Dynamically migratable low-surface-energy polymer modifier and preparation method thereof

Abstract

The invention discloses a dynamically migratable low-surface-energy polymer modifier and a preparation method thereof, the polymer main chain of the low-surface-energy polymer modifier comprises a temperature-sensitive dynamic structure, and the polymer chain end group of the low-surface-energy polymer modifier is a fluorinated structure. The 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 migrates to the surface of a material in a processing heat treatment and use process, so that multiple effects of water resistance, pollution resistance, dust prevention, anticoagulation, antithrombus, antibiosis, self-cleaning and the like can be achieved; the modifier not only can achieve an excellent low surface energy modification effect, but also has no influence on the performance of matrix resin. The invention further discloses a low-surface-energy blending composition containing the low-surface-energy polymer modifier and application of the low-surface-energy blending composition.

Description

Technical Field

[0001] The invention belongs to the field of surface modification materials, and in particular relates to a low-surface-energy polymer modifier capable of dynamic migration. Background Art

[0002] The phenomenon that a liquid can spread on a solid surface is called wetting; conversely, it is called non-wetting. Using Young's equation for thermodynamic equilibrium, an angle appears at the point where a droplet contacts a smooth material surface, defined as the contact angle θ. This angle is used as an indicator to define the degree of wetting to characterize the hydrophilicity / hydrophobicity of the material surface. The smaller the contact angle, the greater the wettability and the greater the spreadability. 0°<θ<90°, the liquid can wet the solid, and the smaller the angle, the better the wettability, which is called the hydrophilic contact angle. 90°<θ<180°, the liquid does not wet the solid, which is also called the hydrophobic contact angle or the hydrophobic contact angle. Recent studies have defined the hydrophilicity / hydrophobicity boundary as 90°, i.e., θ<90° is a hydrophilic surface, θ>90° is a hydrophobic surface, and θ>150° is a super-hydrophobic surface.

[0003] At present, people have an increasing demand for high-quality, multifunctional materials, coatings and textiles. Improving the hydrophobic, anti-fouling, anti-sticking and anti-graffiti properties of existing resin materials, paint coatings or paint film surfaces has always been a hot topic and difficulty in the field of coatings research, especially 3C coatings used on the surfaces of computers, communications and consumer electronic products, as well as hardening coatings used on the surfaces of optical films such as displays and touch screens, and anti-graffiti coatings used to prevent and treat urban psoriasis. From a technical perspective, there are two main ways to achieve the hydrophobic and oleophobic functions of the material surface. One is to add low-surface-energy substances, mainly organic fluorine and organic silicon, to the surface of the material; the other is to construct a rough structure on the surface of the material. The existing technologies currently use coatings on the surface of the material to improve its surface properties, but the coatings are prone to scratching, loss, shedding and cracking, which greatly reduces the hydrophobic and oleophobic effects of the material surface. How to avoid the problems of shedding, peeling, cracking, elution and scratching of the coatings is a difficult problem that has been waiting to be solved in this field. There is no doubt that studying the addition of an efficient low surface energy modifier to the existing material formula without changing its other original properties is a quick, efficient and practical method, but there are currently no modified materials with good effects.

[0004] In current research, introducing siloxane units into the coating matrix component to reduce its surface energy and improve its hydrophobicity is a common method in the existing technology.

[0005] WO 2017 / 151621 A1 discloses non-isocyanate-functionalized, siloxane-modified glycidyl carbamates for coatings. The glycidyl carbamates are obtained by reacting an organic polyisocyanate, glycidol, and at least one bis(hydroxyalkyl)-terminated polydimethylsiloxane.

[0006] Document US 2008 / 0213599 A1 describes a polymeric material obtained by reacting a mixture comprising amino-functional polyorganosiloxanes, polyisocyanates and polyols, and the use of this material as an antifouling coating.

[0007] CN 114829443 A discloses a polysiloxane-functionalized polyurethane for improving the hydrophobicity of a surface. The polyurethane is applied to the surface of a substrate by spraying, but the contact angle of the substrate is only increased by 20°, which is not an ideal effect.

[0008] CN 115894846A discloses a hydrophobic polyurethane, its preparation method and application. Silicon-containing groups with low surface energy are introduced into the polyurethane main chain in the form of a silane coupling agent, so that a high density of hydrophobic groups is formed on the polymer chain, reducing the surface energy. The water contact angle of the prepared material is only 90°.

[0009] In known prior art systems, siloxane structural units present compatibility issues with other systems. Due to their inherent poor bonding with the substrate, the siloxane layer is susceptible to shedding and delamination upon contact with water or surface scratching, resulting in a loss of the surface hydrophobicity provided by the siloxane chains. Furthermore, the hydrophobicity enhancement provided by the siloxane structure is limited, far inferior to that achieved by organofluorine systems.

[0010] With the continuous deepening of research on fluorinated compounds, multifunctional coatings and fabrics with water repellency, anti-fouling, and easy-to-remove properties have attracted widespread attention. Due to the high bond energy and relative stability of the carbon-fluorine bond in fluoropolymers, the fluorine atoms not only firmly bind to the carbon atoms but are also arranged very tightly on the outer layer of the carbon skeleton, effectively preventing the exposure of carbon atoms and carbon chains. Therefore, fluorocarbon polymers exhibit excellent chemical stability, weather resistance, corrosion resistance, and oxidation resistance. Their coatings have low surface energy and excellent water repellency, oil repellency, and anti-fouling properties. They are widely used in a wide range of fields, including aerospace, aviation, automobiles, electronics, textiles, carpets, leather, papermaking, packaging, washing, machinery, and construction.

[0011] CN 106220839 B discloses a perfluoropolyether-based anti-graffiti additive. This additive uses perfluoropolyether carboxylic acid or perfluoropolyether ester compounds as raw materials. By grafting polyurethane segments and introducing reactive alcoholic hydroxyl groups at the ends, the additive improves its compatibility and reactivity with polyurethane, alkyd, or epoxy coatings, enhancing the coating's stain resistance and preventing haze in the paint film. However, the examples only provide a textual description of the product's stain resistance without providing detailed data, making it difficult to intuitively understand its anti-graffiti effectiveness.

[0012] CN 114133519 A discloses a thermoplastic polyurethane elastomer, its preparation method, and application. The preparation method for the medical thermoplastic polyurethane elastomer comprises adding a polyol, a fluorinated small molecule alcohol, a fluorescent small molecule alcohol, a cyclic small molecule alcohol, a polyisocyanate, and a catalyst to a reactor, and thoroughly mixing and reacting to prepare the thermoplastic polyurethane elastomer. This method of synthesizing fluorinated polyurethane elastomers using fluorinated small molecules is not practical. The high raw material costs and complex synthesis process limit its application to small batches, and using this modified fluorinated polyurethane directly as a finished product is not practical. Furthermore, the hydrophobicity-enhancing effect demonstrated in the examples is not significant.

[0013] Evonik's patent series (CN 110167995 B, US8071683B2, US8178620B2, CN 110891620 B, CN110891621B, CN 112135882 A) disclose a fluorinated surface-modified macromolecule. These patents characterize the effects of the modified molecules on the thermal properties and contact angle of the product, and conduct DEHP leaching analysis, BCA analysis of protein deposition, analysis of deposition in blood, and application research on bacterial adhesion on polyurethane (PU) rods. However, none of these patents disclose the effects of the addition of the modified molecules on substrate properties, and the effect of improving the contact angle is not very significant.

[0014] How to further improve the hydrophobic effect of the organic fluorine system and obtain a low surface energy modifier with excellent low surface energy modification effect, strong practicality and wide applicability has always been a difficult problem that needs to be solved urgently. Summary of the Invention

[0015] The present invention addresses the problem that the prior art cannot solve, which requires the hydrophobic modifier to have excellent migration ability, ensure good bonding with the matrix, and not affect the strength of the matrix. The following technical solutions are adopted to solve the problem:

[0016] The present invention provides a low-surface-energy polymer modifier capable of dynamic migration, characterized in that the polymer main chain includes a temperature-sensitive dynamic structure, and the polymer chain end groups are fluorinated structures; the modifier is prepared using at least the following raw materials in parts by weight:

[0017]

[0018] The temperature-sensitive dynamic structure can undergo dynamic dissociation and generation-conversion based on dynamic covalent bonds at a temperature of at least 50-80°C, and contains at least one of the following structures:

[0019] Class I, organic borate ester structure:

[0020]

[0021] wherein the boron atom B is connected to one carbon atom via a boron-carbon bond and at least one organic group is connected to the boron atom via said boron-carbon bond; K is selected from substituted forms of 1,2-ethylene, substituted forms of 1,3- propylene, substituted forms of ortho-disubstituted phenyl, substituted forms of ortho-disubstituted benzyl; X1, X2are each independently selected from carbon atom, silicon atom;

[0022] Class II, imine type structure:

[0023]

[0024] wherein R is a substituent; G is selected from organic linker, oxygen atom linker, nitrogen atom linker, amide group;

[0025] Class III, bulky urea bond structure:

[0026]

[0027] wherein R is a bulky group directly connected to the nitrogen atom; b is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring, and n represents the number of linkers connected to the ring-forming atoms of the cyclic structure;

[0028] wherein the fluorinated structure is selected from the following structures:

[0029]

[0030] wherein each 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 one hydrogen atom; y is the number of repeating units, which is an integer from 3 to 9.

