl-modified siloxane chains.

[0085] In the present invention, the term "organic group" refers to a group mainly composed of carbon atoms as the backbone, which can or can not contain hetero atoms, and includes but is not limited to any one of the following groups, the unsaturated form of any one, the substituted form of any one, the hetero-hybridized form of any one, and combinations thereof: alkyl groups, cycloalkyl groups, aryl groups, carbonyl groups; the organic group is preferably selected from the group consisting of methyl groups, ethyl groups, vinyl groups, propyl groups, propenyl groups, butyl groups, butenyl groups, pentyl groups, pentenyl groups, hexyl groups, hexenyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, cyclohexyl groups, phenyl groups, benzyl groups, ester groups, amide groups, urethane groups, urea groups.

[0086] In the present invention, the term "organic linking group" refers to a divalent or multivalent linking group mainly composed of carbon atoms as the backbone, which can or can not contain hetero atoms, and includes but is not limited to any one of the following groups, the unsaturated form of any one, the substituted form of any one, the hetero-hybridized form of any one, and combinations thereof: divalent or multivalent alkyl groups, divalent or multivalent cycloalkyl groups, divalent or multivalent aryl groups, divalent or multivalent alkyl silane groups.

[0087] In the present invention, the term "hetero atom" refers to a common non-carbon atom such as a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, and the like.

[0088] In the present application, the term "aliphatic ring" refers to any kind of alicyclic or aliphatic heterocyclic ring, and the ring-forming atoms are each independently carbon atoms or heteroatoms; the hydrogen atoms on the ring-forming atoms of the aliphatic ring can be substituted with any substituent or can not be substituted; it can be a monocyclic structure, a polycyclic structure, a spiro ring structure, a fused ring structure, a bridged ring structure, or a nested ring structure.

[0089] In the present application, the term "aromatic ring" refers to any kind of aromatic or aromatic heterocyclic ring, and the ring-forming atoms are each independently carbon atoms or heteroatoms; the hydrogen atoms on the ring-forming atoms of the aromatic ring can be substituted with any substituent or can not be substituted; it can be a monocyclic structure, a polycyclic structure, a spiro ring structure, a fused ring structure, a bridged ring structure, or a nested ring structure.

[0090] In the present application, the term "polymerization reaction" refers to the polymerization reaction of active groups such as hydroxyl, amino, mercapto, hydrazine, and hydrazide groups in the compound raw material with isocyanate groups in another compound raw material, unless otherwise specified.

[0091] In the present application, the term "hydrogen bonding" refers to a supramolecular interaction established by hydrogen bonds, which is generally formed by a hydrogen atom covalently connected to an atom Z with high electronegativity and an atom Y with high electronegativity and small radius, with hydrogen as the medium between Z and Y, forming a hydrogen bond link of the form Z-H…Y, wherein Z and Y are any suitable atoms with high electronegativity and small radius, which can be the same element or different elements, and can be selected from F, N, O, C, S, Cl, P, Br, and I, more preferably F, N, and O, and more preferably O and N.

[0092] The present application provides a durable low-surface-energy polymer modifier that can be frozen on the surface of a substrate, characterized in that it contains a multi-dentate hydrogen bond monomer structure capable of forming a tridentate or more hydrogen bond structure in its main chain, and its polymer chain end group is a fluorinated structure; it is prepared using at least the following weight parts of raw materials:

[0093]

[0094] The multi-dentate hydrogen bond reactant can form a multi-dentate hydrogen bond monomer structure after polymerization with isocyanate groups;

[0095] The multi-dentate hydrogen bond monomer structure contains at least one of the following structures:

[0096]

[0097] R is selected from the group consisting of hydroxyl, amino, alkyl; X is independently selected from the group consisting of nitrogen atom, carbon atom; i is the number of connecting units, i = 0 or 1 when X is selected from nitrogen atom, i = 1 or 2 when X is selected from carbon atom;

[0098] wherein the fluorinated structure is selected from the group consisting of:

[0099]

[0100] wherein x is independently the number of fluorine atoms connected to the carbon atom, which is an integer from 1 to 2, wherein when x is 1, the carbon atom is also connected to a hydrogen atom; y is the number of repeating units, which is an integer from 3 to 9.

[0101] In the present application, the durable low surface energy polymer modifier which can be frozen on the surface of the substrate preferably has the following structure:

[0102]

[0103] wherein P, I, A, F t , m, n, r are defined as follows:

[0104] P is independently at least one unit formed by polymerization of a fatty polymer diol or a fatty polymer diamine, wherein the fatty polymer diol or the fatty polymer diamine has a number average molecular weight selected from the range of 400-2000 Da;

[0105] I is independently at least one unit formed by polymerization of a fatty diisocyanate;

[0106] A is independently at least one unit formed by polymerization of a multi-dentate hydrogen bond former;

[0107] F t is independently at least one unit formed by polymerization of a monohydroxy fluoroalcohol compound;

[0108] m, n, r are the number of repeating units, which are independently integers from 1 to 5, and m+n+r≤10.

[0109] In the present application, a typical structure of the unit P is as follows:

[0110]

[0111] wherein M is independently a fatty carbon chain, a fatty carbon hetero chain, a siloxane chain, and k is an integer greater than or equal to 1.

[0112] In the present application, a typical structure of the unit I is as follows:

[0113]

[0114] wherein L' is an aliphatic linker.

[0115] In the present application, the typical structure of unit A is as follows:

[0116]

[0117] wherein G1 is an organic linker, R is selected from hydroxyl, amino, alkyl; X is independently selected from nitrogen atom, carbon atom; i is the number of connecting units, i = 0 or 1 when X is selected from nitrogen atom, i = 1 or 2 when X is selected from carbon atom.

[0118] In the present application, the typical structure of unit F t is as follows:

[0119]

[0120] wherein G2 is an organic linker, x is independently the number of fluorine atoms connected to the carbon atom, which is an integer from 1 to 2, wherein when x is 1, the carbon atom is also connected to a hydrogen atom; y is the number of repeating units, which is an integer from 3 to 9.

[0121] In the present application, the multi-dentate hydrogen bond monomer structure, which can form a tri-dentate or more hydrogen bond structure, contains at least one of the following structures:

[0122]

[0123] wherein R is selected from hydroxyl, amino, alkyl; X is independently selected from nitrogen atom, carbon atom; i is the number of connecting units, i = 0 or 1 when X is selected from nitrogen atom, i = 1 or 2 when X is selected from carbon atom.

[0124] In the present application, the number of hydrogen bond dentate of the multi-dentate hydrogen bond monomer structure is determined by the number of hydrogen bonds composed of hydrogen bond donors (D, i.e. hydrogen atoms) and hydrogen bond acceptors (A, i.e. electronegative atoms that accept hydrogen atoms), each D…A combination is a dentate (as shown in the following formula, examples of tri-dentate, tetra-dentate, and hexa-dentate hydrogen bonds are given respectively), the more the number of hydrogen bond dentate, the stronger the hydrogen bond effect, which can improve the strength and stability of the polymer structure of the multi-dentate hydrogen bond monomer-containing modifier.

[0125] In the present application, the hydrogen bond donor can be any suitable donor group containing hydrogen atoms, preferably containing at least one of the following structural components:

[0126]

[0127] In the present application, the hydrogen bond acceptor can be an acceptor group containing any suitable electronegative atom (such as O, N, S, F, etc.), preferably containing at least one of the following structural components:

[0128]

[0129] In the present application, the hydrogen bond structure formed by the polydentate hydrogen bond monomer structure has a hydrogen bond dentation number greater than or equal to three.

[0130]

[0131] In the embodiments of the present application, the bonding of the three-, four-, and six-dentate hydrogen bond structures formed by the polydentate hydrogen bond monomer structure are exemplified as follows, respectively:

[0132]

[0133] In the present application, the durable low surface energy polymer modifier that can be frozen on the surface of the substrate has a weight average molecular weight Mw of 4000-10000, and a fluorine element content of 2-10%.

[0134] In the present application, the aliphatic polymer diol and the aliphatic polymer diamine are respectively selected from the following structures:

[0135]

[0136] wherein each M is independently an aliphatic carbon chain, an aliphatic carbon hetero chain, a siloxane chain, and k is an integer greater than or equal to 1.

[0137] In the embodiments of the present application, the aliphatic polymer diol includes but is not limited to polyether diol, polyester diol, polyurethane diol, polylactic acid diol, polysiloxane diol, polycarbonate diol, polyolefin diol, polyacrylate diol, polymethacrylate diol, and copolymers of the above segment structures and mixtures containing the above structures.

[0138] Further, the aliphatic polymer diol includes, but is not limited to, a combination of one or more of polytetrahydrofuran diol, polyethylene oxide diol, polypropylene oxide diol, polypropylene oxide-ethylene oxide diol, polytrimethylene ether diol, polyethylene adipate diol, polypropylene adipate diol, polybutylene adipate diol, polyhexylene adipate diol, polyneopentyl glycol adipate, polydiethylene glycol adipate diol, polycaprolactone diol, polycarbonate diol, polyhexamethylene carbonate diol, polypropylene carbonate diol, polylactic acid diol, polyacrylate diol, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated epoxidized polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated polyisoprene, hydroxyl-terminated hydrogenated polyisoprene, polysiloxane diol, hydroxyl-terminated hydrocarbon polysiloxane diol.

[0139] In embodiments of the present application, the aliphatic polymer diamine includes, but is not limited to, polyethylene oxide diamine, polypropylene oxide diamine, polytetrahydrofuran diamine, hydrocarbon amino-terminated polysiloxane diamine.

[0140] In embodiments of the present application, the aliphatic diisocyanate includes, but is not limited to, butane 1,4-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), octane 1,8-diisocyanate, dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), 1,4-cyclohexane dimethyl diisocyanate (HXDI), trimethyl-1,6-hexamethylene diisocyanate (TMDI), methylcyclohexane diisocyanate (HTDI), norbornane diisocyanate (NBDI), lysine diisocyanate (LDI), and mixtures thereof.

[0141] In the present application, the multi-dentate hydrogen bond reactant contains two reactive groups, and contains at least one of the following structures:

[0142]

[0143] wherein R is selected from the group consisting of hydroxyl, amino, alkyl; X is independently selected from the group consisting of nitrogen atom, carbon atom; i is the number of linking units, i = 0 or 1 when X is selected from the group consisting of nitrogen atom, i = 1 or 2 when X is selected from the group consisting of carbon atom.

[0144] In the present application, the reactive group is selected from the group consisting of hydroxyl, amino, thiol, hydrazine, hydrazide.

[0145] In embodiments of the present application, the multi-dentate hydrogen bond reactant includes, but is not limited to, the following structure:

[0146] One, hydrazide structure:

[0147] including but not limited to carbazic acid oxalyl dihydrazide maleic acid dihydrazide succinic acid dihydrazide adipic acid dihydrazide azelaic acid dihydrazide sebacic acid dihydrazide dodecanedioic acid dihydrazide phthalic acid dihydrazide isophthalic acid dihydrazide terephthalic acid dihydrazide 6-aminonicotinoyl hydrazine

[0148] II. Pyrimidinone Derivatives Structure:

[0149] including but not limited to 2,6-diaminopyrimidin-4(lH)-one 2-amino-6-hydroxypyrimidin-4(lH)-one 5-(2-hydroxyethyl)-6-methyl-2-aminooxime pyrimidine

[0150] III. Pyridine Derivatives Structure:

[0151] including but not limited to 2,6-diaminopyridine

[0152] IV. Five-membered Nitrogen Heterocyclic Compounds Structure:

[0153] including but not limited to 3-amino pyrazole 3-amino-5-hydroxypyrazole 2-aminoimidazole 2-amino-l,3,4-triazole 3,5-diamino-l,2,4-triazole

[0154]

[0155] In the present invention, the monohydroxy fluoroalcohol compound has the following structure:

[0156]

[0157] wherein L2 is an organic linker, each x is independently the number of fluorine atoms attached to a carbon atom, which is an integer from 1 to 2, wherein when x is 1, the carbon atom is also attached to a hydrogen atom; and y is the number of repeating units, which is an integer from 3 to 9.

[0158] In the specific embodiments of the present application, the monohydroxy fluorinated alcohol compound includes but is not limited to hexafluorobutanol (CAS: 382-31-0), 2,2,3,3,4,4,4-heptafluorobutanol (CAS: 375-01-9), 2,2,3,3,4,4,5,5-octafluoropentanol (CAS: 355-80-6), heptafluoro hexanol (CAS: 679-02-7), 1H, 1H, 2H, 2H-perfluorohexanol (CAS: 2043-47-2), undecafluoro-n-hexanol (CAS: 423-46-1), 1H, 1H, 2H, 2H-perfluorooctanol (CAS: 647-42-7), 1H, 1H, 8H-perfluorooctanol (CAS: 10331-08-5), 1H, 1H-heptadecafluorononanol (CAS: 423-56-3), 1H, 1H, 2H, 2H-perfluorodecanol (CAS: 678-39-7), 1H, 1H-perfluorodecanol (CAS: 307-37-9), preferably hexafluorobutanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol, 1H, 1H, 2H, 2H-perfluorohexanol, 1H, 1H, 2H, 2H-perfluorooctanol, 1H, 1H, 2H, 2H-perfluorodecanol.

[0159] The present application also provides a preparation method of a durable low surface energy polymer modifier which can be frozen on the surface of a substrate, characterized in that the preparation is carried out by the following steps:

[0160] S1: heat the aliphatic polymer diol or aliphatic polymer diamine to 80-120°C, vacuumize and remove water for 2-4h;

[0161] S2: stir the aliphatic polymer diol or aliphatic polymer diamine with the aliphatic diisocyanate at a fixed molar ratio under nitrogen at 60-110°C for 2-6h until the -NCO content in the system reaches stability to obtain a prepolymer;

[0162] S3: add the multi-dentate hydrogen bond reactant to the prepolymer of S2, control the reaction temperature at 40-80°C, continue to stir under nitrogen heating for 2-8h, and then add the monohydroxy fluorinated alcohol compound to continue heating and stirring for 2-12h for end-capping;

[0163] S4: wash and purify the crude product obtained in S3, and sequentially dry in a vacuum oven at room temperature and 60-120°C.

[0164] Further, the molar ratio of the four of the aliphatic polymer diol or aliphatic polymer diamine, aliphatic diisocyanate, multi-dentate hydrogen bond reactant, and monohydroxy fluorinated alcohol compound is 1:1.3-4.5:0.2-3.5:0.3-1.1.

[0165] In one embodiment of the present application, the polyurethane catalyst is added to the system to promote the reaction; the polyurethane catalyst mainly includes tertiary amine catalyst (including its quaternary ammonium salt) and organic metal compound. The tertiary amine catalyst mainly includes fatty amine, aromatic amine, alcohol amine and ammonium salt compound. The organic metal compound includes carboxylate, metal alkyl compound, etc., and the metal elements mainly include tin, potassium, lead, mercury, zinc, titanium, bismuth, etc., and the most commonly used are organic tin compound, potassium carboxylate catalyst, organic heavy metal catalyst, zinc carboxylate and bismuth carboxylate catalyst.

[0166] In the present application, the fatty amine catalyst includes but is not limited to N,N-dimethylcyclohexylamine (DMCHA), bis(2-dimethylaminoethyl) ether (BDMAEE), N,N,N',N'-tetramethylalkylenediamine, N,N,N',N,N-pentamethyldiethylene triamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, triethylenediamine (TEDA), N-ethylmorpholine, N-methylmorpholine, N,N'-diethylpiperazine, N,N'-diethyl-2-methylpiperazine, N,N-bis-(-hydroxypropyl)-2-methylpiperazine, N-2-hydroxypropyldimethylmorpholine.

[0167] In the present application, the aromatic amine catalyst includes but is not limited to pyridine, N,N'-dimethylpyridine.

[0168] In the present application, the alcohol amine catalyst includes but is not limited to triethanolamine, N,N-dimethylethanolamine. Alcohol amine is a kind of reactive catalyst, which can be used in combination with other high-activity catalysts.

[0169] In the present application, the organic tin catalyst includes but is not limited to dibutyltin dilaurate (DBTDL), stannous octoate, bis(dodecylthio)dibutyltin, dibutyltin diacetate.

[0170] In the present application, the potassium carboxylate catalyst includes but is not limited to potassium isooctoate, potassium acetate, potassium oleate.

[0171] In the present application, the organic heavy metal catalyst includes but is not limited to lead isooctoate, phenylmercury acetate.

[0172] In the present application, the zinc carboxylate and bismuth carboxylate catalyst includes but is not limited to zinc isooctoate, bismuth isooctoate.

[0173] In the present application, the titanate catalyst includes but is not limited to tetrabutyl titanate, tetraisopropyl titanate.

[0174] Further, the polyurethane catalyst is added in an amount of 0.02-0.5wt% of the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0175] In one specific embodiment of the present application, the non-aqueous aprotic solvent is added in steps S2 and S3. The aprotic solvent acts as a heat transfer medium, which can reduce the viscosity of the system, facilitate the dissipation of polymerization heat, and thus more easily control the reaction temperature, reduce the risk of local overheating, and also facilitate the control of the molecular weight of the polymer, obtain a polymer with uniform structure and molecular weight distribution, and also facilitate the diffusion of monomers and reaction products in the solvent.

[0176] In the present application, the non-aprotic solvent does not contain easily substituted hydrogen atoms, and the solvation is mainly achieved by the interaction of dipole moment or van der Waals force. The non-protic solvent is further divided into non-protic polar solvent and non-protic non-polar solvent. The non-protic solvent includes but is not limited to acetonitrile, acetone, butanone, methyl ethyl ketone, benzene, toluene, xylene, nitromethane, nitrobenzene, pyridine, quinoline, n-hexane, heptane, cyclohexane, petroleum ether, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, chloroform, dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, N-methyl pyrrolidone, hexamethylphosphoramide, isopropyl acetate, n-butyl acetate, trichloroethylene, mesitylene, dioxane, carbon tetrachloride, dioxane; preferably acetone, toluene, chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide.

[0177] Further, the non-protic solvent is added in an amount of 1-10 times the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0178] In the present application, the washing method of the crude product in step S4 can be selected from the commonly used product washing methods in the art, which are actually selected according to the properties and solubility of the product, including but not limited to extraction separation with a separatory funnel, dissolution of a good solvent to precipitate and separate the non-good solvent (the separation process can be carried out by centrifugation, pouring, separation, suction filtration, etc.). The good solvent and the non-good solvent of the product are selected according to the actual solubility of the product. The number of washing times is selected according to the actual washing condition, and the product purity can be increased by repeated washing. The specific washing method can be referred to the washing method used in the examples of the present application.

[0179] The present application also provides a durable low surface energy material, which is characterized in that it comprises 80-100 parts by weight of a base resin, 2-10 parts by weight of the durable low surface energy polymer modifier capable of freezing on the surface of the base as described in the present application, 0-10 parts by weight of an additive, and 0-30 parts by weight of a filler.

[0180] Further, the base resin includes, but is not limited to, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylic resin, unsaturated polyester, polyurethane, polyamide, polycarbonate, thermoplastic polyester, thermoplastic elastomer, polysulfone, polyethersulfone, polyarylsulfone, polyaryletherketone, silicone resin.

[0181] Further, the additive includes, but is not limited to, antioxidant, light stabilizer, heat stabilizer, toughening agent, lubricant, release agent, plasticizer, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant.

[0182] Further, the filler includes, but is not limited to, inorganic non-metallic filler, metal filler, organic filler, organic metal compound filler.

[0183] The antioxidant can delay the oxidation process of the material, ensure the smooth preparation and processing of the material, and prolong the service life of the material, and includes, but is not limited to, any one or several of the following antioxidants: hindered phenol, such as 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol); sulfur-containing hindered phenol, such as 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert-butylphenol]; triazine hindered phenol, such as 1,3,5-di[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydro-s-triazine; trimer isocyanate hindered phenol, such as tris(3,5-di-tert-butyl-4-hydroxybenzyl)-triisocyanate; amine, such as N,N'-di(β-naphthyl)para-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine; sulfur-containing, such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; phosphite, such as triphenyl phosphite, tris(nonylphenyl)phosphite, tris[2.4-di-tert-butylphenyl]phosphite, etc.; wherein the antioxidant is preferably tea polyphenol (TP), butylated hydroxyanisole (BHA), dibutylated hydroxytoluene (BHT), tertiary butyl hydroquinone (TBHQ), tris[2.4-di-tert-butylphenyl]phosphite (antioxidant 168), tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (antioxidant 1010). The amount of antioxidant used is not particularly limited, and is generally 0.01-1 wt%.

[0184] The light stabilizer can prevent the material from light aging and prolong its service life, and includes but is not limited to any one or several of the following light stabilizers: light shielding agents such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2,4,6-tris(2-hydroxy-4-n-butyloxyphenyl)-1,3,5-triazine, 2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester; pioneer ultraviolet absorbers such as p-tert-butyl phenyl salicylate, bisphenol A disalicylate; ultraviolet quenching agents such as bis(3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester), 2,2'-thiobis(4-t-octylphenyloxy)nickel; hindered amine light stabilizers such as bis(2,2,6,6-tetramethylpiperidine) sebacate, (2,2,6,6-tetramethylpiperidine) benzoate, tris(1,2,2,6,6-pentamethylpiperidyl) phosphite; other light stabilizers such as 3,5-di-tert-butyl-4-hydroxybenzoic acid (2,4-di-tert-butylphenyl) ester, alkyl phosphoric acid amide, zinc N,N'-di-n-butyl dithiocarbamate, nickel N,N'-di-n-butyl dithiocarbamate, etc.; wherein the light stabilizer is preferably carbon black, bis(2,2,6,6-tetramethylpiperidine) sebacate (light stabilizer 770). The amount of light stabilizer used is not particularly limited, and is generally 0.01-0.5 wt%.

[0185] The heat stabilizer can prevent the material from chemical change due to heat during processing or use, or delay the change to prolong the service life, and includes, but is not limited to, one or more of the following heat stabilizers: lead salts, such as lead tri-basic sulfate, lead di-basic phosphite, lead di-basic stearate, lead di-basic phthalate, lead tri-basic maleate, lead basic silicate, lead stearate, lead salicylate, lead di-basic phthalate, basic lead carbonate, silica co-precipitated lead silicate; metal soaps, such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organic tin compounds, such as di-n-butyl tin dilaurate, di-n-octyl tin dilaurate, di-n-butyl tin maleate, di-n-octyl tin bis maleate, di-n-octyl tin isooctyl dimercaptacetate, Kenzinc C-102, di-n-octyl tin isooctyl dimethyl mercaptacetate; antimony stabilizers, such as thiol antimony salt, mercaptoacetate thiol antimony, mercapto carboxylate antimony, carboxylate antimony; epoxide compounds, such as epoxidized oil, epoxidized fatty acid ester; phosphite esters, such as triaryl phosphite, trialkyl phosphite, triarylalkyl phosphite, alkylaryl mixed ester, polymeric phosphite; and the heat stabilizer is preferably barium stearate, calcium stearate, di-n-butyl tin dilaurate, di-n-butyl tin maleate. The amount of the heat stabilizer used is not particularly limited, and is generally 0.1-0.5 wt%.

[0186] The toughening agent can reduce the brittleness of the material, increase the toughness, and improve the load bearing strength of the material, and includes, but is not limited to, one or more of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modified product, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, terpolymer ethylene-propylene rubber, cis-butadiene rubber, butadiene-styrene rubber, styrene-butadiene-styrene block copolymer, etc.; and the toughening agent is preferably ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS), and chlorinated polyethylene resin (CPE). The amount of the toughening agent used is not particularly limited, and is generally 5-10 wt%.

[0187] The lubricant can improve lubricity of the material, reduce friction and interfacial adhesion, and includes, but is not limited to, any one or more of the following lubricants: saturated hydrocarbons and halogenated hydrocarbons, such as solid paraffin, microcrystalline paraffin, liquid paraffin, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids, such as stearic acid, hydroxystearic acid; fatty acid esters, such as fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, natural wax, ester wax and saponified wax; fatty amides, such as stearic amide or stearic acid amide, oleic amide or oleic acid amide, erucic acid amide, N,N'-ethylene bis-stearamide; fatty alcohols, such as stearyl alcohol; metal soaps, such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, etc.; preferably, the lubricant is solid paraffin, liquid paraffin, stearic acid or low molecular weight polyethylene. The amount of the lubricant used is not particularly limited, and is generally 0.5-1 wt%.

[0188] The release agent can make the material easy to release, smooth and clean, and includes, but is not limited to, any one or more of the following release agents: paraffin hydrocarbons, soaps, dimethyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, chlorovinyl resin, polystyrene, silicone rubber, etc.; preferably, the release agent is dimethyl silicone oil. The amount of the release agent used is not particularly limited, and is generally 0.5-2 wt%.

[0189] The plasticizer can increase plasticity of the material, reduce hardness, modulus, softening temperature and embrittlement temperature of the polymer, and improve elongation, flexibility and flexibility, and includes, but is not limited to, any one or more of the following plasticizers: phthalic acid esters, such as dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl phthalate butyl glycolate, dicyclohexyl phthalate, bis(tridecyl) phthalate, bis(2-ethyl)hexyl terephthalate; phosphoric acid esters, such as tritolyl phosphate, bis(2-ethyl)hexyl diphenyl phosphate; fatty acid esters, such as bis(2-ethyl)hexyl adipate, bis(2-ethyl)hexyl sebacate; epoxy compounds, such as epoxy glycerol esters, epoxy fatty acid monoesters, epoxy tetrahydrophthalic acid esters, epoxy soybean oil, epoxy (2-ethyl)hexyl stearate, epoxy 2-ethylhexyl soyate, 4,5-epoxy bis(2-ethyl)hexyl tetrahydrophthalate, methyl acetyl ricinoleate; glycol lipids, such as C 5～9 acid glycol ester, C 5～9acid di-triethylene glycol ester; chlorine-containing agents such as green wax, chlorine fatty acid ester; polyester such as 1,2-propylene glycol ethanedioate, 1,2-propylene glycol sebacate, phenyl petroleum sulfonate, trimellitate, citrate, etc.; mineral oil such as all suitable refined liquid hydrocarbon mixtures obtained from petroleum such as paraffin oil, naphthenic oil, aromatic oil, etc.; wherein the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP), naphthenic oil. The amount of plasticizer used is not particularly limited, and is generally 5-20 wt%.

[0190] The antistatic agent can guide or eliminate harmful electric charges accumulated in the material, so as not to cause inconvenience or harm to production and life, and includes but is not limited to any one or more of the following antistatic agents: anionic antistatic agents such as alkyl sulfonate, sodium p-nonyl phenoxypropane sulfonate, alkyl phosphate diethanolamine salt, potassium p-nonyl diphenyl ether sulfonate, phosphate ester derivative, phosphate, phosphate ester derivative, fatty amine sulfonate, sodium butyrate sulfonate; cationic antistatic agents such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, dodecyl trimethylamine bromide, alkyl hydroxyethyl dimethyl ammonium perchlorate; zwitterionic antistatic agents such as alkyl dicarboxymethyl ammonium zwitterion, lauryl betaine, N,N,N-trialkyl ammonium acetyl (N'-alkyl) amine zwitterion, N-lauryl-N,N-dimethyl oxyethylene sodium phosphonate, N-alkyl amino acid salt; non-ionic antistatic agents such as fatty acid oxirane adduct, alkyl phenol oxirane adduct, phosphate trimeric oxyethylene ether ester, glycerol fatty acid ester; high molecular weight antistatic agents such as polyallyl amide N-quaternary ammonium salt substitution, poly-4-vinyl-1-acetonyl pyridine phosphate-p-butyl phenyl ester salt, etc.; wherein the antistatic agent is preferably lauryl trimethyl ammonium chloride, alkyl phosphate diethanolamine salt (antistatic agent P). The amount of antistatic agent used is not particularly limited, and is generally 0.3-3 wt%.