[0031] In the present application, the low surface energy polymer modifier structure is preferably as shown below:

[0032]

[0033] wherein P, I, D, F t , m, n are defined as follows:

[0034] P is each 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 300-3000 Da;

[0035] I is each independently a unit formed by polymerization of at least one aliphatic diisocyanate; ​

[0036] D is independently a unit formed by polymerization of at least one temperature-sensitive dynamic compound raw material;

[0037] F t Each independently is a unit formed by polymerization of at least one monohydroxy fluoroalcohol compound;

[0038] m and n are the number of repeating units, and are each independently an integer of 1 to 5.

[0039] In the present invention, the weight average molecular weight Mw of the dynamically migratable low surface energy polymer modifier is preferably 2000-20000, and the fluorine content is preferably 1-10%.

[0040] In the present invention, the aliphatic polymer diol and aliphatic polymer diamine are respectively selected from the following structures:

[0041]

[0042] 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.

[0043] In an embodiment of the present invention, 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 chain segment structures and mixtures containing the above structures.

[0044] Furthermore, the aliphatic polymer diol includes but is not limited to polytetramethylene glycol, polyethylene oxide glycol, polypropylene oxide glycol, polypropylene oxide-ethylene oxide glycol, polytrimethylene ether glycol, polyethylene adipate glycol ester glycol, polypropylene adipate glycol ester glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, polyneopentyl adipate glycol ester glycol, polydiethylene adipate glycol, 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, and a combination of one or more of hydrocarbon hydroxyl-terminated polysiloxane diols.

[0045] In an embodiment of the present invention, the aliphatic polymer diamine includes but is not limited to polyethylene oxide diamine, polypropylene oxide diamine, polytetramethylene oxide diamine, and hydrocarbon amino-terminated polysiloxane diamine.

[0046] 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.

[0047] In the present application, the temperature-sensitive dynamic compound raw material contains two reactive groups, which are selected from at least one of the following structures:

[0048] E1-DCB-E2, E3-L1-E4,

[0049] wherein DCB is a temperature-sensitive dynamic structure, E3-L1-E4 is a temperature-sensitive dynamic structure precursor, L1 is an organic linking group; E1, E2, E3, E4 are reactive groups, E1, E2 are each independently selected from -OH, -NH2, -SH, E3 is each independently selected from -NH-R b 、 E4 is each independently selected from -OH, -NH2, -SH, -NH-R b 、 wherein R b is a steric hindering group directly connected to the nitrogen atom, is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring; n represents the number of connections to the ring-forming atoms of the cyclic structure.

[0050] In a specific embodiment of the present invention, the temperature-sensitive dynamic compound raw material is selected from organic borate diol, organic borate silicon ester diol, 1,3-bis(hydroxyimino)propan-2-one, azine salicylaldehyde, 4-(hydroxyiminomethyl)benzylamine oxime, 3-(hydroxyiminomethyl)benzylamine oxime, glyoxime, methylglyoxime, dimethylglyoxime, dimethylglyoxime, 3-hydroxy-3-methyl-2-butanone oxime, 5-hydroxyvaleraldehyde oxime, 4-hydroxybenzaldehyde oxime, 4'-hydroxyacetophenone oxime, 3-aminobenzylamine oxime, 3'-aminoacetophenone oxime, 4-aminoacetophenone oxime, 2-amino-1-toluene acetonide oxime, salicylaldehyde oxime, salicylaldehyde hydrazone, salicylaldehyde carbonyl hydrazone, acetone Amipropionic acid semicarbazone, N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, N-tert-butylethanolamine, N,N'-di-tert-butylethylenediamine, tert-butylhydrazine, (2-amino-2-methylpropyl)(tert-butyl)amine, 2,2,6,6-tetramethylpiperidinamine, 2,2,6,6-tetramethyl-4-piperidinol, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, N-(sec-butyl)-2,2,6,6-tetramethylpiperidin-4-amine, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, 4-(hydroxymethyl)imidazole, 4-hydroxyethylimidazole, 2-(3-hydroxypropyl)benzimidazole, 4-hydroxybenzimidazole.

[0051] In the present invention, the monohydroxy fluoroalcohol compound has the following structure:

[0052]

[0053] Wherein, L2 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.

[0054] 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.

[0055] In the present application, the organic borate structure is preferably selected from the following structure:

[0056]

[0057] In which the boron atom is connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond.

[0058] In the present application, the imine structure is preferably selected from the following structure:

[0059]

[0060] In which L3 is an organic linking group.

[0061] In the present application, the large steric ure bond structure is preferably selected from the following structure:

[0062]

[0063] The present application also provides a preparation method of a low surface energy polymer modifier capable of dynamic migration, characterized by the following steps:

[0064] S1: heat the aliphatic polymer diol or aliphatic polymer diamine to 80-120°C, vacuumize and remove water for 2-4h;

[0065] 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 content in the system reaches a stable level to obtain a prepolymer;

[0066] S3. Add the temperature-sensitive dynamic compound raw material to the S2 prepolymer, control the reaction temperature at 40-80°C, continue heating and stirring with nitrogen for 2-8 hours, and then add the monohydroxy fluoroalcohol compound and continue heating and stirring for 2-12 hours to cap the end;

[0067] S4. Wash and purify the crude product obtained in S3, and dry it in a vacuum oven at room temperature and 60-120°C in sequence.

[0068] Furthermore, the molar ratio of the aliphatic polymer diol or aliphatic polymer diamine, aliphatic diisocyanate, temperature-sensitive dynamic compound raw material, and monohydroxy fluoroalcohol compound is 1:1.2-2.1:0.2-0.8:0.1-1.1.

[0069] In one embodiment of the present invention, a polyurethane catalyst is added to the system to promote the reaction. These polyurethane catalysts primarily include tertiary amine catalysts (including their quaternary ammonium salts) and organometallic compounds. Tertiary amine catalysts can be further categorized into aliphatic amines, aromatic amines, alcoholamines, and their ammonium salts. Organometallic compounds include carboxylates and metal alkyl compounds, primarily containing metal elements such as tin, potassium, lead, mercury, zinc, titanium, and bismuth. Organotin compounds, potassium carboxylates, organoheavy metal catalysts, zinc carboxylates, and bismuth carboxylates are the most commonly used.

[0070] Furthermore, the added amount of the polyurethane catalyst is 0.02-0.5 wt% of the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0071] In a specific embodiment of the present invention, an aprotic solvent free of water is added in steps S2 and S3. The aprotic solvent serves as a heat transfer medium, which can reduce the viscosity of the system and is beneficial to the dissipation of polymerization heat, thereby making it easier to control the reaction temperature and reduce the risk of local overheating. It is also beneficial to the control of the polymer molecular weight, thereby obtaining a polymer with a uniform structure and molecular weight distribution, and is also beneficial to the diffusion of monomers and reaction products in the solvent.