[0191] The emulsifier can improve the surface tension between various components in the polymer mixture containing the auxiliary agent, and form a uniform and stable dispersion system or emulsion, which is preferably used for emulsion polymerization. The emulsifier includes, but is not limited to, any one or more of the following: anionic, such as higher fatty acid salt, alkyl sulfonate, alkyl benzene sulfonate, sodium alkyl naphthalene sulfonate, succinate sulfonate, petroleum sulfonate, castor oil sulfate, sulfated butyl ricinoleate, phosphate ester, fatty acyl-peptide condensate; cationic, such as alkyl ammonium salt, alkyl quaternary ammonium salt, alkyl pyridine salt; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; non-ionic, such as alkyl phenol polyoxyethylene ether, fatty acid polyoxyethylene ester, glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alcohol amine fatty amide, etc. The emulsifier is preferably sodium dodecyl benzene sulfonate, sorbitan fatty acid ester, and triethanolamine stearate (emulsifier FM). The amount of the emulsifier used is not particularly limited, and is generally 1-5 wt%.

[0192] The dispersant can make the solid flocculation in the polymer mixture dispersed into fine particles and suspended in the liquid, uniformly disperse the solid and liquid particles that are difficult to dissolve in the liquid, prevent the particles from settling and agglomerating, and form a stable suspension. The dispersant includes, but is not limited to, any one or more of the following: anionic, such as sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium petroleum sulfonate; cationic; non-ionic, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic, such as silicate, condensed phosphate, etc. The dispersant is preferably sodium dodecyl benzene sulfonate, naphthalene methylene sulfonate (dispersant N), and fatty alcohol polyoxyethylene ether. The amount of the dispersant used is not particularly limited, and is generally 0.3-0.8 wt%.

[0193] The colorant can make the product present the required color and increase the surface color. The colorant includes, but is not limited to, any one or more of the following: inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigment, such as lithol scarlet BK, lake red C, perylene red, Kay R red, phthalocyanine red, permanent magenta HF3C, plastic scarlet R and cloisonne red BR, permanent orange HL, light fast yellow G, Ciba plastic yellow R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, phthalocyanine green, plastic purple RL, aniline black; organic dye, such as sulfur indigo red, vat yellow 4GF, threne blue RSN, salt-based rose, oil-soluble yellow, etc. The colorant is selected according to the color requirement of the sample, and is not particularly limited. The amount of the colorant used is not particularly limited, and is generally 0.01-5 wt%, more preferably 0.2-2 wt%.

[0194] The fluorescent whitening agent can make the dyed material obtain the sparkling effect similar to fluorite, and includes but is not limited to any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazin type, phthalimide type, etc.; preferably, the fluorescent whitening agent is sodium stilbene biphenyl disulfonate (fluorescent whitening agent CBS), 4,4-bis(5-methyl-2-benzoxazolyl) stilbene (fluorescent whitening agent KSN), 2,2-(4,4'-diphenylvinyl) bisbenzoxazole (fluorescent whitening agent OB-1). The amount of the fluorescent whitening agent used is not particularly limited, and is generally 0.002-0.03 wt%.

[0195] The matting agent can cause diffuse reflection when incident light reaches the surface of the polymer, and produce a low-gloss, matt and matting appearance, and includes but is not limited to any one or more of the following matting agents: precipitated barium sulfate, silicon dioxide, hydrated gypsum powder, talc powder, titanium dioxide, polymethylurea resin, etc.; preferably, the matting agent is silicon dioxide. The amount of the matting agent used is not particularly limited, and is generally 2-5 wt%.

[0196] The flame retardant can increase the flame resistance of the material, and includes but is not limited to any one or more of the following flame retardants: phosphorus-based, such as red phosphorus, trimethylphenyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate; halogen-containing phosphates, such as tris(2,3-dibromopropyl) phosphate, tris(2,3-dichloropropyl) phosphate; organic halides, such as high-chlorine-content chlorinated paraffin, 1,1,2,2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentadecane; inorganic flame retardants, such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants, such as chloro-bridged anhydride, bis(2,3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, etc.; preferably, the flame retardant is decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, antimony trioxide. The amount of the flame retardant used is not particularly limited, and is generally 1-20 wt%.

[0197] In the present application, the filler mainly plays the following roles in the material: ①reducing the shrinkage of the shaped product, and improving the dimensional stability, surface finish, smoothness and flatness or non-gloss of the product, etc.; ②adjusting the viscosity of the polymer; ③meeting different performance requirements, such as improving the impact strength and compression strength, hardness, stiffness and modulus of the polymer material, improving the wear resistance, improving the heat distortion temperature, improving the electrical conductivity and thermal conductivity, etc.; ④improving the coloring effect of the pigment; ⑤imparting light stability and chemical corrosion resistance; ⑥playing a compatibilizing role, which can reduce the cost and improve the competitiveness of the product in the market.

[0198] The filler includes but is not limited to inorganic non-metallic fillers, metal fillers, organic fillers, and organic metal compound fillers.

[0199] The inorganic non-metallic filler includes, but is not limited to, any one or more of the following: calcium carbonate, clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon black, quartz, mica powder, clay, asbestos, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene, graphene oxide, fullerene, carbon nanotube, molybdenum disulfide, silicon dioxide, zinc oxide, aluminum oxide, diatomite, red mud, wollastonite, silicon aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano silicon dioxide, nano Fe3O4 particles, nano γ-Fe2O3 particles, nano MgFe2O4 particles, nano MnFe2O4 particles, nano CoFe2O4 particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), up-conversion crystal particles, oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass microbeads, resin microbeads, glass powder, glass fiber, carbon fiber, quartz fiber, carbon core boron fiber, titanium diboride fiber, calcium titanate fiber, silicon carbide fiber, ceramic fiber, whisker, and the like.

[0200] The metal filler includes metal compounds, including but not limited to any one or more of the following: metal powder, fiber, including but not limited to copper, silver, nickel, iron, gold, and the like and alloys thereof; nano metal particles, including but not limited to nano gold particles, nano silver particles, nano palladium particles, nano iron particles, nano cobalt particles, nano nickel particles, nano CoPt3 particles, nano FePt particles, nano FePd particles, nickel-iron bimetallic magnetic nano particles, and other nano metal particles that can generate heat under the action of at least one of infrared, near-infrared, ultraviolet, and electromagnetic waves; liquid metal, including but not limited to mercury, gallium, gallium-indium liquid alloy, gallium-indium-tin liquid alloy, and other gallium-based liquid metal alloys.

[0201] The organic filler includes, but is not limited to, any one or more of the following: ① natural organic filler; ② synthetic resin filler; ③ synthetic rubber filler; ④ synthetic fiber filler; ⑤ foamable polymer particles; ⑥ conjugated polymer; ⑦ organic functional dye / pigment. Organic fillers with properties including ultraviolet absorption, fluorescence, luminescence, and photothermal properties are of great significance to the present application and can be fully utilized to obtain multifunctionality.

[0202] The organic metal compound filler contains a metal organic complex component, in which a metal atom is directly connected to a carbon atom by a bond (including a coordination bond and a sigma bond, etc.), and can be a small molecule or a large molecule, and can be amorphous or a crystal structure. The metal organic compound often has excellent properties, including ultraviolet absorption, fluorescence, luminescence, magnetism, catalysis, photothermal, electromagnetic heat, etc.

[0203] The type of the added filler is not limited, and is mainly determined according to the required material properties. The amount of the used filler is not particularly limited, and is generally 1-30 wt%.

[0204] In an embodiment of the present application, the durable low surface energy polymer modifier that can freeze on the surface of the matrix can be blended into the matrix resin through conventional processing and mixing means in a standard production process, and migrates to the material surface during processing and heat treatment and use, to achieve the effects of waterproofing, stain resistance, dust resistance, anti-clotting, anti-thrombosis, antibacterial, self-cleaning, etc.

[0205] In an embodiment of the present application, the processing and mixing means used include but are not limited to solution stirring and mixing, melting stirring and mixing, kneading, internal mixing, open mixing, melt extrusion, ball milling, etc. The energy providing form during material mixing includes but is not limited to heating, illumination, radiation, microwave, ultrasound. The product forming methods used include but are not limited to extrusion molding, injection molding, mold pressing, flow casting, calendering, casting.

[0206] In an embodiment of the present application, the durable low surface energy material is used as a matrix component, and is prepared into a coating or paint with a solvent.

[0207] Further, the solvent includes but is not limited to deionized water, methanol, ethanol, isopropanol, acetonitrile, acetone, butanone, methyl ethyl ketone, benzene, toluene, xylene, nitromethane, nitrobenzene, pyridine, quinoline, n-hexane, heptane, cyclohexane, petroleum ether, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, chloroform, dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, isopropyl acetate, n-butyl acetate, trichloroethylene, mesitylene, dioxane, carbon tetrachloride, dioxane, and a mixed solvent composed of the above-mentioned solvents.

[0208] Further, suitable substrates for the coating include, but are not limited to, glass (e.g., windows, optical elements, lenses, mirrors), ceramics (e.g., tiles), cement, stone, painted surfaces (e.g., automotive body panels and boat surfaces), metals (e.g., architectural columns), paper (e.g., adhesive release liners), paperboard (e.g., food containers), thermoset and thermoplastic plastics (e.g., polycarbonates, acrylics, polyolefins, polyurethanes, polyesters, polyamides, polyimides, phenolics, cellulose diacetate, cellulose triacetate, polystyrene, and styrene-acrylonitrile copolymers), and combinations thereof. The substrate can be in the form of a film, sheet, or other form. The substrate can include a transparent or translucent display element that can optionally have a ceramic polymeric hardcoat thereon.

[0209] In the detailed description of the application, the durable low surface energy material of the present application can be applied to a substrate using conventional coating techniques such as, for example, spray coating, knife coating, slot coating, reverse roll coating, gravure coating, dip coating, bar coating, flow coating, or spin coating. Then, any optional solvent is typically removed at least partially (e.g., using a forced air oven), followed by at least partial curing of the durable low surface energy material to form a durable coating.

[0210] In the detailed description of the application, the prepared durable low surface energy material can optionally be heat treated to more rapidly migrate the modifying agent to the surface of the matrix resin without affecting the matrix resin, by heating. Suitable optional heat treatment temperatures range from 60 to 80 °C, and suitable optional heat treatment times range from 12 hours to 7 days.

[0211] The present application also discloses the use of the durable low surface energy material in the field of coating, the field of textiles, the field of electronic products, the field of automotive parts, and the field of filtration membranes.

[0212] The application also discloses application of the durable low-surface-energy material in the field of medical products. The medical products include medical instruments, medical equipment, surgical instruments, drug delivery devices, drug release devices, grafts, stents, pacemakers, implantable cardioverter-defibrillators, cardiac stents, cardiovascular device leads, ventricular assist devices and transmission systems, heart valves, vena cava filters, intravascular coils, catheters, catheter joints, catheter valves, intravenous delivery lines, intravenous delivery manifolds, shunts, wound drains, drainage catheters, infusion ports, cochlear implants, endotracheal tubes, tracheostomy tubes, breathing machine breathing tubes and lines, implantable sensors, ophthalmic devices, orthopedic devices, dental equipment, dental implants, periodontal implants, breast implants, penile implants, maxillofacial implants, orthopedic implants, valves, artificial blood vessels, artificial skin, orthotics, oxygen masks, scaffolds, suture materials, needles, hernia repair meshes, tension-free vaginal tape and vaginal slings, prosthetic nerve devices and ear tubes, medical dressings, medical bandages, medical gauze, medical adhesive tapes, medical pads, medical sponges, blood oxygenators, breathing machines, contraceptive devices, feminine hygiene products, endoscopes, dialysis membranes, guide wires, fluid collection bags, blood bags, infusion bags, drug delivery bags and tubing, feeding tubes, tissue regeneration or cell culture devices.

[0213] Further, the durable low-surface-energy material is applied to the fields of medical polyurethane products and medical polyamide products, especially medical polyurethane products and medical polyamide products which are in contact with body fluids.

[0214] Hereinafter, a specific embodiment of the present application will be described in detail. The described examples are exemplary and are intended to explain the present application, and cannot be understood as a limitation of the present application. If a specific technique or condition is not mentioned in the examples, the technique or condition described in the literature in the art or according to the product manual is used. If the manufacturer of the raw material, reagent or instrument is not mentioned, it is a conventional product which can be obtained by market purchase.

[0215] For the sake of simplicity, the raw materials or reagents used in the examples are represented by the following abbreviations:

[0216] PEG: polyethylene glycol

[0217] PPG: polypropylene glycol

[0218] PTMG: polytetramethylene glycol

[0219] HTPB: hydroxyl-terminated polybutadiene

[0220] HLBH: hydroxyl-terminated hydrogenated polybutadiene

[0221] HHTPI: hydroxyl-terminated hydrogenated polyisoprene

[0222] PDMS-COH: hydroxyl-terminated hydrocarbon-modified silicone oil

[0223] PDMS-CNH2: amino-terminated hydrocarbon modified silicone oil

[0224] PCDL: Polycarbonate Diol

[0225] PEA: polyethylene adipate

[0226] PBA: polybutylene adipate

[0227] PCL: Polycaprolactone

[0228] PO3G: Polytrimethylene ether glycol

[0229] ATPE: polyoxypropylene diamine

[0230] HDI: Hexamethylene diisocyanate

[0231] IPDI: Isophorone diisocyanate

[0232] TMDI: Trimethyl-1,6-hexamethylene diisocyanate

[0233] HMDI: dicyclohexylmethane diisocyanate

[0234] CHDI: 1,4-cyclohexane diisocyanate

[0235] HXDI: 1,4-cyclohexanedimethyl diisocyanate

[0236] HTDI: Methylcyclohexane diisocyanate

[0237] MDI: diphenylmethane diisocyanate

[0238] TEDA: triethylenediamine

[0239] DMCHA: N,N-dimethylcyclohexylamine

[0240] C4F6OH: Hexafluorobutanol (CAS: 382-31-0)

[0241] C4F7OH: 2,2,3,3,4,4,4-heptafluorobutanol (CAS: 375-01-9)

[0242] C5F8OH: 2,2,3,3,4,4,5,5-octafluoropentanol (CAS: 355-80-6)

[0243] C6F9OH: 1H,1H,2H,2H-perfluorohexanol (CAS: 2043-47-2)

[0244] C8F13OH: 1H,1H,2H,2H-perfluorooctanol (CAS: 647-42-7)

[0245] C10F17OH: 1H, 1H, 2H, 2H-perfluorodecanol (CAS: 678-39-7)

[0246] DMAc: dimethylacetamide

[0247] THF: tetrahydrofuran

[0248] MeOH: methanol

[0249] CHCl3: chloroform

[0250] IPA: isopropanol

[0251] Infrared spectrum test was carried out by using iS50 Fourier infrared spectrometer of Thermo Fisher Scientific Corporation, USA.

[0252] Hardness test was carried out by using Shore A or Shore D hardness tester, and the test was carried out at 23°C, and the test method was as follows: the hardness value displayed on the dial was the hardness value of the measured material when the Shore hardness tester was inserted into the measured material.

[0253] Contact angle test was carried out by using Attension Theta Lite optical contact angle measuring instrument of Sweden Biotekniska AB. The droplets used in the experiment were deionized water and diiodomethane. The volume of the droplets used was 5 μL, and the test was carried out at 25°C and 65% RH. By testing the contact angles of water and diiodomethane on the surface of the product, the free energy contribution of the polar part and the dispersion part in the free energy of the surface of the product was calculated. According to Fowkes theory, the free energy of the surface of the sample was calculated (Fowkes FM. Attractive forces at interface [J]. Indust Eng Chem 1964, 56: 40-52.).

[0254] Gel permeation chromatography (GPC) was used to determine the molecular weight and molecular weight distribution of the product, and the test was carried out on Waters-150C gel chromatograph (Waters Corporation, USA). Polystyrene standard sample was used as reference polymer to calibrate the relative molecular mass and elution time, tetrahydrofuran (chromatographic pure) was used as mobile phase, the test temperature was 35°C, the sample addition amount was 25 μL, the flow rate was 0.8 mL / min, and before the test, the polymer solution was filtered by using 0.45 μm polytetrafluoroethylene (PTFE) porous filter head.

[0255] The fluorine element content was determined by the burning method on an Elementar vario EL III elemental analyzer. The sample was placed in an oxygen stream for combustion, and the organic components were fully oxidized with an oxidizing agent. The various elements were quantitatively converted into volatile oxides corresponding to them, and the products were allowed to flow through a silica gel packed column chromatograph, and the concentrations were determined by a thermal conductivity cell detector. The fluorine content was calculated by titration with a thorium nitrate standard solution.

[0256] The tensile property test was performed using a CMT-6104 microcomputer series electronic universal testing machine of Shenzhen Xin Sansi Measurement Technology Co., Ltd., and the test standard was GB 1040-79.

[0257] The tear property test was performed using a CMT-6104 microcomputer series electronic universal testing machine of Shenzhen Xin Sansi Measurement Technology Co., Ltd., and the test standard was GB / T529-2008.

[0258] The SEM test was performed using a Sigma 300 scanning electron microscope of Carl Zeiss, Germany, and the percentage of fluorine atoms on the surface of the sample was analyzed by EDS mapping.

[0259] The durability test was performed by placing the test sample in the following environments: 1. placed in an open environment at room temperature; 2. immersed in a PBS buffer solution with a pH of 7.4; 3. immersed in a TL2 blood simulation test solution (purchased from Fulin Plastic Raw Material Co., Ltd.). Water contact angle test was performed every 10 days (the samples in 2 and 3 were washed with clean water and dried before testing), and the sample was determined to be invalid when the water contact angle decreased by 15%.

[0260] The tests in the examples, comparative examples, application comparative examples, and application examples were all performed after the samples were prepared and placed for 1-2 weeks; the contact angle test samples in the application comparative examples and application examples were all heat treated in an oven at 60-80°C for 3-5 days before testing.

[0261] Preparation of pyrimidinone derivatives:

[0262] Preparation of 5-(2-hydroxyethyl)-6-methyl-2-semicarbazide pyrimidine:

[0263] First, 6.41 g (50 mmol) of α-acetyl-γ-butyrolactone and 9.04 g (50 mmol) of guanidine carbonate were added to a 250 mL single-necked flask, followed by the addition of 64 mL of ethanol and 16.6 mL of triethylamine. The mixture was stirred and refluxed at 80°C for 10 h. The crude product was filtered with ethanol three times, dispersed in water, and neutralized with hydrochloric acid to remove excess triethylamine. The product was filtered again, washed with water and ethanol three times, and then dried in an oven at 80°C for 9 h to obtain a white powdery product.

[0264] Example 1

[0265] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 20 g of PEG (50 mmol, PETRONAS Malaysia Petroleum PEG-400, Mn = 400) and the flask containing the PEG was heated to 90 °C and vacuumed for 3 h to remove water. To the flask was added 200 ml of anhydrous DMAc and the flask was placed in an oil bath at 60 °C and the PEG was dissolved with stirring under a nitrogen atmosphere. To the flask was added 16.67 g (75 mmol) of IPDI and the mixture was stirred until dissolved. To the mixture was added 10 mg (0.05 wt% based on the mass of the PEG) of bismuth carboxylate catalyst. The mixture was stirred at 70 °C for 2 h under a continuous nitrogen atmosphere and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0266] To the flask containing the prepolymer was added 2.54 g (15 mmol) of 5-(2-hydroxyethyl)-6-methyl-2-aminouracil. The resulting mixture was heated to 50 °C and stirred for 4 h and the -NCO content of the system was determined to be stable using a potentiometric titrator. To the mixture was added 6.60 g (25 mmol) of C6F9OH and the mixture was heated to 50 °C and stirred for an additional 8 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator. The crude product from the DMAc was precipitated into distilled water and washed several times in methanol and dried at room temperature for 12 h and then dried in a vacuum oven at 80 °C for 8 h to give a clear viscous liquid which was designated Modifier 1. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are shown in Table 1.

[0267] Example 2

[0268] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 30 g of PEG (50 mmol, PETRONAS Malaysia Petroleum PEG-600, Mn = 600) and the flask containing the PEG was heated to 100 °C and vacuumed for 3 h to remove water. To the flask was added 200 ml of anhydrous DMAc and the flask was placed in an oil bath at 60 °C and the PEG was dissolved with stirring under a nitrogen atmosphere. To the flask was added 12.61 g (75 mmol) of HDI and the mixture was stirred until dissolved. To the mixture was added 15 mg (0.05 wt% based on the mass of the PEG) of bismuth carboxylate catalyst. The mixture was stirred at 60 °C for 3 h under a continuous nitrogen atmosphere and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0269] Prepolymer was prepared by adding 12 g PPG (30 mmol, Sinochem Shandong BlueStar Dongda Chemical Co., Ltd., Mn = 400) into a four-necked flask equipped with a stirring rod. The flask containing PPG was heated to 100 °C and vacuumed for 3 h to remove water. 100 mL of anhydrous DMAc was added into the flask, which was then placed in an oil bath at 70 °C and stirred under nitrogen to dissolve PPG. 15.74 g (60 mmol) of HMDI was added into the flask, followed by 50 mL of anhydrous DMAc. The mixture was stirred to dissolve the mixture, and 10 mg (0.08 wt% based on the mass of PPG) of tin catalyst was added. The mixture was continuously stirred under nitrogen at 90 °C for 3 h until the -NCO content in the system reached a stable value, thereby obtaining a prepolymer.

[0270] Example 3

[0271] All glassware used for the synthesis reaction was dried in an oven at 110 °C for 2 h. 12 g of PPG (30 mmol, Sinochem Shandong BlueStar Dongda Chemical Co., Ltd., Mn = 400) was added into a four-necked flask equipped with a stirring rod. The flask containing PPG was heated to 100 °C and vacuumed for 3 h to remove water. 100 mL of anhydrous DMAc was added into the flask, which was then placed in an oil bath at 70 °C and stirred under nitrogen to dissolve PPG. 15.74 g (60 mmol) of HMDI was added into the flask, followed by 50 mL of anhydrous DMAc. The mixture was stirred to dissolve the mixture, and 10 mg (0.08 wt% based on the mass of PPG) of tin catalyst was added. The mixture was continuously stirred under nitrogen at 90 °C for 3 h until the -NCO content in the system reached a stable value, thereby obtaining a prepolymer.

[0272] Prepolymer was prepared by adding 12 g PPG (30 mmol, Sinochem Shandong BlueStar Dongda Chemical Co., Ltd., Mn = 400) into a four-necked flask equipped with a stirring rod. The flask containing PPG was heated to 100 °C and vacuumed for 3 h to remove water. 100 mL of anhydrous DMAc was added into the flask, which was then placed in an oil bath at 70 °C and stirred under nitrogen to dissolve PPG. 15.74 g (60 mmol) of HMDI was added into the flask, followed by 50 mL of anhydrous DMAc. The mixture was stirred to dissolve the mixture, and 10 mg (0.08 wt% based on the mass of PPG) of tin catalyst was added. The mixture was continuously stirred under nitrogen at 90 °C for 3 h until the -NCO content in the system reached a stable value, thereby obtaining a prepolymer.

[0273] Example 4

[0274] All glassware used for the synthesis was dried in an oven at 1 10 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 40 g PPG (20 mmol, Shandong Lansheng East Chemical Co., Ltd., Mn = 2000) and the flask containing PPG was heated to 100 °C and vacuumed to remove water for 3 h. The flask was charged with 150 mL of anhydrous DMAc and placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve the PPG. The flask was charged with 8.89 g (40 mmol) of IPDI and 50 mL of anhydrous DMAc was added and the mixture was stirred to dissolve and 32 mg (0.08 wt% based on the mass of PPG) of tin catalyst was added. The mixture was stirred at 90 °C under a nitrogen atmosphere for 3 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0275] A four-necked flask equipped with a stir bar was charged with 40 g PPG (20 mmol, Shandong Lansheng East Chemical Co., Ltd., Mn = 2000) and the flask containing PPG was heated to 100 °C and vacuumed to remove water for 3 h. The flask was charged with 150 mL of anhydrous DMAc and placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve the PPG. The flask was charged with 8.89 g (40 mmol) of IPDI and 50 mL of anhydrous DMAc was added and the mixture was stirred to dissolve and 32 mg (0.08 wt% based on the mass of PPG) of tin catalyst was added. The mixture was stirred at 90 °C under a nitrogen atmosphere for 3 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0276] Example 5

[0277] All glassware used for the synthesis was dried in an oven at 1 10 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 40 g PPG (20 mmol, Shandong Lansheng East Chemical Co., Ltd., Mn = 2000) and the flask containing PPG was heated to 100 °C and vacuumed to remove water for 3 h. The flask was charged with 150 mL of anhydrous DMAc and placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve the PPG. The flask was charged with 8.89 g (40 mmol) of IPDI and 50 mL of anhydrous DMAc was added and the mixture was stirred to dissolve and 32 mg (0.08 wt% based on the mass of PPG) of tin catalyst was added. The mixture was stirred at 90 °C under a nitrogen atmosphere for 3 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0278] To the flask containing the prepolymer was added 2.88 g (32 mmol) of carbazic acid hydrazide and 50 ml of anhydrous acetone to reduce the viscosity, the resulting mixture was heated at 60 °C and stirred for 4 h, the -NCO content of the system was determined to be stable using a potentiometric titrator, then 5.28 g (20 mmol) of C6F9OH was added, the reaction was continued at 65 °C for 5 h, the polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator, and the crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution, after drying at room temperature for 12 h, the product was dried in a vacuum oven at 80 °C for 12 h, to obtain a light gray paste, which was labeled as Modifier 5, the weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0279] Example 6

[0280] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. To a four-necked flask equipped with a stir bar was added 19.50 g of PTMG (30 mmol, Mitsubishi Chemical Corporation PTMG 650, Mn = 650), the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 23.61 g (90 mmol) of HMDI. The mixture was stirred at 95 °C for 3 h under a continuous nitrogen flow, the -NCO content of the system was determined to be stable using a potentiometric titrator, to obtain a prepolymer.

[0281] To the flask containing the prepolymer was added 7.84 g (45 mmol) of adipic acid dihydrazide and 100 ml of anhydrous acetone to reduce the viscosity, the resulting mixture was heated at 50 °C and stirred for 4 h, the -NCO content of the system was determined to be stable using a potentiometric titrator, then 6.96 g (30 mmol) of C5F8OH was added, the reaction was continued at 50 °C for 7 h, the polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator, and the crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution, after drying at room temperature for 12 h, the product was dried in a vacuum oven at 80 °C for 12 h, to obtain a light gray paste, which was labeled as Modifier 6, the weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0282] Example 7

[0283] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn = 1000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 4.99 g (30 mmol) of CHDI. The mixture was stirred at 100 °C for 3 h under a constant stream of nitrogen and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0284] To the flask containing the prepolymer was added 0.76 g (6 mmol) of 2,6-diaminopyrimidin-4(lH)-one and 50 ml of anhydrous acetone to reduce the viscosity and the resulting mixture was heated at 55 °C and stirred for 4 h. The -NCO content of the system was determined to be stable using a potentiometric titrator and an additional 2.00 g (10 mmol) of C4F7OH was added. The reaction was continued at 60 °C for 8 h and the polymer solution was cooled to room temperature. The solvent was removed on a rotary evaporator and the crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution. After drying at room temperature for 12 h, the crude product was dried in a vacuum oven at 80 °C for 12 h to give a off-white elastomer, designated as Modifier 7, whose infrared spectrum is shown in FIG. 1. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1. Figure 1

[0285] Example 8

[0286] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn = 1000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 6.65 g (40 mmol) of CHDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst. The mixture was stirred at 90 °C for 2 h under a constant stream of nitrogen and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0287] ​To the flask containing the prepolymer, 1.18 g (10 mmol) of oxalyl dihydrazide was added and 50 ml of anhydrous acetone was added to reduce the viscosity. The resulting mixture was heated to 55 °C and stirred for 5 h. The -NCO content of the system was determined to be stable using a potentiometric titrator. Then, 5.28 g (20 mmol) of C6F9OH was added and the reaction was continued at 60 °C for 8 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator. The crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution. After drying at room temperature for 12 h, the product was further dried in a vacuum oven at 80 °C for 12 h to obtain a gray solid, which was labeled as Modifier 8. The infrared spectrum of Modifier 8 is shown in FIG. 1. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1. Figure 2

[0288] Example 9

[0289] All glassware used for the synthesis was dried in a 110 °C oven for 2 h. To a four-necked flask equipped with a stir bar, 40 g of PEA (40 mmol, Yantai Huada Chemical Industry CMA-1024, Mn = 1000) was added. The flask containing PEA was heated to 90 °C and vacuumed for 3 h to remove water. To the flask, 200 ml of anhydrous DMAc was added and the flask was placed in a 70 °C oil bath and stirred under a nitrogen atmosphere to dissolve PEA. To the flask, 19.94 g (76 mmol) of HMDI was added, followed by the addition of 32 mg (0.08 wt% based on the mass of PEA) of TEDA catalyst. The mixture was continuously stirred under a nitrogen atmosphere at 80 °C for 3 h. The -NCO content of the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0290] To the flask containing the prepolymer, 19.42 g (100 mmol) of isophthalic dihydrazide was added. The resulting mixture was heated to 60 °C and stirred for 3 h. The -NCO content of the system was determined to be stable using a potentiometric titrator. Then, 13.11 g (36 mmol) of C8F13OH was added and the reaction was continued at 65 °C for 4 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator. The crude product from DMAc was precipitated in distilled water and washed several times in an ethanol solution. After drying at room temperature for 12 h, the product was further dried in a vacuum oven at 80 °C for 12 h to obtain a white paste, which was labeled as Modifier 9. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1.