[0072] Furthermore, the amount of the aprotic solvent added is 1-10 times the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0073] The present invention also provides a solvent-free preparation method for a dynamically migratable low-surface-energy polymer modifier, characterized in that a low-viscosity aliphatic polymer diol is selected as a reaction raw material and no solvent is used during the entire reaction process. The preparation steps are as follows:

[0074] S1: Heat the low-viscosity aliphatic polymer diol to 80-120°C and remove water in a vacuum for 2-4 hours;

[0075] S2. A fixed molar amount of a low-viscosity aliphatic polymer diol and an aliphatic diisocyanate are heated to 60-110° C. under nitrogen and stirred for reaction for 2-6 hours until the -NCO groups in the system are stabilized to obtain a prepolymer;

[0076] S3, adding the temperature-sensitive dynamic compound raw material to the S2 prepolymer, mechanically stirring and reacting at 40-90° C. for 5-120 minutes, then adding the monohydroxy fluoroalcohol compound and continuing to stir and react for 5-30 minutes, pouring the mixture into a mold and continuing to react in a forced air oven at 80-100° C. for 12-48 hours to obtain a low surface energy polymer modifier;

[0077] The low-viscosity aliphatic polymeric diol has a number average molecular weight selected from 300-2000 Da, and its viscosity satisfies at least one of the following conditions: viscosity ≤ 1000 mPa·s at 25°C, viscosity ≤ 500 mPa·s at 40°C, and viscosity ≤ 200 mPa·s at 75°C;

[0078] The molar ratio of the low-viscosity aliphatic polymer diol, aliphatic diisocyanate, temperature-sensitive dynamic compound raw material, and monohydroxy fluoroalcohol compound is 1:1.9-2.1:0.4-0.6:0.9-1.1.

[0079] The present invention also provides a low surface energy blend composition, characterized in that it comprises 80-100 parts by weight of a base resin, 2-10 parts by weight of the dynamically migratable low surface energy polymer modifier described in the present invention, 0-10 parts by weight of an additive, and 0-30 parts by weight of a filler.

[0080] Furthermore, the matrix 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, and silicone resin.

[0081] Furthermore, the additives include but are not limited to antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, release agents, plasticizers, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, matting agents, and flame retardants.

[0082] Furthermore, the filler includes but is not limited to inorganic non-metal fillers, metal fillers, organic fillers, and organometallic compound fillers.

[0083] The present invention also discloses an application of the low surface energy blend composition in the fields of coatings, textiles, electronic products, automotive parts, and filtration membranes.

[0084] The present invention also discloses an application of the low surface energy blend composition in the field of medical products. The medical products include medical instruments, medical equipment, 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 circuits, 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.

[0085] Compared with the prior art, the present invention has the following beneficial effects:

[0086] The present invention regulates the molecular weight of low surface energy polymer modifier by using thermosensitive dynamic structure, realizes the organic unity of modifier mobility and stability, and by using the fluorinated structure at the end group of polymer chain, improves the enrichment efficiency and enrichment degree of substrate surface fluorine. First, the low surface energy polymer modifier that can be dynamically migrated in the present invention, it is in processing, heat treatment and use process, the thermosensitive dynamic structure in the polymer chain is owing to being able to produce dissociation under relatively low temperature conditions, so that the molecular weight of modifier is reduced, has good migration ability, can be well dispersed in the matrix, and efficiently completes from the inside of the matrix to the surface aggregation, and the thermosensitive dynamic structure in the system is in the process of migration completion and room temperature cooling, and can be recombined into dynamic covalent bond, so that modifier is restored to original molecular weight, strengthens its binding force with matrix, realizes stability on matrix surface, effectively reduces the risk of modifier elution, loss. In addition, by introducing fluorinated structure at the end group of modifier, not only the mobility of fluorine segment is improved, but also the binding ability of modifier main chain and matrix is ​​not affected. The fluorinated structure at the end of the polymer molecular chain is subject to minimal segment entanglement and steric hindrance during movement, which makes the end group fluorine segment have higher activity and mobility than the main chain fluorine segment and the side chain fluorine segment, making the fluorine enrichment efficiency on the substrate surface higher. The fluorine atoms at the chain end are ultimately enriched in an extremely thin surface layer, and the composition and structure inside the polymer matrix are basically unaffected, allowing the polymer to retain its original excellent bulk properties, such as mechanical strength, toughness, thermal stability, processability, transparency, etc. In contrast, the main chain and side chain fluorinated structures generally have the problems of difficult processing, high cost, poor binding to the matrix, and easy falling off. The low surface energy polymer modifier in the present invention combines a temperature-sensitive dynamic structure with an end group fluorinated structure, so that it has excellent migration ability and hydrophobic segment surface enrichment ability.

[0087] The migration ability of the fluorine-containing modifier directly affects the fluorine enrichment on the surface of the substrate, and then affects the hydrophobic anti-fouling ability of the substrate. The present invention not only improves the migration ability of the modifier by introducing a temperature-sensitive dynamic structure and a terminal fluorination mechanism, but also uses flexible aliphatic polymer diols, aliphatic polymer diamines, and aliphatic diisocyanates with strong chain movement ability as raw materials, and explores suitable and effective raw material components, raw material molecular weight ranges, and polymer polymerization degrees through a large number of experiments, so that the modifier polymer chain structure has high migration ability and achieves high surface fluorine enrichment in the matrix resin; the addition of the modifier can reduce the surface energy of the matrix by more than 90%, and increase the contact angle by more than 50-65°, achieving a super-hydrophobic effect (contact angle>150°) comparable to that of lotus leaves in nature, and does not affect the appearance and basic performance of the matrix resin. These beneficial effects are closely related to the structure of the polymer modifier. If the molecular weight of the polymer modifier is too low, its binding to the matrix resin will be weakened, which will easily lead to the risk of elution loss and affect the performance of the matrix resin itself. Conversely, if the molecular weight of the polymer modifier is too high, its dispersibility and mobility in the matrix resin will be affected, resulting in a poor low-surface-energy modification effect. The technical solution of the present invention effectively solves the conflicting problem between mobility and stability of low-surface-energy modifiers, achieving a combination of high-efficiency hydrophobicity and antifouling properties with long-term durability.

[0088] Low surface energy polymer modifier in the present invention, it can be blended into matrix resin by conventional processing mixing means in standard production process, and migrate to material surface during processing heat treatment and use, can play the multiple action effects such as waterproof, antifouling, dustproof, anticoagulant, antithrombotic, antibacterial, self-cleaning, etc., different from traditional coating by being coated on the mode that realizes surface hydrophobicity on matrix surface, low surface energy modifier in the present invention is embedded in matrix resin, and can supplement the fluorine content at surface wear by migration, belong to long-lasting passive modification, there is no loss, fall off, peeling risk faced by traditional coating, avoid the generation of various accidents (especially medical accidents).Meanwhile, the temperature-sensitive dynamic structure in modifier structure, also makes surface structure can realize the reversible self-repair to physical and chemical damage, so that matrix surface has the modification effect of persistence, the durability of product is significantly improved, greatly prolongs the service life of product.In addition, due to the passive attribute of modifier, it can be applicable to the product of various shape structures (comprising complex structure, small size structure), is not limited by product appearance modeling, can be evenly distributed on each surface of product.

[0089] The dynamically migratable low surface energy polymer modifier of the present invention also has a wide range of applicability. By adjusting the polymer segment structure in the modifier structure, it can be applied to different matrix resins (such as polyurethane, polycarbonate, polyester, polyamide, polysulfone, silicone resin, polyolefin, thermoplastic elastomer, etc.).

[0090] The above beneficial effects fully demonstrate the excellent performance and wide applicability of the dynamically migratable low surface energy polymer modifier of the present invention. These features and advantages of the present invention will become apparent with reference to the following specific embodiments and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] Figure 1 This is the infrared spectrum of the modifier 5 obtained in Example 5 of the present invention.

[0092] Figure 2 This is the infrared spectrum of the modifier 10 obtained in Example 10 of the present invention.

[0093] Figure 3 This is the infrared spectrum of the modifier 14 obtained in Example 14 of the present invention.

[0094] Figure 4 This is the infrared spectrum of the modifier 16 obtained in Example 16 of the present invention.

[0095] Figure 5 This is the EDS fluorine element mapping surface spectrum of the sample surface obtained in Application Example 2.2 of the present invention.

[0096] Figure 6 These are SEM images of the surface morphology of the samples obtained in the comparative example and the application examples of the present invention; wherein, A is the sample obtained in the comparative example 2, and B is the sample obtained in the application example 2.2.

[0097] Figure 7 These are demonstration diagrams of the hydrophobicity of samples obtained from the comparative example and the example of the present invention; wherein, A is the sample obtained from the comparative example 2, and B is the sample obtained from the example 2.2.

[0098] Figure 8 This is a tensile stress-strain curve diagram of the samples obtained in Application Comparative Example 2, Application Example 2.1, Application Example 2.2, and Application Example 2.3 of the present invention.

[0099] Figure 9 This is a comparison chart of the tear strength of samples obtained from the comparative example and the example of the present invention; wherein, A is the sample obtained from the comparative example 2, B is the sample obtained from the example 2.1, C is the sample obtained from the example 2.2, and D is the sample obtained from the example 2.3.