[0291] Example 10

[0292] ​All glassware used for the synthesis was dried in an oven at 1 10 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 40 g of PBA (20 mmol, Yantai Huada Chemical Industry CMA-44, Mn = 2000), and the flask containing PBA was heated to 90 °C and vacuumed to remove water for 3 h. The flask was charged with 200 ml of anhydrous DMAc and placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve PBA. The flask was charged with 8.89 g (40 mmol) of IPDI and 32 mg (0.08 wt% based on the mass of PBA) of TEDA catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 3 h, and the -NCO content of the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0293] A four-necked flask equipped with a stir bar was charged with 40 g of PBA (20 mmol, Yantai Huada Chemical Industry CMA-44, Mn = 2000), and the flask containing PBA was heated to 90 °C and vacuumed to remove water for 3 h. The flask was charged with 200 ml of anhydrous DMAc and placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve PBA. The flask was charged with 8.89 g (40 mmol) of IPDI and 32 mg (0.08 wt% based on the mass of PBA) of TEDA catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 3 h, and the -NCO content of the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0294] Example 11

[0295] All glassware used for the synthesis was dried in an oven at 1 10 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 40 g of PBA (20 mmol, Yantai Huada Chemical Industry CMA-44, Mn = 2000), and the flask containing PBA was heated to 90 °C and vacuumed to remove water for 3 h. The flask was charged with 200 ml of anhydrous DMAc and placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve PBA. The flask was charged with 8.89 g (40 mmol) of IPDI and 32 mg (0.08 wt% based on the mass of PBA) of TEDA catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 3 h, and the -NCO content of the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0296] Prepolymer was prepared by adding 5.85 g (40 mmol) of succinic dihydrazide to a flask containing the prepolymer. The resulting mixture was heated to 70 °C and stirred for 2 h, after which the -NCO content of the system was determined to be stable using a potentiometric titrator. Then, 7.28 g (20 mmol) of C8F13OH was added, and the reaction was continued at 70 °C for 10 h. The polymer solution was cooled to room temperature, and the solvent was removed on a rotary evaporator. The crude product from DMAc was precipitated in distilled water and washed several times in an IPA solution, followed by an IPA / n-hexane wash. After drying at room temperature for 12 h, the product was dried in a vacuum oven at 120 °C for 12 h to obtain a white solid powder, which was labeled Modifier 12. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are reported in Table 1.

[0297] Example 12

[0298] All glassware used for the synthesis was dried in a 110 °C oven for 2 h. A four-necked flask equipped with a stir bar was charged with 10 g of PCDL (20 mmol, Daiso Corporation CD205PL, Mn = 500), and the flask containing the PCDL was heated to 100 °C and vacuumed for 3 h to remove water. The flask was charged with 50 mL of anhydrous DMAc and placed in a 70 °C oil bath and stirred under a nitrogen atmosphere to dissolve the PCDL. The flask was charged with 14.72 g (70 mmol) of TMDI and 0.02 g (0.2 wt% based on the mass of PCDL) of bismuth carboxylate catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 4 h, after which the -NCO content of the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0299] Prepolymer was prepared by adding 5.85 g (40 mmol) of succinic dihydrazide to a flask containing the prepolymer. The resulting mixture was heated to 70 °C and stirred for 2 h, after which the -NCO content of the system was determined to be stable using a potentiometric titrator. Then, 7.28 g (20 mmol) of C8F13OH was added, and the reaction was continued at 70 °C for 10 h. The polymer solution was cooled to room temperature, and the solvent was removed on a rotary evaporator. The crude product from DMAc was precipitated in distilled water and washed several times in an IPA solution, followed by an IPA / n-hexane wash. After drying at room temperature for 12 h, the product was dried in a vacuum oven at 120 °C for 12 h to obtain a white solid powder, which was labeled Modifier 12. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are reported in Table 1.

[0300] Example 13

[0301] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 10 g of PCDL (20 mmol, Daiso CD205PL, Mn = 500) and the flask containing the PCDL was heated to 100 °C and vacuumed for 3 h to remove water. To the flask was added 50 mL of anhydrous DMAc and the flask was placed in an oil bath at 70 °C and the PCDL was dissolved with stirring under a nitrogen atmosphere. To the flask was added 9.08 g (54 mmol) of HDI and 0.02 g (0.2 wt% based on the mass of the PCDL) of bismuth carboxylate catalyst. The mixture was stirred at 90 °C for 3 h under a nitrogen atmosphere and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0302] To the flask containing the prepolymer was added 2.58 g (26 mmol) of 3,5-diamino-1,2,4-triazole. The resulting mixture was heated to 65 °C and stirred for 3 h and the -NCO content of the system was determined to be stable using a potentiometric titrator. To the flask was added 6.50 g (14 mmol) of C10F17OH and the mixture was heated to 70 °C and stirred for an additional 8 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator. The crude product from the DMAc was precipitated into distilled water and washed several times in an IPA solution and then again in an IPA / n-hexane solution. The resulting white solid powder was dried at room temperature for 12 h and then in a vacuum oven at 120 °C for 12 h to give a modified agent 13. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modified agent were determined and the results are shown in Table 1.

[0303] Example 14

[0304] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 20 g of PCDL (20 mmol, Daiso CD210, Mn = 1000) and the flask containing the PCDL was heated to 100 °C and vacuumed for 3 h to remove water. To the flask was added 100 mL of anhydrous DMAc and the flask was placed in an oil bath at 70 °C and the PCDL was dissolved with stirring under a nitrogen atmosphere. To the flask was added 7.70 g (40 mmol) of HTDI and 50 mL of anhydrous DMAc was added and the mixture was stirred to dissolve and 16 mg (0.08 wt% based on the mass of the PCDL) of tin catalyst was added. The mixture was stirred at 80 °C for 4 h under a nitrogen atmosphere and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0305] A sample of 6.36 g (50 mmol) of 2-amino-6-hydroxypyrimidine-4(lH)-one was weighed into a flask containing the prepolymer. The resulting mixture was heated to 40 °C and stirred for 8 h, until the -NCO content of the system reached a plateau as determined by potentiometric titration. Then, 5.81 g (22 mmol) of C6F9OH was added and the reaction was continued at 40 °C for 12 h. The polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator, and the crude product from DMAc was precipitated into distilled water and washed several times in IPA solution, followed by IPA / n-hexane, and then dried at room temperature for 12 h and in a vacuum oven at 120 °C for 12 h to give a white solid powder, which was designated Modifier 14. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are shown in Table 1.

[0306] Example 15

[0307] All glassware used for the synthesis was dried in a 110 °C oven for 2 h. A four-necked flask equipped with a stir bar was charged with 40 g of PCDL (20 mmol, Wako Chemicals USA, Inc., T5652, Mn = 2000), and the flask containing the PCDL was heated to 100 °C and vacuumed for 3 h to remove water. The flask was charged with 150 mL of anhydrous DMAc and placed in a 70 °C oil bath and stirred under a nitrogen atmosphere to dissolve the PCDL. The flask was charged with 8.89 g (40 mmol) of IPDI and 50 mL of anhydrous DMAc, and the mixture was stirred to dissolve the contents, followed by the addition of 40 mg (0.1 wt% based on the mass of PCDL) of bismuth carboxylate catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 4 h, until the -NCO content of the system reached a plateau as determined by potentiometric titration, to give the prepolymer.

[0308] A sample of 2.58 g (10 mmol) of dodecanedioic acid dihydrazide was weighed into a flask containing the prepolymer. The resulting mixture was heated to 75 °C and stirred for 3 h, until the -NCO content of the system reached a plateau as determined by potentiometric titration. Then, 3.64 g (20 mmol) of C4F6OH was added and the reaction was continued at 75 °C for 4 h. The polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator, and the crude product from DMAc was precipitated into distilled water and washed several times in IPA solution, followed by IPA / n-hexane, and then dried at room temperature for 12 h and in a vacuum oven at 120 °C for 12 h to give a white solid powder, which was designated Modifier 15. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are shown in Table 1.

[0309] Example 16

[0310] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 20 g of PCL (20 mmol, Daicel Corp. 210N, Mn = 1000) and the flask containing PCL was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 150 mL of anhydrous DMAc and the flask was placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve the PCL. To the flask was added 6.99 g (36 mmol) of HXDI and 10 mg (0.05 wt% based on the mass of PCL) of DMCHA catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 3 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0311] To the flask containing the prepolymer was added 0.91 g (10 mmol) of carbohydrazide. The resulting mixture was heated to 60 °C and stirred for 7 h and the -NCO content of the system was determined to be stable using a potentiometric titrator and 0.53 g (10 mmol) of C4F7OH was added and the mixture was heated to 60 °C and stirred for an additional 12 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator and the crude product from the DMAc was precipitated into distilled water and washed several times in ethanol and dried at room temperature for 12 h and then placed in a vacuum oven at 80 °C for 12 h to give a light grey solid, which was designated Modifier 16. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are shown in Table 1.

[0312] Example 17

[0313] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 20 g of PCL (20 mmol, Daicel Corp. 210N, Mn = 1000) and the flask containing PCL was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 150 mL of anhydrous DMAc and the flask was placed in an oil bath at 70 °C and stirred under a nitrogen atmosphere to dissolve the PCL. To the flask was added 6.99 g (36 mmol) of HXDI and 10 mg (0.05 wt% based on the mass of PCL) of DMCHA catalyst. The mixture was stirred under a nitrogen atmosphere at 80 °C for 3 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0314] Into a flask containing the prepolymer, 0.64 g (5 mmol) of 2-amino-6-hydroxy pyrimidin-4(lH)-one was weighed. The resulting mixture was heated to 50 °C and stirred for 5 h, the -NCO content of the system was determined to be stable by potentiometric titrator, then 4.01 g (11 mmol) of C8F13OH was added and the reaction was continued at 60 °C for 5 h. The polymer solution was cooled to room temperature, precipitated in MeOH, and the resulting precipitate was repeatedly washed with a THF / MeOH mixed solvent, dried at room temperature for 12 h, and then placed in a vacuum oven at 120 °C for 12 h to obtain a translucent elastomer, which was labeled as Modifier 18. The weight average molecular weight (Mw), polydispersity, and fluorine element content of the modifier were determined, and the results are listed in Table 1.

[0315] Example 18

[0316] All glassware used for the synthesis reaction was dried in a 110 °C oven for 2 h. Into a four-necked flask equipped with a stir bar, 15 g of HLBH (10 mmol, Nisso PB GI-1000, Mn = 1500, Nisso PB Co., Ltd.) was added, and the flask containing HLBH was heated to 120 °C and vacuumed for 2 h to remove water. 100 mL of anhydrous toluene was added to the flask, and the flask was placed in an 80 °C oil bath and stirred to dissolve HLBH under nitrogen. 6.82 g (26 mmol) of HMDI was added to the flask, followed by the addition of 30 mL of anhydrous toluene, and the mixture was stirred to dissolve, followed by the addition of 0.03 g (0.2 wt% based on the mass of HLBH) of bismuth carboxylate catalyst. The mixture was continuously stirred under nitrogen at 110 °C for 2 h, and the -NCO content of the system was determined to be stable by potentiometric titrator to obtain a prepolymer.

[0317] Into a flask containing the prepolymer, 0.64 g (5 mmol) of 2-amino-6-hydroxy pyrimidin-4(lH)-one was weighed. The resulting mixture was heated to 50 °C and stirred for 5 h, the -NCO content of the system was determined to be stable by potentiometric titrator, then 4.01 g (11 mmol) of C8F13OH was added and the reaction was continued at 60 °C for 5 h. The polymer solution was cooled to room temperature, precipitated in MeOH, and the resulting precipitate was repeatedly washed with a THF / MeOH mixed solvent, dried at room temperature for 12 h, and then placed in a vacuum oven at 120 °C for 12 h to obtain a translucent elastomer, which was labeled as Modifier 18. The weight average molecular weight (Mw), polydispersity, and fluorine element content of the modifier were determined, and the results are listed in Table 1.

[0318] Example 19

[0319] All glassware used for the synthesis was dried in a 110 °C oven for 2 h. A four-necked flask equipped with a stir bar was charged with 20 g HHTPI (10 mmol, Epol, Mn = 2000), and the flask containing HHTPI was heated to 120 °C and vacuumed for 2 h to remove water. To the flask was added 100 mL anhydrous CHCl3, and the flask was placed in an oil bath at 60 °C and stirred under a nitrogen atmosphere to dissolve HLBH. To the flask was added 4.21 g (20 mmol) TMDI, and 30 mL anhydrous CHCl3 was added to dissolve the mixture. The mixture was stirred under a nitrogen atmosphere at 60 °C for 5 h, and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0320] A four-necked flask equipped with a stir bar was charged with 20 g HHTPI (10 mmol, Epol, Mn = 2000), and the flask containing HHTPI was heated to 120 °C and vacuumed for 2 h to remove water. To the flask was added 100 mL anhydrous CHCl3, and the flask was placed in an oil bath at 60 °C and stirred under a nitrogen atmosphere to dissolve HLBH. To the flask was added 4.21 g (20 mmol) TMDI, and 30 mL anhydrous CHCl3 was added to dissolve the mixture. The mixture was stirred under a nitrogen atmosphere at 60 °C for 5 h, and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0321] Example 20

[0322] All glassware used for the synthesis was dried in a 110 °C oven for 2 h. A four-necked flask equipped with a stir bar was charged with 20 g HHTPI (10 mmol, Epol, Mn = 2000), and the flask containing HHTPI was heated to 120 °C and vacuumed for 2 h to remove water. To the flask was added 100 mL anhydrous CHCl3, and the flask was placed in an oil bath at 60 °C and stirred under a nitrogen atmosphere to dissolve HLBH. To the flask was added 4.21 g (20 mmol) TMDI, and 30 mL anhydrous CHCl3 was added to dissolve the mixture. The mixture was stirred under a nitrogen atmosphere at 60 °C for 5 h, and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0323] To the flask containing the prepolymer, 1.18 g (10 mmol) of oxalyl dihydrazide was added. The resulting mixture was heated to 40 °C and stirred for 8 h, until the -NCO content of the system reached a plateau as determined by potentiometric titration. Then, 5.81 g (22 mmol) of C6F9OH was added and the reaction was continued at 45 °C for 10 h. The polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator and the crude product was dissolved in chloroform. The solution was washed with deionized water in a separatory funnel. The crude product was dried at room temperature for 12 h and then in a vacuum oven at 60 °C for 12 h to give a light yellow elastomer, which was designated as Modifier 20. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1.

[0324] Example 21

[0325] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. To a four-necked flask equipped with a stir bar, 40 g of PDMS-CNH2(20 mmol, UC-2330, Mn = 2000, Jiaxing Union Chemical Co., Ltd.) was added. The flask containing the PDMS-CNH2was heated to 80 °C and vacuumed for 3 h to remove water. To the flask, 8.83 g (42 mmol) of TMDI was added, followed by 0.2 g (0.5 wt% based on the mass of PDMS-CNH2) of bismuth carboxylate catalyst. The mixture was stirred at 70 °C under a continuous nitrogen flow for 4 h, until the -NCO content of the system reached a plateau as determined by potentiometric titration, to give a prepolymer.

[0326] To the flask containing the prepolymer, 1.88 g (16 mmol) of dodecanedioic acid dihydrazide was added, and 50 mL of anhydrous THF was added to reduce the viscosity. The resulting mixture was heated to 45 °C and stirred for 6 h, until the -NCO content of the system reached a plateau as determined by potentiometric titration. Then, 2.32 g (10 mmol) of C5F8OH was added and the reaction was continued at 45 °C for 12 h. The crude product was dissolved in chloroform and the solution was washed with deionized water in a separatory funnel. The crude product was dried at room temperature for 12 h and then in a vacuum oven at 60 °C for 12 h to give an amber viscous liquid, which was designated as Modifier 21. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1.

[0327] Comparative Example 1

[0328] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 60 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 3000, Mn = 3000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 6.65 g (40 mmol) of CHDI and 12 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst and the mixture was stirred at 90 °C under a constant stream of nitrogen for 3 h. The -NCO content of the system was determined using a potentiometric titrator until it reached a plateau, resulting in a prepolymer.

[0329] To the flask containing the prepolymer was added 100 ml of anhydrous acetone to reduce the viscosity and 10.56 g (40 mmol) of C6F9OH was added and the mixture was heated to 60 °C and stirred for 8 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator and the crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution. The crude product was dried at room temperature for 12 h and then placed in a vacuum oven at 80 °C for 12 h to give a translucent solid, which was designated as Modifier 22. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are reported in Table 1.

[0330] Comparative Example 2

[0331] All glassware used for the synthesis was dried in an oven at 110 °C for 2 h. A four necked flask equipped with a stir bar was charged with 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn = 1000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 6.65 g (40 mmol) of CHDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst and the mixture was stirred at 90 °C under a constant stream of nitrogen for 2 h. The -NCO content of the system was determined using a potentiometric titrator until it reached a plateau, resulting in a prepolymer.

[0332] To the flask containing the prepolymer was added 0.90 g (10 mmol) of 1,4-butanediol and 50 ml of anhydrous acetone to reduce the viscosity and the resulting mixture was heated to 70 °C and stirred for 3 h. The -NCO content of the system was determined using a potentiometric titrator until it reached a plateau and 5.28 g (20 mmol) of C6F9OH was added and the mixture was heated to 70 °C and stirred for an additional 4 h. The polymer solution was cooled to room temperature and the solvent was removed on a rotary evaporator and the crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution. The crude product was dried at room temperature for 12 h and then placed in a vacuum oven at 80 °C for 12 h to give a translucent elastomer, which was designated as Modifier 23. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are reported in Table 1.

[0333] Comparative Example 3

[0334] All glassware used in the synthesis was dried in an oven at 110 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn = 1000), and the flask containing PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 6.65 g (40 mmol) of CHDI, and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst was added, and the mixture was stirred at 90 °C for 2 h under a continuous flow of nitrogen. The -NCO content of the system was determined to be stable using a potentiometric titrator, and a prepolymer was obtained.

[0335] To the flask containing the prepolymer was added 1.18 g (10 mmol) of oxalyl dihydrazide, and 50 ml of anhydrous acetone was added to reduce the viscosity. The resulting mixture was heated and stirred at 55 °C for 5 h. The -NCO content of the system was determined to be stable using a potentiometric titrator, and 4.43 g (20 mmol) of silane coupling agent KH550 was added. The mixture was heated to 60 °C and stirred for 2 h. The polymer solution was cooled to room temperature, and the solvent was removed on a rotary evaporator. The crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution. After drying at room temperature for 12 h, the crude product was dried in a vacuum oven at 80 °C for 12 h to obtain a translucent elastomer, which was designated as Modifier 24. The weight average molecular weight (Mw) and polydispersity of the modifier were determined, and the results are shown in Table 1.

[0336] Comparative Example 4

[0337] All glassware used in the synthesis was dried in an oven at 110 °C for 2 h. A four-necked flask equipped with a stir bar was charged with 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn = 1000), and the flask containing PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 6.65 g (40 mmol) of CHDI, and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst was added, and the mixture was stirred at 90 °C for 2 h under a continuous flow of nitrogen. The -NCO content of the system was determined to be stable using a potentiometric titrator, and a prepolymer was obtained.

[0338] To the flask containing the prepolymer was added 1.18 g (10 mmol) of oxalyl dihydrazide. The resulting mixture was heated to 60 °C and stirred for 4 h, the -NCO content of the system was determined to be stable using a potentiometric titrator, 5.28 g (20 mmol) of C6F9OH was added, and the reaction was continued at 60 °C for 6 h. The polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator, and the crude product from DMAc was precipitated in distilled water and washed several times in ethanol solution. After drying at room temperature for 12 h, the product was dried in a vacuum oven at 80 °C for 12 h to obtain a white solid, which was designated as Modifier 25. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0339] Comparative Example 5

[0340] All glassware used for the synthesis was dried in a 110 °C oven for 2 h. To a four-necked flask equipped with a stir bar was added 30 g of PTMG (10 mmol, Mitsubishi Chemical Corporation PTMG 3000, Mn = 3000), and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 3.32 g (20 mmol) of CHDI. The mixture was stirred at 90 °C for 3 h under a continuous flow of nitrogen, and the -NCO content of the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0341] To the flask containing the prepolymer was added 0.83 g (7 mmol) of oxalyl dihydrazide, and 100 ml of anhydrous acetone was added to reduce the viscosity. The resulting mixture was heated to 55 °C and stirred for 6 h, the -NCO content of the system was determined to be stable using a potentiometric titrator, 1.85 g (7 mmol) of C6F9OH was added, and the reaction was continued at 60 °C for 8 h. The polymer solution was cooled to room temperature, the solvent was removed on a rotary evaporator, and the crude product was dissolved in MeOH and washed repeatedly with a MeOH / water solution. After drying at room temperature for 12 h, the product was dried in a vacuum oven at 80 °C for 12 h to obtain a white solid, which was designated as Modifier 26. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0342] Comparative Example 1

[0343] The 100 parts by weight of LDPE (Dow Chemical DFDA-1648NT, USA) as the base resin, adding 2 parts by weight of polyethylene wax, 0.4 parts by weight of antioxidant 1010, 0.8 parts by weight of antioxidant 168, 0.5 parts by weight of dibutyltin dilaurate were mixed uniformly, the mixture was added to the extruder for mixing, the temperature of each zone of the extruder was set to 140-180℃, the screw speed was 500 rpm, and the mixture was granulated by a granulator, and then dried to obtain mixed granules. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 140-200℃, and the test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The tensile strength comparison chart of the sample is shown in Figure 5 The tear strength comparison chart of the sample is shown in Figure 6 The water contact angle test chart of the sample is shown in Figure 7

[0344] Application Example 1.1

[0345] The 100 parts by weight of LDPE (Dow Chemical DFDA-1648NT, USA) as the base resin, adding 2 parts by weight of polyethylene wax, 0.4 parts by weight of antioxidant 1010, 0.8 parts by weight of antioxidant 168, 0.5 parts by weight of dibutyltin dilaurate were mixed uniformly, the mixture was added to the extruder for mixing, the temperature of each zone of the extruder was set to 140-180℃, the screw speed was 500 rpm, and the mixture was granulated by a granulator, and then dried to obtain mixed granules. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 140-200℃, and the test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The tensile strength comparison chart of the sample is shown in

[0346] Application Example 1.2

[0347] The 100 parts by weight of LDPE (Dow Chemical DFDA-1648NT, USA) as the base resin, adding 2 parts by weight of polyethylene wax, 0.4 parts by weight of antioxidant 1010, 0.8 parts by weight of antioxidant 168, 0.5 parts by weight of dibutyltin dilaurate were mixed uniformly, the mixture was added to the extruder for mixing, the temperature of each zone of the extruder was set to 140-180℃, the screw speed was 500 rpm, and the mixture was granulated by a granulator, and then dried to obtain mixed granules. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 140-200℃, and the test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The tensile strength comparison chart of the sample is shown in Figure 5 The tear strength comparison chart of the sample is shown in Figure 6 The water contact angle test chart of the sample is shown in Figure 7

[0348] Application Comparative Example 2

[0349] ​​With 100 parts by weight of TPU (Wanhua Chemical M885) as the base resin, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 0.3 parts by weight of di-n-octyltin dilaurate were uniformly mixed, the mixture was added to an extruder for mixing and kneading, the temperature of each zone of the extruder was set to 170-200°C, the screw rotation speed was 500 rpm, a granulator was used for granulation, and after drying, mixed granules were obtained. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 170-220°C, and test samples were obtained. The hardness, water contact angle, and mechanical properties of the samples were tested, and the results are shown in Table 2. The SEM images of the surface morphology of the samples are shown in Figure 4 (A). The tensile strength comparison chart of the samples is shown in Figure 5 (A). The tear strength comparison chart of the samples is shown in Figure 6 (A). The water contact angle test chart of the samples is shown in Figure 9 (A).

[0350] Application Example 2.1

[0351] With 100 parts by weight of TPU (Wanhua Chemical M885) as the base resin, 5 parts by weight of modifier 5, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 0.3 parts by weight of di-n-octyltin dilaurate were uniformly mixed, the mixture was added to an extruder for mixing and kneading, the temperature of each zone of the extruder was set to 170-200°C, the screw rotation speed was 500 rpm, a granulator was used for granulation, and after drying, mixed granules were obtained. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 170-220°C, and test samples were obtained. The hardness, water contact angle, and mechanical properties of the samples were tested, and the results are shown in Table 2.

[0352] Application Example 2.2

[0353] In application example 2.1, 5 parts by weight of modifier 4 was replaced by 5 parts by weight of modifier 6, and the rest remained unchanged, and test samples were obtained. The hardness, water contact angle, and mechanical properties of the samples were tested, and the results are shown in Table 2. The tensile stress-strain curve of the samples is shown in Figure 7 (A).

[0354] Application Example 2.3

[0355] In application example 2.1, 5 parts by weight of modifier 4 was replaced by 4 parts by weight of modifier 8, and the rest remained unchanged, and test samples were obtained. The hardness, water contact angle, and mechanical properties of the samples were tested, and the results are shown in Table 2. The EDS fluorine element mapping spectrum of the surface of the samples is shown in Figure 3 (A). The SEM images of the surface morphology of the samples are shown in Figure 4 (A). The tensile strength comparison chart of the samples is shown in Figure 5The sample tear strength comparison chart is shown as follows Figure 6 The sample water contact angle test chart is shown as follows Figure 9 .

[0356] Application Comparative Example 3

[0357] 100 parts by weight of nylon elastomer Pebax (Arkema PEBA 2533) was used as the base resin, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 0.3 parts by weight of di-n-octyltin dilaurate were added and uniformly mixed, the mixture was added to an extruder for mixing, the temperature of each zone of the extruder was set to 180-210°C, the screw rotation speed was 500 rpm, a granulator was used for granulation, and after drying, mixed granules were obtained. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 200-230°C, and a test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The sample tensile strength comparison chart is shown as follows Figure 5 The sample tear strength comparison chart is shown as follows Figure 6 The sample water contact angle test chart is shown as follows Figure 7 .