[0100] Figure 10The water contact angle of the samples obtained in the application comparative examples and application examples is tested, and the test diagram is shown in the figure; wherein, A is the sample obtained in the application comparative example 1, B is the sample obtained in the application example 1.2, C is the sample obtained in the application comparative example 3, D is the sample obtained in the application example 3.2, E is the sample obtained in the application comparative example 4, and F is the sample obtained in the application example 4.2.

[0101] Figure 11 The samples obtained in the application comparative examples and application examples are shown in the figure; wherein, A is the sample obtained in the application comparative example 5, B is the sample obtained in the application example 5.1, C is the sample obtained in the application comparative example 6, D is the sample obtained in the application example 6.2, E is the sample obtained in the application comparative example 7, and F is the sample obtained in the application example 7.1.

[0102] Figure 12 The samples obtained in the application comparative examples and application examples are shown in the figure; wherein, A is the sample obtained in the application comparative example 2, B is the sample obtained in the application example 2.2, C is the sample obtained in the application comparative example 8, D is the sample obtained in the application comparative example 9, E is the sample obtained in the application comparative example 10, F is the sample obtained in the application comparative example 11, G is the sample obtained in the application comparative example 12, and H is the sample obtained in the application comparative example 13. DETAILED DESCRIPTION

[0103] In the present application, the term "main chain" refers to the chain having the most number of chain bones in the polymer structure.

[0104] In the present application, the term "end group" refers to the chemical group located at the end of the chain skeleton and connected with the main chain of the polymer in the polymer structure.

[0105] In the present application, the term "aliphatic" refers to the chain hydrocarbon and the cyclic hydrocarbon and its derivatives except the aromatic compound, which can be the saturated compound connected by single bond or the unsaturated compound containing double bond and / or triple bond, and can contain oxygen, nitrogen, sulfur, chlorine and other elements in addition to carbon and hydrogen.

[0106] In the present invention, the term "aliphatic carbon chain" as used herein refers to an aliphatic chain structure having only carbon 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, any one of the unsaturated forms, any one of the substituted forms, any one of the hetero-substituted forms, and combinations thereof: polyolefin chains such as polyethylene chains, polypropylene chains, polyisobutylene chains, polyvinyl chloride chains, polyvinylidene chloride chains, polyvinyl fluoride chains, polytetrafluoroethylene chains, polytrifluorochloroethylene chains, polyvinyl acetate chains, polyvinyl alkyl ether chains, polybutadiene chains, polyisoprene chains, polychloroprene chains, polynorbornene chains, and the like; polyacrylic chains such as polyacrylic acid chains, polyacrylamide chains, polymethyl acrylate chains, polymethyl methacrylate chains, and the like; polyacrylonitrile chains such as polyacrylonitrile chains, and the like.

[0107] In the present invention, the term "aliphatic carbon hetero chain" as used herein refers to an aliphatic chain structure having both carbon atoms and any one or more heteroatoms 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, any one of the unsaturated forms, any one of the substituted forms, any one of the hetero-substituted forms, and combinations thereof: polyether chains such as polyethylene oxide chains, polypropylene oxide chains, polytetrahydrofuran chains, epoxy resin chains, and the like; polyester chains such as polycaprolactone chains, polyvalerolactone chains, polylactide chains, unsaturated polyester chains, alkyd resin chains, polycarbonate chains, and the like; polyamine chains such as polyamide chains, polyimide chains, polyurethane chains, polyurea chains, polythiourethane chains, and the like.

[0108] In the present invention, the term "siloxane chain" as used herein refers to a chain structure having both silicon atoms and oxygen atoms in the backbone skeleton, and also includes hydrocarbon-substituted siloxane chain structures in the backbone skeleton, and includes but is not limited to any one of the following groups, any one of the substituted forms, any one of the hetero-substituted forms, and combinations thereof: polydimethylsiloxane chains, polymethylphenylsiloxane chains, polymethylhydrosiloxane chains, polyether-modified siloxane chains, amino-hydrocarbyl-modified siloxane chains, epoxy-modified siloxane chains, fluorocarbyl-modified siloxane chains, methyl-alkyl-modified siloxane chains.

[0109] In the present invention, the term "organic group" as used herein refers to a group mainly composed of carbon atoms as the backbone, which can or can not contain heteroatoms, and includes but is not limited to any one of the following groups, any one of the unsaturated forms, any one of the substituted forms, any one of the hetero-substituted forms, and combinations thereof: alkane groups, cycloalkane groups, arene 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.

[0110] In the present invention, the term "organic linking group" refers to a divalent or polyvalent linking group mainly composed of carbon atoms as a skeleton, which may or may not contain heteroatoms, including but not limited to any one of the following groups, any unsaturated form, any substituted form, any hybridized form and combinations thereof: divalent or polyvalent alkane groups, divalent or polyvalent cycloalkyl groups, divalent or polyvalent aromatic groups, divalent or polyvalent alkylsilane groups.

[0111] In the present invention, the term "heteroatom" refers to common non-carbon atoms such as nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, etc.

[0112] In the present invention, the term "aliphatic ring" refers to any alicyclic ring or alicyclic heterocyclic ring, and the ring atoms are independently carbon atoms or heteroatoms; the hydrogen atoms on the ring atoms of the aliphatic ring may be substituted by any substituent or may not be substituted; it may be a monocyclic structure, a polycyclic structure, a spirocyclic structure, a condensed ring structure, a bridged ring structure, or a nested ring structure.

[0113] In the present invention, the term "aromatic ring" refers to any aromatic ring or aromatic heterocycle, and the ring atoms are independently carbon atoms or heteroatoms; the hydrogen atoms on the ring atoms of the aromatic ring may be substituted by any substituent or may not be substituted; it may be a monocyclic structure, a polycyclic structure, a spirocyclic structure, a condensed ring structure, a bridged ring structure, or a nested ring structure.

[0114] In the present invention, the term "dynamic covalent bond" refers to a type of covalent bond that can be reversibly broken and formed under appropriate conditions.

[0115] In the present invention, the term "polymerization reaction" used, unless otherwise specified, refers to the polymerization reaction between active groups such as hydroxyl, primary amino, secondary amino, and thiol contained in a compound raw material and isocyanate groups contained in another compound raw material.

[0116] The present invention provides a low-surface-energy polymer modifier capable of dynamic migration, characterized in that the polymer main chain includes a temperature-sensitive dynamic structure, and the polymer chain end groups are fluorinated structures; the modifier is prepared using at least the following raw materials in parts by weight:

[0117]

[0118] The temperature-sensitive dynamic structure can undergo dynamic dissociation and generation-conversion based on dynamic covalent bonds at a temperature of at least 50-80°C, and contains at least one of the following structures:

[0119] Class I, organic borate ester structure:

[0120]

[0121] wherein the boron atom B is connected to one carbon atom via a boron-carbon bond and at least one organic group is connected to the boron atom via said boron-carbon bond; K is selected from substituted forms of 1,2-ethylene, substituted forms of 1,3- propylene, substituted forms of ortho-disubstituted phenyl, substituted forms of ortho-disubstituted benzyl; X1, X2are each independently selected from carbon atom, silicon atom;

[0122] Class II, imine-based structure:

[0123]

[0124] wherein R is a substituent; G is selected from organic linking group, oxygen atom linking group, nitrogen atom linking group, amide group;

[0125] Class III, bulky urea bond structure:

[0126]

[0127] wherein R is a bulky group directly connected to the nitrogen atom; b is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring, and n represents the number of connections to the ring-forming atoms of the cyclic structure;

[0128] wherein the fluorinated structure is selected from the following structures:

[0129]

[0130] wherein each x is independently the number of fluorine atoms connected to the carbon atom, which is an integer from 1 to 2, and wherein when x is 1, the carbon atom is also connected to one hydrogen atom; and y is the number of repeating units, which is an integer from 3 to 9.

[0131] In the present application, the low surface energy polymer modifier structure is preferably as shown below:

[0132]

[0133] wherein P, I, D, F t , m, n are defined as follows:

[0134] each 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 300-3000 Da;

[0135] each I is independently a unit formed by polymerization of at least one aliphatic diisocyanate; ​

[0136] D is independently a unit formed by polymerization of at least one temperature-sensitive dynamic compound raw material;

[0137] F t Each independently is a unit formed by polymerization of at least one monohydroxy fluoroalcohol compound;

[0138] m and n are the number of repeating units, and are each independently an integer of 1 to 5.

[0139] In the present invention, the typical structure of the unit P is as follows:

[0140]

[0141] 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.

[0142] In the present invention, the typical structure of the unit I is as follows:

[0143]

[0144] Wherein, L' is an aliphatic linking group.

[0145] In the present invention, the typical structure of the unit D is as follows:

[0146]

[0147] Wherein, DCB is a temperature-sensitive dynamic structure, and E' is independently selected from E" are each independently selected from -O-, Among them, R b is a steric group directly connected to the nitrogen atom, is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring; n represents the number of links connected to the ring atoms of the cyclic structure.

[0148] In the present invention, the unit F t The typical structure is as follows:

[0149]

[0150] Wherein, L2 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.

[0151] In the present invention, the temperature-sensitive dynamic structure can undergo dynamic dissociation and generation-conversion based on dynamic covalent bonds at a temperature of at least 50-80°C. The temperature-sensitive dynamic structure includes at least one of the following structures:

[0152] Class I, organic borate ester structure:

[0153]

[0154] The boron atom B is connected to a carbon atom via a boron-carbon bond, and at least one organic group is connected to the boron atom via the boron-carbon bond; K is selected from a substituted form of 1,2-ethylene, a substituted form of 1,3-propylene, a substituted form of an o-disubstituted phenyl, and a substituted form of an o-disubstituted benzyl; X1 and X2 are each independently selected from a carbon atom and a silicon atom;

[0155] Class II, imine structure:

[0156]

[0157] Wherein, R is a substituent; G is selected from an organic linking group, an oxygen atom linking group, a nitrogen atom linking group, and an amide group;

[0158] Class III, large hindered urea bond structure:

[0159]

[0160] Among them, R b It is a steric group directly connected to the nitrogen atom; is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring, and n represents the number of links connected to the ring atoms of the cyclic structure.

[0161] In the present invention, the fluorinated structure is selected from the following structures:

[0162]

[0163] 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.

[0164] In the present invention, the weight average molecular weight Mw of the dynamically migratable low surface energy polymer modifier is preferably 2000-20000, and the fluorine content is preferably 1-10%.

[0165] In the present invention, the aliphatic polymer diol and aliphatic polymer diamine are respectively selected from the following structures:

[0166]

[0167] 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.

[0168] In an embodiment of the present invention, 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 chain segment structures and mixtures containing the above structures.

[0169] Furthermore, the aliphatic polymer diol includes but is not limited to polytetramethylene glycol, polyethylene oxide glycol, polypropylene oxide glycol, polypropylene oxide-ethylene oxide glycol, polytrimethylene ether glycol, polyethylene adipate glycol ester glycol, polypropylene adipate glycol ester glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, polyneopentyl adipate glycol ester glycol, polydiethylene adipate glycol, 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, and a combination of one or more of hydrocarbon hydroxyl-terminated polysiloxane diols.

[0170] In an embodiment of the present invention, the aliphatic polymer diamine includes but is not limited to polyethylene oxide diamine, polypropylene oxide diamine, polytetramethylene oxide diamine, and hydrocarbon amino-terminated polysiloxane diamine.

[0171] In an embodiment of the present invention, 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.

[0172] In the present invention, the temperature-sensitive dynamic compound raw material contains two reactive groups, which are selected from at least one of the following structures:

[0173] E1-DCB-E2, E3-L1-E4,

[0174] Among them, DCB is a temperature-sensitive dynamic structure, E3-L1-E4 is a temperature-sensitive dynamic structure precursor, L1 is an organic linker; E1, E2, E3, E4 are reactive groups, E1, E2 are each independently selected from -OH, -NH2, -SH, E3 are each independently selected from -NH-R b 、 E4 are each independently selected from -OH, -NH2, -SH, -NH-R b 、 Among them, R b is a steric group directly connected to the nitrogen atom, is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring; n represents the number of links connected to the ring atoms of the cyclic structure.

[0175] In the present invention, the reactive group refers to a group that can react with isocyanate.

[0176] In the present invention, the temperature-sensitive dynamic structure is sensitive to the ambient temperature and can undergo dynamic dissociation and generation of dynamic covalent bonds at a temperature of at least 50-80°C.

[0177] In the present invention, the temperature-sensitive dynamic structure precursor, as a compound raw material, can form a temperature-sensitive dynamic structure after reacting with isocyanate, so it is called a temperature-sensitive dynamic structure precursor in the present invention.

[0178] In the present invention, the nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring is preferably a pyrrole ring, an imidazole ring, a piperidine ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring.

[0179] In the present invention, the steric hindering group directly attached to the nitrogen atom or the cyclic structure formed by the nitrogen atom can weaken the chemical bond strength between the carbon atom in the carbonyl group and the adjacent nitrogen atom, thereby allowing the carbon-nitrogen bond to exhibit dynamic properties and undergo a dynamic reversible reaction under heating conditions. It should be noted that the steric hindering effect brought about by the steric hindering group or cyclic structure is not necessarily greater, but rather should be of moderate size to ensure that the carbon-nitrogen bond has appropriate dynamic reversibility.

[0180] For example, the following temperature-sensitive dynamic structure can undergo dynamic exchange reaction at 60°C, reflecting dynamic characteristics:

[0181]

[0182] In the present invention, the steric hindering group R bselected from the group consisting of ethyl, isopropyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylbenzyl.

[0183] In the detailed description of the present application, the temperature-sensitive dynamic compound raw material is selected from the group consisting of organic borate diol, organic borate siloxane diol, 1,3-bis(hydroxyimino)propan-2-one, oxime of 4-hydroxybenzaldehyde, 3-(hydroxyimino)methylbenzylamine oxime, 3-(hydroxyimino)methylbenzylamine oxime, glycolaldehyde oxime, methylglycolaldehyde oxime, butanedione oxime, dimethylglyoxime, 3-hydroxy-3-methyl-2-butanone oxime, 5-hydroxypentanal oxime, 4-hydroxybenzaldehyde oxime, 4'-hydroxyacetophenone oxime, 3-aminobenzylideneamine oxime, 3'-aminophenylacetophenone oxime, 4-aminophenylacetophenone oxime, 2-amino-1-tolylacetophenone oxime, salicylaldehyde oxime, salicylaldehyde hydrazone, salicylaldehyde carbohydrazone, levulinic acid hemiketazine, N,N'-diethyl ethylenediamine, N,N'-diisopropyl ethylenediamine, N-t-butyl ethanolamine, N,N'-di-t-butyl ethylenediamine, t-butyl hydrazine, (2-amino-2-methylpropyl)(t-butyl)amine, 2,2,6,6-tetramethylpiperidinamine, 2,2,6,6-tetramethyl-4-piperidinol, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, N-(sec-butyl)-2,2,6,6-tetramethylpiperidin-4-amine, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, 4-(hydroxymethyl)imidazole, 4-hydroxyethylimidazole, 2-(3-hydroxypropyl)benzimidazole, 4-hydroxybenzimidazole.

[0184] In the present application, the monohydroxy fluoroalcohol compound has the following structure:

[0185]

[0186] wherein L2 is an organic linker, each of 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.

[0187] In a specific embodiment of the present invention, the monohydroxy fluoroalcohol 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), heptylfluorohexanol (CAS: 679-02-7), 1H,1H,2H,2H-perfluorohexanol (CAS: 2043-47-2), undecyl-n-hexanol (CAS: 423-46-1), 1H,1H,2H,2H-perfluorooctanol (CAS: 64 7-42-7)), 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.

[0188] In the present invention, the substituted form of 1,2-ethylene refers to a trivalent group structure formed after at least one hydrogen atom in the 1,2-ethylene structure (*-CH2-CH2-*) is replaced by any suitable substituent; * indicates the position connected to the oxygen atom.

[0189] In the present invention, the substituted form of 1,3-propylene refers to a trivalent group structure formed after at least one hydrogen atom in the 1,3-propylene structure (*-CH2-CH2-CH2-*) is replaced by any suitable substituent; * indicates the position connected to the oxygen atom.

[0190] In the present invention, the substituted form of the ortho-disubstituted phenyl group refers to an ortho-disubstituted phenyl structure ( ) is replaced by any suitable substituent to form a trivalent group structure; * indicates the position connected to the oxygen atom.

[0191] In the present invention, the substituted form of the o-disubstituted benzyl group refers to the o-disubstituted benzyl structure ( ) is replaced by any suitable substituent to form a trivalent group structure; * indicates the position connected to the oxygen atom.

[0192] In the present invention, the organic borate ester structure is preferably selected from the following structures:

[0193]

[0194] The boron atom must be connected to a carbon atom via a boron-carbon bond, and at least one organic group must be connected to the boron atom via the boron-carbon bond.