[0358] Application Example 3.1

[0359] 100 parts by weight of nylon elastomer Pebax (Arkema PEBA 2533) was used as the base resin, 5 parts by weight of modifier 6, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 0.3 parts by weight of di-n-octyltin dilaurate were added and uniformly mixed, the mixture was added to an extruder for mixing, the temperature of each zone of the extruder was set to 170-200°C, the screw rotation speed was 500 rpm, a granulator was used for granulation, and after drying, mixed granules were obtained. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 170-220°C, and a test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2.

[0360] Application Example 3.2

[0361] In Application Example 3.1, 5 parts by weight of modifier 6 was replaced by 10 parts by weight of modifier 7, and the rest remained unchanged, and a test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2.

[0362] Application Example 3.3

[0363] In Application Example 3.1, 5 parts by weight of modifier 6 was replaced by 4 parts by weight of modifier 8, and the rest remained unchanged, and a test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The sample tensile strength comparison chart is shown as followsFigure 5 The sample tear strength contrast chart is shown as Figure 6 The sample water contact angle test chart is shown as Figure 7 .

[0364] Application Comparative Example 4

[0365] 30 parts by weight of carbon black, 2 parts by weight of titanium dioxide, 8 parts by weight of dispersant fatty alcohol polyoxyethylene ether, 18 parts by weight of ethylene glycol monomethyl ether, 30 parts by weight of deionized water were uniformly dispersed by ultrasonic, 0.3 mm zirconium oxide beads were added, and ball milling was carried out at 500 r / min for 2 h to obtain a color paste; 100 parts by weight of acrylic resin (Japan Mitsubishi Rayon BR-106), 20 parts by weight of color paste, 3 parts by weight of initiator benzoyl peroxide were uniformly mixed at 1200 r / min to obtain an acrylate coating, which was coated on the surface of stainless steel, baked in an oven at 80℃ for 15 min, and irradiated under ultraviolet light for 5 min to obtain an acrylate coating layer with a thickness of 50 μm. The water contact angle and surface fluorine content of the coating layer were tested, and the results are shown in Table 2. The sample water contact angle test chart is shown as Figure 7 .

[0366] Application Example 4.1

[0367] 30 parts by weight of carbon black, 2 parts by weight of titanium dioxide, 8 parts by weight of dispersant fatty alcohol polyoxyethylene ether, 18 parts by weight of ethylene glycol monomethyl ether, 30 parts by weight of deionized water were uniformly dispersed by ultrasonic, 0.3 mm zirconium oxide beads were added, and ball milling was carried out at 500 r / min for 2 h to obtain a color paste; 100 parts by weight of acrylic resin (Japan Mitsubishi Rayon BR-106), 20 parts by weight of color paste, 3 parts by weight of initiator benzoyl peroxide were uniformly mixed at 1200 r / min to obtain an acrylate coating, which was coated on the surface of stainless steel, baked in an oven at 80℃ for 15 min, and irradiated under ultraviolet light for 5 min to obtain an acrylate coating layer with a thickness of 50 μm. The water contact angle and surface fluorine content of the coating layer were tested, and the results are shown in Table 2. The sample water contact angle test chart is shown as

[0368] Application Example 4.2

[0369] 30 parts by weight of carbon black, 2 parts by weight of titanium dioxide, 8 parts by weight of dispersant fatty alcohol polyoxyethylene ether, 18 parts by weight of ethylene glycol monomethyl ether, 30 parts by weight of deionized water were uniformly dispersed by ultrasonic, 0.3 mm zirconium oxide beads were added, and ball milling was carried out at 500 r / min for 2 h to obtain a color paste; 100 parts by weight of acrylic resin (Japan Mitsubishi Rayon BR-106), 20 parts by weight of color paste, 3 parts by weight of initiator benzoyl peroxide were uniformly mixed at 1200 r / min to obtain an acrylate coating, which was coated on the surface of stainless steel, baked in an oven at 80℃ for 15 min, and irradiated under ultraviolet light for 5 min to obtain an acrylate coating layer with a thickness of 50 μm. The water contact angle and surface fluorine content of the coating layer were tested, and the results are shown in Table 2. The sample water contact angle test chart is shown as Figure 7 .

[0370] Application Comparative Example 5

[0371] With 100 parts by weight of polycarbonate (Taihua Guagu PC IR2200CB) as the base resin, 4 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 0.05 parts by weight of antioxidant BHT, and 0.3 parts by weight of di-n-octyltin dilaurate were uniformly mixed, the mixture was added to an extruder for mixing, the temperature of each zone of the extruder was set to 220-260°C, the screw speed was 500 rpm, and a granulator was used for granulation. After drying, mixed granules were obtained. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 240-280°C, and a test sample was obtained. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested, and the results are shown in Table 2. The water contact angle test diagram of the sample is shown in FIG. Figure 8 .

[0372] Application Example 5.1

[0373] With 100 parts by weight of polycarbonate (Taihua Guagu PC IR2200CB) as the base resin, 4 parts by weight of modifier 12, 4 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 0.05 parts by weight of antioxidant BHT, and 0.3 parts by weight of di-n-octyltin dilaurate were uniformly mixed, the mixture was added to an extruder for mixing, the temperature of each zone of the extruder was set to 220-260°C, the screw speed was 500 rpm, and a granulator was used for granulation. After drying, mixed granules were obtained. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 240-280°C, and a test sample was obtained. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested, and the results are shown in Table 2.

[0374] Application Example 5.2

[0375] In application example 5.1, 4 parts by weight of modifier 12 were replaced by 2 parts by weight of modifier 13, and the rest remained unchanged, to obtain a test sample. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested, and the results are shown in Table 2. The water contact angle test diagram of the sample is shown in FIG. Figure 8 .

[0376] Application Example 5.3

[0377] In application example 5.1, 4 parts by weight of modifier 12 were replaced by 4 parts by weight of modifier 14, and the rest remained unchanged, to obtain a test sample. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested, and the results are shown in Table 2.

[0378] Application Comparative Example 6

[0379] With 100 parts by weight of TPE (German glue TPE K TF9AAC) as the base resin, 5 parts by weight of naphthenic oil, 2 parts by weight of triphenyl phosphate, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, 0.5 parts by weight of light stabilizer 770, 0.5 parts by weight of zinc stearate were mixed uniformly, the mixed material was added to the extruder for mixing, the temperature of each zone of the extruder was set to 160-210℃, the screw speed was 500rpm, the granulator was used for granulation, and the mixed granules were obtained after drying. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 170-220℃, the test sample was obtained, the hardness, water contact angle, mechanical properties of the sample were tested, the results were listed in Table 2, the sample tensile strength comparison chart was shown in Figure 5 , the sample tear strength comparison chart was shown in Figure 6 , and the sample water contact angle test chart was shown in Figure 8 .

[0380] Application Example 6.1

[0381] With 100 parts by weight of TPE (German glue TPE K TF9AAC) as the base resin, 5 parts by weight of naphthenic oil, 2 parts by weight of triphenyl phosphate, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, 0.5 parts by weight of light stabilizer 770, 0.5 parts by weight of zinc stearate were mixed uniformly, the mixed material was added to the extruder for mixing, the temperature of each zone of the extruder was set to 160-210℃, the screw speed was 500rpm, the granulator was used for granulation, and the mixed granules were obtained after drying. The mixed granules were injection molded by an injection molding machine, the temperature range of each zone of the injection molding machine was 170-220℃, the test sample was obtained, the hardness, water contact angle, mechanical properties, surface fluorine content of the sample were tested, the results were listed in Table 2, the sample tensile strength comparison chart was shown in Figure 5 , the sample tear strength comparison chart was shown in Figure 6 , and the sample water contact angle test chart was shown in Figure 8 .

[0382] Application Example 6.2

[0383] 8 parts by weight of modifier 8 in application example 6.1 was replaced by 5 parts by weight of modifier 18, and the rest was unchanged, the test sample was obtained, the hardness, water contact angle, mechanical properties, surface fluorine content of the sample were tested, and the results were listed in Table 2.

[0384] Application Comparative Example 7

[0385] With 100 parts by weight of silicone rubber (Shenzhen Jiahai Silicon Rubber Co., Ltd. GA-1081) as the base resin, 1 part by weight of vulcanizing agent DBPMH, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 10 parts by weight of white carbon black were added, and the mixture was uniformly mixed at room temperature using an open mill to produce a sheet. The temperature of the vulcanizing machine was set to 150°C, the mold was preheated, and then the mixed sample sheet was placed in the mold. The sample was vulcanized at 15 MPa for 15 min, and then hot-molded and demolded to obtain a test sample. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The tensile strength comparison chart of the sample is shown in Figure 5 The tear strength comparison chart of the sample is shown in Figure 6 The water contact angle test chart of the sample is shown in Figure 8

[0386] Application Comparative Example 7.1

[0387] With 100 parts by weight of silicone rubber (Shenzhen Jiahai Silicon Rubber Co., Ltd. GA-1081) as the base resin, 6 parts by weight of modifier 20, 1 part by weight of vulcanizing agent DBPMH, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 10 parts by weight of white carbon black were added, and the mixture was uniformly mixed at room temperature using an open mill to produce a sheet. The temperature of the vulcanizing machine was set to 150°C, the mold was preheated, and then the mixed sample sheet was placed in the mold. The sample was vulcanized at 15 MPa for 15 min, and then hot-molded and demolded to obtain a test sample. The hardness, water contact angle, and mechanical properties of the sample were tested, and the results are shown in Table 2. The tensile strength comparison chart of the sample is shown in Figure 5 The tear strength comparison chart of the sample is shown in Figure 6 The water contact angle test chart of the sample is shown in Figure 8

[0388] Application Example 7.2

[0389] In application example 4.1, 6 parts by weight of modifier 12 were replaced with 6 parts by weight of modifier 21, and the rest remained unchanged to obtain a test sample. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested, and the results are shown in Table 2.

[0390] Application Comparative Example 8

[0391] In application example 2.3, 4 parts by weight of modifier 8 were replaced with 5 parts by weight of modifier 22, and the rest remained unchanged to obtain a test sample. The contact angle, surface energy, mechanical properties, and surface fluorine content of the sample were tested, and the results are shown in Table 3. The water contact angle test chart of the sample is shown in Figure 9

[0392] Application Comparative Example 9

[0393] ​​​Replace 4 parts by weight of modifier 8 in application example 2.3 with 5 parts by weight of modifier 23, and the rest remains unchanged to obtain a test sample, test the contact angle, surface energy, mechanical property, and surface fluorine content of the sample, and the results are listed in Table 3, and the water contact angle test diagram of the sample is as shown in Figure 9 .

[0394] Application Comparative Example 10

[0395] Replace 4 parts by weight of modifier 8 in application example 2.3 with 5 parts by weight of modifier 24, and the rest remains unchanged to obtain a test sample, test the contact angle, surface energy, mechanical property, and surface fluorine content of the sample, and the results are listed in Table 3, and the water contact angle test diagram of the sample is as shown in Figure 9 .

[0396] Application Comparative Example 11

[0397] Replace 4 parts by weight of modifier 8 in application example 2.3 with 5 parts by weight of modifier 25, and the rest remains unchanged to obtain a test sample, test the contact angle, surface energy, mechanical property, and surface fluorine content of the sample, and the results are listed in Table 3, and the water contact angle test diagram of the sample is as shown in Figure 9 .

[0398] Application Comparative Example 12

[0399] Replace 4 parts by weight of modifier 8 in application example 2.3 with 5 parts by weight of modifier 26, and the rest remains unchanged to obtain a test sample, test the contact angle, surface energy, mechanical property, and surface fluorine content of the sample, and the results are listed in Table 3, and the water contact angle test diagram of the sample is as shown in Figure 9 .

[0400] Table 1. Performance test table of the prepared modifier in the embodiment of the application

[0401]

[0402]

[0403] Table 2. Performance test table of application comparative examples and application example samples of the application

[0404]

[0405]

[0406] From the application comparative example and application example comparison data in Table 2, it can be seen that for different base resins (polyolefin, polyurethane, polyamide, acrylic resin, polycarbonate, thermoplastic elastomer, silicone rubber), the durable low surface energy polymer modifier in the application can play a significant hydrophobic antifouling effect. After adding the modifier in the base resin, the water contact angle is increased by more than 40-50°, and the improvement effect is obvious. After adding the modifier in the application, the percentage of fluorine atoms on the surface of the sample is much larger than the theoretical value, indicating that the distribution content of the modifier on the surface of the resin is much larger than the inside of the resin, and it has a tendency to accumulate on the surface of the resin, which also indicates that the modifier itself migrates to the surface of the resin to play a hydrophobic effect. In addition, from the test data, it can be seen that the addition of the low surface energy polymer modifier in the application has little effect on the hardness of the base resin, and the tensile strength and tear strength of the base resin are also significantly improved, which has very outstanding application value. The modifier in the application has a certain molecular weight, and more migrates to the surface of the base resin to play a role. The application not only modifies the base resin with a modifier polymer segment that has good compatibility with the base resin, but also forms strong hydrogen bonding between the modifier segment itself or the base resin through the multi-tooth hydrogen bonding structure and fluorinated segment structure on the modifier polymer segment, which improves the binding degree between the base segments and improves the mechanical strength of the base resin.