[0195] In an embodiment of the present invention, the organic borate ester structure can be formed by reacting a 1,2-diol moiety, a 1,3-diol moiety, an o-diphenol moiety, a 2-hydroxymethylphenol moiety, a monohydroxyl group, or a silanol group contained in the compound raw material with an organic boric acid moiety.

[0196] In an embodiment of the present invention, a typical organic borate ester structure is exemplified by:

[0197]

[0198] In the present invention, the boron atom in the organic borate structure is preferably connected to the aminomethylphenyl group ( * indicates the position of attachment to the boron atom); the aminomethylphenylboronic acid (ester) moiety forming the structure has high reactivity when reacting with 1,2-diol moiety, 1,3-diol moiety, o-diphenol moiety, and 2-hydroxymethylphenol moiety. The dynamic structure formed has strong dynamic reversibility and can undergo dynamic reversible reactions under relatively mild neutral conditions. Examples of such organic borate ester structures with aminomethylphenyl groups are:

[0199]

[0200] In the present invention, the organic boronic acid unit includes but is not limited to any of the following structures:

[0201]

[0202] Among them, K1 and K2 are organic groups directly connected to oxygen atoms, which are directly connected to oxygen atoms through carbon atoms; K3 is a divalent organic group directly connected to two oxygen atoms, which are directly connected to oxygen atoms through carbon atoms; wherein, the boron atom in the structure needs to be connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond.

[0203] In the present invention, the 1,2-diol moiety is ethylene glycol ( ) and its substituted forms after losing at least one non-hydroxyl hydrogen atom.

[0204] In the present invention, the 1,3-diol moiety is 1,3-propylene glycol ( ) and its substituted forms after losing at least one non-hydroxyl hydrogen atom.

[0205] In the present invention, the o-diphenol unit is o-diphenol ( ) and its substituted forms and its hybrid forms and their combinations thereof are residues formed after losing at least one non-hydroxyl hydrogen atom.

[0206] In the present invention, the 2-hydroxymethylphenol moiety is 2-hydroxymethylphenol ( ) and its substituted forms and its hybrid forms and their combinations thereof are residues formed after losing at least one non-hydroxyl hydrogen atom.

[0207] In the present invention, the organic borate diol and its derivatives contain the organic borate structure in their structure, which can be formed by a condensation reaction of an organic boron compound raw material containing an organic boronic acid unit and a polyol compound raw material containing a 1,2-diol unit or a 1,3-diol unit or an o-diphenol unit or a 2-hydroxymethylphenol unit.

[0208] In a specific embodiment of the present invention, the organic boron compound raw materials containing organic boronic acid units include but are not limited to 2-hydroxyphenylboric acid, 3-hydroxyphenylboric acid, 4-hydroxyphenylboric acid, 3-methyl-2-hydroxyphenylboric acid, 2-hydroxy-5-methylphenylboric acid, 3-hydroxy-2-methylphenylboric acid, 3-hydroxy-5-methylphenylboric acid, 4-hydroxy-3-methoxyphenylboric acid, 2-hydroxymethylphenylboric acid, 4-hydroxymethylphenylboric acid, 2,3-difluoro-4-hydroxyphenylboric acid, 3,5-difluoro-4-hydroxyphenylboric acid, 3-trifluoromethyl-4-hydroxyphenylboric acid, 3-hydroxy-5-trifluoromethylphenylboric acid, 5-hydroxy-2-trifluoromethoxyphenylboric acid, 6-hydroxynaphthalene-2-boric acid, 3-hydroxyphenylboric acid pinacol ester, 4-hydroxyphenylboric acid pinacol ester, 3-fluoro-4-hydroxyphenylboric acid pinacol ester ...3-hydroxy-2-trifluoromethoxyphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy-2-trifluoromethylphenylboric acid, 3-hydroxy 1-Chloro-5-hydroxyphenylboronic acid pinacol ester, 4-fluoro-2-hydroxyphenylboronic acid pinacol ester, 4-hydroxy-3-methoxyphenylboronic acid pinacol ester, 3-hydroxy-4-methoxyphenylboronic acid pinacol ester, (dihydroxyboryl)boronic acid, 2-aminophenylboronic acid, 3-aminophenylboronic acid, 4-aminophenylboronic acid, 1-aminoethylboronic acid, [(1E)-6-hydroxy-1-hexen-1-yl]boronic acid, 2-aminoethylboronic acid The boronic acid is preferably 2-hydroxyphenylboronic acid, 3-hydroxyphenylboronic acid, 4-hydroxyphenylboronic acid, 6-hydroxynaphthalene-2-boronic acid, 3-hydroxyphenylboronic acid pinacol ester, 4-hydroxyphenylboronic acid pinacol ester, 4-hydroxyphenylboronic acid pinacol ester, 2-aminophenylboronic acid, 3-aminophenylboronic acid, 4-aminophenylboronic acid, 2-hydroxymethylnaphthaleneboronic acid, hydroxymethylpyridineboronic acid, 1,4-phenyldiboronic acid, and 4,4'-biphenyldiboronic acid.

[0209] In a specific embodiment of the present invention, the polyol compound raw material containing 1,2-diol moiety includes but is not limited to glycerol, 1,2,6-hexanetriol, dipropylene glycol, 3-amino-1,2-propylene glycol, 2-(4-aminobutyl)propane-1,3-diol, and 3-mercapto-1,2-propylene glycol.

[0210] In a specific embodiment of the present invention, the polyol compound raw material containing 1,3-diol moiety includes but is not limited to 2-amino-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, 2-hydroxymethyl-1,4-butanediol, 2-amino-2-ethyl-1,3-propanediol, 2-(aminomethyl)-1,3-propanediol, 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol, and pentaerythritol.

[0211] In a specific embodiment of the present invention, the polyol compound raw material containing o-diphenol units includes but is not limited to 3-aminomethylcatechol, 3-(hydroxymethyl)catechol, and dopamine.

[0212] In a specific embodiment of the present invention, the polyol compound raw material containing 2-hydroxymethylphenol includes but is not limited to 5-amino-2-(hydroxymethyl)phenol.

[0213] In a specific embodiment of the present invention, the monohydroxyl-containing compound raw material includes but is not limited to aliphatic polymer diols, butanediol, hexanediol, diethylene glycol, and dipropylene glycol.

[0214] In a specific embodiment of the present invention, the compound raw material containing silanol groups includes but is not limited to hydroxyl-terminated polydimethylsiloxane.

[0215] In the present invention, the imine structure is preferably selected from the following structures:

[0216]

[0217] Wherein, L3 is an organic linking group.

[0218] In an embodiment of the present invention, typical imine structures are exemplified by:

[0219]

[0220] In an embodiment of the present invention, the imine structure can be formed by a condensation reaction between a ketone group, an aldehyde group, or an acyl group contained in a compound raw material and an amino group, a hydroxylamine group, a hydrazine group, or a hydrazide group, respectively. Alternatively, the compound raw material containing the imine structure can be directly introduced into the polymer structure through a polymerization reaction between the reactive groups (such as hydroxyl, amino, thiol, etc.) contained therein.

[0221] In a specific embodiment of the present invention, the compound raw materials containing imine structures include but are not limited to 1,3-bis(hydroxyimino)propan-2-one, azine salicylaldehyde, 4-(hydroxyiminomethyl)benzylamine oxime, 3-(hydroxyiminomethyl)benzylamine oxime, glyoxime, methylglyoxime, dimethylglyoxime, dimethylglyoxime, 3-hydroxy-3-methyl-2-butanone oxime, 5-hydroxyvaleraldehyde oxime, 4-hydroxybenzaldehyde oxime, 4'-hydroxyacetophenone oxime, 3-aminobenzylamine oxime, 3'-aminoacetophenone oxime, 4-aminoacetophenone oxime, 2-amino-1-p-methylphenylacetophenone oxime, salicylaldehyde oxime, salicylaldehyde hydrazone, salicylaldehyde carbonyl hydrazone, and levulinic acid semicarbazone.

[0222] In the present invention, the large hindered urea bond structure is preferably selected from the following structures:

[0223]

[0224] In an embodiment of the present invention, the large hindered urea bond structure can be formed by a polymerization reaction between the isocyanate group contained in the compound raw material and the secondary amino group connected to the steric hindered group, or it can be directly introduced into the polymer structure by a polymerization reaction between the reactive groups (such as hydroxyl, amino, thiol, etc.) contained in the compound raw material.

[0225] In a specific embodiment of the present invention, the compound raw materials containing a large hindered urea bond structure include but are not limited to N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, N-tert-butylethanolamine, N,N'-di-tert-butylethylenediamine, tert-butylhydrazine, (2-amino-2-methylpropyl) (tert-butyl) amine, 2,2,6,6-tetramethylpiperidinamine, 2,2,6,6-tetramethyl-4-piperidinol, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, N-(sec-butyl)-2,2,6,6-tetramethylpiperidin-4-amine, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, 4-(hydroxymethyl)imidazole, 4-hydroxyethylimidazole, 2-(3-hydroxypropyl)benzimidazole, and 4-hydroxybenzimidazole.

[0226] The present invention also provides a method for preparing a low surface energy polymer modifier capable of dynamic migration, which is characterized by being prepared by the following steps:

[0227] S1: Heat the aliphatic polymer diol or aliphatic polymer diamine to 80-120°C and vacuum-drain for 2-4 hours;

[0228] 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 content in the system reaches a stable level to obtain a prepolymer;

[0229] S3. Add the temperature-sensitive dynamic compound raw material to the S2 prepolymer, control the reaction temperature at 40-80°C, continue heating and stirring with nitrogen for 2-8 hours, and then add the monohydroxy fluoroalcohol compound and continue heating and stirring for 2-12 hours to cap the end;

[0230] S4. Wash and purify the crude product obtained in S3, and dry it in a vacuum oven at room temperature and 60-120°C in sequence.

[0231] Furthermore, the molar ratio of the aliphatic polymer diol or aliphatic polymer diamine, aliphatic diisocyanate, temperature-sensitive dynamic compound raw material, and monohydroxy fluoroalcohol compound is 1:1.2-2.1:0.2-0.8:0.1-1.1.

[0232] In one embodiment of the present invention, a polyurethane catalyst is added to the system to promote the reaction. These polyurethane catalysts primarily include tertiary amine catalysts (including their quaternary ammonium salts) and organometallic compounds. Tertiary amine catalysts can be further categorized into aliphatic amines, aromatic amines, alcoholamines, and their ammonium salts. Organometallic compounds include carboxylates and metal alkyl compounds, primarily containing metal elements such as tin, potassium, lead, mercury, zinc, titanium, and bismuth. Organotin compounds, potassium carboxylates, organoheavy metal catalysts, zinc carboxylates, and bismuth carboxylates are the most commonly used.

[0233] In the present invention, the aliphatic 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-pentamethyldiethylenetriamine, 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, and N-2-hydroxypropyldimethylmorpholine.

[0234] In the present invention, the aromatic amine catalyst includes but is not limited to pyridine and N,N'-dimethylpyridine.

[0235] In the present invention, the alcoholamine catalyst includes but is not limited to triethanolamine and N,N-dimethylethanolamine. Alkylamine is a type of reactive catalyst that can be used in conjunction with other highly active catalysts.

[0236] In the present invention, the organotin catalyst includes but is not limited to dibutyltin dilaurate (DBTDL), stannous octoate, dibutyltin didodecylsulfide, and dibutyltin diacetate.

[0237] In the present invention, the potassium carboxylate catalyst includes but is not limited to potassium isooctanoate, potassium acetate, and potassium oleate.

[0238] In the present invention, the organic heavy metal catalyst includes but is not limited to lead isooctanoate and phenylmercuric acetate.

[0239] In the present invention, the zinc carboxylate and bismuth carboxylate catalysts include but are not limited to zinc isooctanoate and bismuth isooctanoate.

[0240] In the present invention, the titanate catalyst includes but is not limited to tetrabutyl titanate and tetraisopropyl titanate.

[0241] Furthermore, the added amount of the polyurethane catalyst is 0.02-0.5 wt% of the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0242] In a specific embodiment of the present invention, an aprotic solvent free of water is added in steps S2 and S3. The aprotic solvent serves as a heat transfer medium, which can reduce the viscosity of the system and is beneficial to the dissipation of polymerization heat, thereby making it easier to control the reaction temperature and reduce the risk of local overheating. It is also beneficial to the control of the polymer molecular weight, thereby obtaining a polymer with a uniform structure and molecular weight distribution, and is also beneficial to the diffusion of monomers and reaction products in the solvent.

[0243] In the present invention, the aprotic solvent does not contain easily replaceable hydrogen atoms and mainly relies on the interaction of dipole moment or van der Waals force to produce solvation. Aprotic solvents are further divided into aprotic polar solvents and aprotic non-polar solvents. The aprotic 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, ethyl 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, and dioxane; preferably acetone, toluene, chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and dimethylacetamide.

[0244] Furthermore, the amount of the aprotic solvent added is 1-10 times the mass of the aliphatic polymer diol or aliphatic polymer diamine.

[0245] In the present invention, the washing method for crude product in step S4 can be selected from the product washing method commonly used in this area, and it is actually selected according to product properties and solubility, including but not limited to adopting separating funnel to carry out extraction separation, utilizing good solvent to dissolve non-good solvent precipitation separation (separation process can be carried out by centrifugation, pouring, separatory, suction filtration, etc.). The good solvent and non-good solvent of product are all selected according to the actual dissolution situation of product. The number of washings is selected according to actual washing situation, and washing can be repeated many times to increase product purity. Specifically can refer to the washing method adopted in the embodiment of the present invention.

[0246] The present invention also provides a solvent-free preparation method for a dynamically migratable low-surface-energy polymer modifier, characterized in that a low-viscosity aliphatic polymer diol is selected as a reaction raw material and no solvent is used during the entire reaction process. The preparation steps are as follows:

[0247] S1: Heat the low-viscosity aliphatic polymer diol to 80-120°C and remove water in a vacuum for 2-4 hours;

[0248] S2. A fixed molar amount of a low-viscosity aliphatic polymer diol and an aliphatic diisocyanate are heated to 60-110° C. under nitrogen and stirred for reaction for 2-6 hours until the -NCO groups in the system are stabilized to obtain a prepolymer;

[0249] S3, adding the temperature-sensitive dynamic compound raw material to the S2 prepolymer, mechanically stirring and reacting at 40-90° C. for 5-120 minutes, then adding the monohydroxy fluoroalcohol compound and continuing to stir and react for 5-30 minutes, pouring the mixture into a mold and continuing to react in a forced air oven at 80-100° C. for 12-48 hours to obtain a low surface energy polymer modifier;

[0250] The low-viscosity aliphatic polymeric diol has a number average molecular weight selected from 300-2000 Da, and its viscosity satisfies at least one of the following conditions: viscosity ≤ 1000 mPa·s at 25°C, viscosity ≤ 500 mPa·s at 40°C, and viscosity ≤ 200 mPa·s at 75°C;

[0251] The molar ratio of the low-viscosity aliphatic polymer diol, aliphatic diisocyanate, temperature-sensitive dynamic compound raw material, and monohydroxy fluoroalcohol compound is 1:1.9-2.1:0.4-0.6:0.9-1.1.

[0252] In this embodiment of the preparation method, a low-viscosity isocyanate prepolymer is prepared using specific low-viscosity aliphatic polymer raw materials and aliphatic isocyanate, and then a warm-sensitive dynamic compound raw material and a monohydroxy fluoroalcohol compound are added respectively to carry out chain extension and end-capping reactions, without adding solvents and catalysts throughout the process, achieving low-viscosity prepolymers, and the product performance does not decrease (see examples), avoiding the need for additional steps and equipment for solvent recovery processing, greatly reducing the limitations on production equipment, production workshop, and production qualifications, as well as the residual problems of solvents and catalysts (which has obvious advantages for medical product applications), and the solvent-free preparation method also improves the process conditions, greatly reducing the production cost of the modifier, making it possible to achieve industrial mass production, which is very creative in the field, while the existing technology still generally uses solvent methods for the synthesis of fluorine-containing modifiers.

[0253] The present application also provides a low surface energy blend composition, characterized in that it comprises 80-100 parts by weight of a base resin, 2-10 parts by weight of the dynamically migratable low surface energy polymer modifier described in the present application, 0-10 parts by weight of additives, and 0-30 parts by weight of fillers.

[0254] 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.

[0255] Further, the additives include but are not limited to antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, release agents, plasticizers, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, matting agents, flame retardants.

[0256] Further, the fillers include but are not limited to inorganic non-metallic fillers, metal fillers, organic fillers, and organic metal compound fillers.