[0407] Table 3. Performance comparison table of application comparative example and application example samples of the application

[0408]

[0409] Table 4. Durability test water contact angle data of application comparative example and application example samples of the application

[0410]

[0411]

[0412] As can be seen from the comparative data of the application examples and the application comparative examples in Table 3 and Table 4, in the case of similar molecular weight of the modifier (weight average molecular weight Mw≈5000 g / mol), the water contact angle of the TPU sample modified by the durable low surface energy polymer modifier in the application (application example 2.3) is increased by 46°, the surface energy is reduced by 85%, and the mechanical strength is also greatly improved, compared with the unmodified sample (application comparative example 2), which has a significant surface energy reduction effect and a relatively high percentage of surface fluorine atoms. After the modified sample is placed in an open environment for 60 days, the hydrophobicity of the sample remains almost unchanged, and after being placed in PBS buffer and blood simulation test liquid for 60 days, the water contact angle of the sample is only decreased by 7%, and the sample still maintains good hydrophobic effect, which shows excellent low surface durability. The low surface energy polymer modifier in the application has a multi-dentate hydrogen bond monomer structure, which is in a dissociated state during processing and heat treatment, has good migration ability, can disperse well in the matrix, and aggregate from the inside of the matrix to the surface. The multi-dentate hydrogen bond monomer structure in the system can be bonded through strong hydrogen bond interaction after migration is completed and cooling, increasing the locking between them and achieving stability on the surface of the matrix, thereby effectively reducing the risk of modifier elution and loss, reducing the possibility of migration, flushing, or dissolving into blood, enhancing the low surface energy durability of the matrix surface, and realizing the combination of hydrophobicity and long-term durability. If the multi-dentate hydrogen bond monomer structure is not introduced into the molecular chain of the modifier (application comparative example 8 and application comparative example 9), and a modifier containing only fluorinated structure is prepared, the water contact angle of the TPU sample modified by the modifier is increased by about 30°, and the surface energy is reduced by about 70%. The hydrophobicity durability in an open environment, PBS buffer, and blood simulation test liquid, and the mechanical strength of the sample are all inferior to those of the modifier in the application. When the fluorinated structure of the modifier in the application is replaced by a siloxane structure (application comparative example 10), the water contact angle and surface energy improvement effect of the modified sample are significantly reduced, indicating that the fluorinated structure used in the modifier has excellent hydrophobic effect. In addition, by using flexible aliphatic polymer diol / diamine and aliphatic diisocyanate with strong chain motion ability as raw materials, the modifier polymer chain structure has high migration ability, and high surface fluorine enrichment is achieved in the matrix resin. As a comparison, the modifier prepared by using aromatic polymer diol and aromatic diisocyanate (application comparative example 11) has poor migration ability, so the water contact angle and surface energy improvement effect of the sample are also significantly reduced compared with application example 2.3. In the durability test, the samples of application comparative example 10 and application comparative example 11 also do not show good hydrophobicity durability, and the hydrophobicity of the samples in an open environment, PBS buffer, and blood simulation test liquid decreases significantly in a short time, and even fails.From the data of application comparative example 12, it can be seen that the molecular weight of the modifier itself is too high, its migration ability is weakened, and the hydrophobic effect is also poor.

[0413] The modifier in each of the above embodiments and the modified product in each of the application embodiments can have the effects of waterproofing, stain resistance, dust resistance, anticoagulation, antithrombosis, antibacterial, self-cleaning, etc., and can be applied in the field of coating (e.g., as a waterproof and stain-resistant polyurethane / acrylate / silicone coating, a waterproof and stain-resistant polyurethane / acrylate / silicone coating), the field of textiles (e.g., as a textile surface coating, or as a surface modifier for chemical fibers such as polyester, nylon, acrylic, vinylon, polypropylene, chlorofiber, and spandex), the field of electronic products (e.g., as a surface dustproof and stain-resistant self-cleaning treatment for the surface of devices such as watches, smartphones, telephones, televisions, video players, video recorders, camcorders, radios, recorders, combination speakers, laser recorders, computers, game consoles, mobile communication products, etc., internal parts, motherboard chips, etc.), the field of automobile accessory products (e.g., as a surface dustproof and stain-resistant treatment for automobile body accessories, car film, bumpers, doors, fenders, windshields, pillars, seats, center consoles, engine covers, trunk covers, sunroofs, roofs, door locks, armrests, floors, door sills, etc.), the field of filtration membranes (e.g., sewage filtration membranes, water purification membranes, seawater desalination membranes, hemodialysis membranes, membranes for medical and pharmaceutical fields, membranes for food and beverage manufacturing fields, membranes for municipal water treatment, membranes for industrial and electronic industries, membranes for material concentration and purification, etc., made of materials such as polypropylene, polysulfone, polyether sulfone, polyvinylidene fluoride, and polytetrafluoroethylene, and having the effects of stain resistance, antibacterial, self-cleaning, etc.), the field of medical products (e.g., medical instruments, medical devices, surgical instruments, drug delivery devices, drug release devices, grafts, stents, pacemakers, implantable cardioverter-defibrillators, cardiac stents, cardiovascular device leads, ventricular assist devices and transmission systems, heart valves, vena cava filters, intravascular coils, catheters, catheter connectors, catheter valves, intravenous delivery lines, intravenous delivery manifolds, shunts, wound drains, drainage catheters, infusion ports, cochlear implants, endotracheal tubes, tracheostomy tubes, breathing machine breathing tubes and lines, implantable sensors, ophthalmic devices, orthopedic devices, dental equipment, dental implants, periodontal implants, breast implants, penile implants, maxillofacial implants, orthopedic implants, valves, artificial blood vessels, artificial skin, orthotics, oxygen masks, scaffolding, suture materials, needles, hernia repair meshes, tension-free vaginal tape and vaginal sling, prosthetic nerve devices and ear tubes, medical dressings, medical bandages, medical gauze, medical tape, medical pads, medical sponges, blood oxygenators, breathing machines, contraceptive devices, feminine hygiene products, endoscopes, dialysis membranes, guide wires, fluid collection bags, blood bags, infusion bags, drug delivery bags and tubing, feeding tubes, tissue regeneration or cell culture devices, etc., having the effects of waterproofing, stain resistance, dust resistance, anticoagulation, antithrombosis, antibacterial, self-cleaning, etc.).

[0414] It should be noted that the above only describes the preferred embodiments of the present application, and is not used to limit the patent scope of the present application. For example, other compound raw materials for synthesizing the described durable low surface energy polymer modifier that can be frozen on the surface of the substrate, the structure of the modifier, the applicable substrate resin, the applicable preparation method, the application field, and the like can be modified, equivalently replaced, and extended according to the technical solutions described in the foregoing embodiments within the protection scope and spirit of the present application. Any modification, equivalent replacement, improvement, and the like made within the spirit and principles of the present application, or directly or indirectly applied to other related technical fields, should be included in the protection scope of the present application.

Claims

1. A durable low surface energy polymer modifier that can freeze on the surface of a substrate, characterized in that: Its main chain contains a multidentate hydrogen bond monomer structure capable of forming a tridentate or higher hydrogen bond structure, and its polymer chain end group is a fluorinated structure; it is prepared using at least the following raw materials in parts by weight: Wherein, the multidentate hydrogen bond reactant can form a multidentate hydrogen bond monomer structure after polymerization reaction with the isocyanate group; Wherein, the multidentate hydrogen bond monomer structure contains at least one of the following structures: wherein R is selected from hydroxyl, amino, and alkane groups; X is independently selected from nitrogen atoms and carbon atoms; i is the number of linking units, and when X is selected from nitrogen atoms, i=0 or 1; when X is selected from carbon atoms, i=1 or 2; Wherein, the fluorinated structure is selected from the following structures: wherein x is independently the number of fluorine atoms connected to the carbon atom, which is an integer from 1 to 2, wherein when x is 1, the carbon atom is also connected to a hydrogen atom; and y is the number of repeating units, which is an integer from 3 to 9.

2. The durable low surface energy polymer modifier capable of freezing on the substrate surface according to claim 1, characterized in that: The durable low surface energy polymer modifier has the following structure: Among them, P, I, A, F t , m, n, r are defined as follows: P is independently a unit formed by polymerization of at least one aliphatic polymer diol or aliphatic polymer diamine, wherein the number average molecular weight of the aliphatic polymer diol or aliphatic polymer diamine is selected from 400-2000 Da; I are each independently a unit formed by polymerization of at least one aliphatic diisocyanate; A is each independently a unit formed by polymerization of at least one multidentate hydrogen bonding reactant; F t Each independently is a unit formed by polymerization of at least one monohydroxy fluoroalcohol compound; m, n, and r are the number of repeating units, each independently an integer from 1 to 5, and m+n+r≤10; The durable low surface energy polymer modifier has a weight average molecular weight Mw of 4000-10000 and a fluorine content of 2-10%.

3. The durable low surface energy polymer modifier capable of freezing on the substrate surface according to claim 1, characterized in that: The aliphatic polymer diol and aliphatic polymer diamine are respectively selected from the following structures: Wherein, M is independently an aliphatic carbon chain, an aliphatic carbon heterochain, or a siloxane chain, and k is an integer greater than or equal to 1.

4. The durable low surface energy polymer modifier capable of freezing on the substrate surface according to claim 3, characterized in that: The aliphatic polymer diol is selected from polyether diol, polyester diol, polyurethane diol, polylactic acid diol, polysiloxane diol, polycarbonate diol, polyolefin diol, polyacrylate diol, polymethacrylate diol and copolymers of the above chain segment structures and mixtures containing the above structures; the aliphatic polymer diamine is selected from polyethylene oxide diamine, polypropylene oxide diamine, polytetramethylene glycol diamine, and polysiloxane diamine terminated with hydrocarbon amino groups.

5. The durable low surface energy polymer modifier capable of freezing on a substrate surface according to claim 1, wherein: The aliphatic diisocyanate is selected from butane 1,4-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octane 1,8-diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-cyclohexane dimethyl diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, norbornane diisocyanate, lysine diisocyanate and mixtures thereof.

6. The durable low surface energy polymer modifier capable of freezing on a substrate surface according to claim 1, wherein: The multidentate hydrogen bond reactant contains two reactive groups and at least one of the following structures: wherein R is selected from hydroxyl, amino, and alkane groups; X is independently selected from nitrogen atoms and carbon atoms; i is the number of linking units, and when X is selected from nitrogen atoms, i=0 or 1; when X is selected from carbon atoms, i=1 or 2; Wherein, the reactive group is selected from hydroxyl, amino, thiol, hydrazine and hydrazide groups.

7. The durable low surface energy polymer modifier capable of freezing on the substrate surface according to claim 6, characterized in that: The multidentate hydrogen bond reactant is selected from at least one of the following structures:

8. The durable low surface energy polymer modifier capable of freezing on a substrate surface according to claim 1, wherein: The monohydroxy fluoroalcohol compound has the following structure: Wherein, L is an organic linking group, x is independently the number of fluorine atoms connected to the carbon atom, which is an integer from 1 to 2, wherein when x is 1, the carbon atom is also connected to a hydrogen atom; y is the number of repeating units, which is an integer from 3 to 9.

9. The durable low surface energy polymer modifier capable of freezing on the substrate surface according to claim 8, characterized in that: The monohydroxy fluoroalcohol compound is selected from hexafluorobutanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol, heptylfluorohexanol, 1H,1H,2H,2H-perfluorohexanol, undecafluorohexanol, 1H,1H,2H,2H-perfluorooctanol, 1H,1H,8H-perfluorooctanol, 1H,1H-heptadecafluorononanol, 1H,1H,2H,2H-perfluorodecanol, and 1H,1H-perfluorodecanol.

10. A method for preparing a durable low surface energy polymer modifier capable of freezing on a substrate surface according to any one of claims 1 to 9, characterized in that: Prepared by the following steps: S1: Heat the aliphatic polymer diol or aliphatic polymer diamine to 80-120°C and remove water in a vacuum for 2-4 hours; S2. heating a fixed molar amount of an aliphatic polymer diol or an aliphatic polymer diamine and an aliphatic diisocyanate to 60-110° C. under nitrogen and stirring for 2-6 hours until the -NCO groups in the system are stable to obtain a prepolymer; S3, adding a multidentate hydrogen bond reactant to the prepolymer in S2, controlling the reaction temperature at 40-80°C, continuously heating and stirring with nitrogen for 2-8 hours, and then adding a monohydroxy fluoroalcohol compound and continuing heating and stirring for 2-12 hours to cap the end; S4, washing and purifying the crude product obtained in S3, and drying it in a vacuum oven at room temperature and 60-120°C in sequence; The molar ratio of the aliphatic polymer diol or aliphatic polymer diamine, aliphatic diisocyanate, multidentate hydrogen bond reactant and monohydroxy fluoroalcohol compound is 1:1.3-4.5:0.2-3.5:0.3-1.

1.

11. A durable low surface energy material, characterized in that: The invention comprises 80-100 parts by weight of a base resin, 2-10 parts by weight of a durable low surface energy polymer modifier capable of freezing on the surface of a base as claimed in any one of claims 1 to 9, 0-10 parts by weight of an additive, and 0-30 parts by weight of a filler; Wherein, the matrix resin is selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylic resin, unsaturated polyester, polyurethane, polyamide, polycarbonate, thermoplastic polyester, thermoplastic elastomer, polysulfone, polyethersulfone, polyarylsulfone, polyaryletherketone, silicone resin; Wherein, the additive is selected from antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, release agents, plasticizers, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, matting agents, and flame retardants; Wherein, the filler is selected from inorganic non-metal fillers, metal fillers, organic fillers, and organometallic compound fillers.

12. Use of the durable low surface energy material according to claim 11 in the fields of coatings, textiles, electronic products, automotive parts, filtration membranes, and medical products, wherein: The medical products include medical instruments, medical devices, surgical instruments, drug delivery devices, drug release devices, implants, stents, pacemakers, implantable cardioverter-defibrillators, cardiac stents, cardiovascular device leads, ventricular assist devices and drive systems, heart valves, vena cava filters, intravascular coils, catheters, catheter connectors, catheter valves, intravenous delivery lines, intravenous delivery manifolds, shunts, wound drains, drainage catheters, infusion ports, cochlear implants, endotracheal tubes, tracheostomy tubes, ventilator breathing tubes and lines, implantable sensors, ophthalmic devices, orthopedic devices, dental equipment, Dental implants, periodontal implants, breast implants, penile implants, maxillofacial implants, plastic implants, valves, artificial blood vessels, artificial skin, braces, oxygen masks, scaffolding, suture materials, needles, hernia repair mesh, tension-free vaginal slings and vaginal slings, prosthetic neural devices and ear tubes, medical dressings, medical bandages, medical gauze, medical tape, medical pads, medical sponges, blood oxygenators, ventilators, contraceptive devices, feminine hygiene products, endoscopes, dialysis membranes, guidewires, fluid collection bags, blood bags, infusion bags, drug delivery bags and tubing, feeding tubes, tissue regeneration or cell culture devices.

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