[0257] Among them, the antioxidant can delay the oxidation process of the material, ensure that the material can be smoothly prepared and processed and prolong its service life, including but not limited to any one or more of the following antioxidants: hindered phenols, such as 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol); sulfur-containing hindered phenols, such as 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert-butylphenol]; triazine hindered phenols, such as 1,3,5-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydro-s-triazine; triisocyanate Hindered phenols, such as tris (3,5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate; amines, such as N,N'-di (β-naphthyl) p-phenylenediamine, N,N'-diphenyl p-phenylenediamine, N-phenyl-N'-cyclohexyl p-phenylenediamine; sulfur-containing compounds, such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; phosphites, such as triphenyl phosphite, trisnonylphenyl phosphite, tris- [2,4-di-tert-butylphenyl] phosphite, etc.; among them, the antioxidant is preferably tea polyphenol (TP), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), tris[2,4-di-tert-butylphenyl] phosphite (Antioxidant 168), and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Antioxidant 1010). The amount of antioxidant used is not particularly limited, but is generally 0.01-1 wt%.

[0258] Among them, the light stabilizer can prevent the material from light aging and extend its service life, including but not limited to any one or more of the following light stabilizers: light shielding agents, such as carbon black, titanium dioxide, zinc oxide, and 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-butoxyphenyl)-1,3,5-s-triazine, and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; pioneer ultraviolet absorbers, such as p-tert-butylphenyl salicylate and bisphenol A disalicylate; UV quenchers, such as bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) and 2,2'-thiobis(4-tert-octylphenoloxy)nickel; hindered amine light stabilizers, such as bis(2,2,6,6-tetramethylpiperidinyl) sebacate, (2,2,6,6-tetramethylpiperidinyl) benzoate, and tris(1,2,2,6,6-pentamethylpiperidinyl) phosphite; other light stabilizers, such as 3,5-di-tert-butyl-4-hydroxybenzoic acid (2,4-di-tert-butylphenyl) ester, alkyl phosphoramide, zinc N,N'-di-n-butyldithiocarbamate, nickel N,N'-di-n-butyldithiocarbamate, etc.; among them, the light stabilizers are preferably carbon black and bis(2,2,6,6-tetramethylpiperidinyl) sebacate (light stabilizer 770). The amount of the light stabilizer used is not particularly limited, and is generally 0.01-0.5 wt %.

[0259] The heat stabilizer can prevent the material from undergoing chemical changes due to heat during processing or use, or delay these changes to achieve the purpose of extending the service life, and includes but is not limited to any one or more of the following heat stabilizers: lead salts, such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, silica gel co-precipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organic tin compounds, such as dilauryl. The present invention also includes the following: di-n-butyltin diol, di-n-octyltin dilaurate, di-n-butyltin maleate, di-n-octyltin bismaleate, di-n-octyltin dimercaptoacetate, Jingtin C-102, dimethyltin dimercaptoacetate; antimony stabilizers such as antimony mercaptides, antimony mercaptoacetate mercaptides, antimony mercaptocarboxylates, antimony carboxylates; epoxy compounds such as epoxidized oils and epoxy fatty acid esters; phosphites such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkylaryl mixed esters, and polymeric phosphites; among them, the heat stabilizer is preferably barium stearate, calcium stearate, di-n-butyltin dilaurate, and di-n-butyltin maleate. The amount of the heat stabilizer used is not particularly limited, and is generally 0.1-0.5wt%.

[0260] The toughening agent can reduce the brittleness of the material, increase the toughness, and improve the bearing strength of the material, including but not limited to any 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 products, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene propylene rubber, ethylene propylene diene monomer (EPDM), butadiene rubber, styrene-butadiene rubber, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; wherein 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), chlorinated polyethylene resin (CPE). The amount of the toughening agent used is not particularly limited, and is generally 5-10wt%.

[0261] 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%.

[0262] 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%.

[0263] 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 5～9The plasticizers include triethylene glycol ether, ...

[0264] Among them, the antistatic agent can guide or eliminate the harmful charges accumulated in the material so that it does not cause inconvenience or harm to production and life, including but not limited to any one or several of the following antistatic agents: anionic antistatic agents, such as alkyl sulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate diethanolamine salt, potassium p-nonyldiphenyl ether sulfonate, phosphate derivatives, phosphates, phosphate derivatives, fatty amine sulfonates, sodium butyrate sulfonate; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryltrimethylammonium chloride, dodecyltrimethylammonium bromide, alkylhydroxyethyldimethylammonium perchlorate; zwitterionic antistatic agents, such as alkyl The present invention also includes the following antistatic agents: dicarboxymethyl ammonium ethyl salt, lauryl betaine, N,N,N-trialkylammonium acetyl (N'-alkyl) amine ethyl salt, N-lauryl-N,N-diethylene glycol dioxy-N-ethylphosphonate sodium, N-alkyl amino acid salt; nonionic antistatic agents such as fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, tripolyoxyethylene phosphate ether esters, glycerol fatty acid esters; polymer antistatic agents such as polyallylamide N-quaternary ammonium salt substitution products, poly-4-vinyl-1-acetonyl pyridine phosphate-p-butylphenyl ester salt, etc. Among them, the antistatic agent is preferably lauryl trimethylammonium chloride or alkyl phosphate diethanolamine salt (antistatic agent P). The amount of the antistatic agent used is not particularly limited, and is generally 0.3-3wt%.

[0265] Among them, the emulsifier can improve the surface tension between various constituent phases in the polymer mixture containing the auxiliary agent, so as to form a uniform and stable dispersion system or emulsion. It is preferably used for emulsion polymerization, and includes but is not limited to any one or several of the following emulsifiers: anionic, such as higher fatty acid salts, alkyl sulfonates, alkylbenzene sulfonates, sodium alkylnaphthalene sulfonate, succinate ester sulfonate, petroleum sulfonate, castor oil sulfate, sulfated ricinoleic acid butyl ester, phosphate ester, fatty acyl-peptide condensate; cationic, such as alkylammonium salts, alkyl quaternary ammonium salts, alkyl pyridinium salts; zwitterionic, such as carboxylate type, sulfonate type, sulfate type, phosphate type; nonionic, such as alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and anhydrous sorbitan fatty acid ester, sucrose fatty acid ester, alcoholamine fatty amide, etc.; among them, the emulsifier is preferably sodium dodecylbenzene sulfonate, anhydrous sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM). The amount of the emulsifier used is not particularly limited, and is generally 1-5 wt %.

[0266] The dispersant can disperse solid flocs in the polymer mixture into fine particles that are suspended in the liquid, uniformly dispersing those solid and liquid particles that are difficult to dissolve in the liquid, and preventing particle sedimentation and aggregation, thereby forming a stable suspension. Dispersants include, but are not limited to, any one or more of the following: anionic dispersants, such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, and sodium petroleum sulfonate; cationic dispersants; nonionic dispersants, such as fatty alcohol polyoxyethylene ether and sorbitan fatty acid polyoxyethylene ether; and inorganic dispersants, such as silicates and condensed phosphates. Preferred dispersants include sodium dodecylbenzene sulfonate, naphthalene methylene sulfonate (Dispersant N), and fatty alcohol polyoxyethylene ether. The amount of dispersant used is not particularly limited, but is generally 0.3-0.8 wt%.

[0267] Wherein, the colorant can make the product present the desired color and increase the surface color, including but not limited to any one or more of the following colorants: inorganic pigments, such as titanium dioxide, chrome yellow, cadmium red, iron oxide red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, such as Lithol Ruby BK, Lake Red C, Perylene Red, Geigy R Red, Phthalocyanine Red, Permanent Carmine HF3C, Plastic Red R and Cromer Red BR, Permanent Orange HL, Fast Yellow G, Ciba Plastic Yellow R, Permanent Yellow 3G, Permanent Yellow H2G, Phthalocyanine Blue B, Phthalocyanine Green, Plastic Violet RL, Aniline Black; organic dyes, such as thioindigo red, vat yellow 4GF, Shihlin Blue RSN, basic rose essence, oil-soluble yellow, etc.; wherein, the selection of colorant depends on the color requirements of the sample and does not need to be particularly limited. The amount of colorant used is not particularly limited, generally 0.01-5wt%, more preferably 0.2-2wt%.

[0268] The fluorescent whitening agent, which can impart a fluorite-like shimmering effect to the dyed material, includes but is not limited to any one or more of the following fluorescent whitening agents: stilbene-type, coumarin-type, pyrazoline-type, benzoxazine-type, phthalimide-type, etc.; among these, preferred fluorescent whitening agents include sodium stilbene biphenyl disulfonate (fluorescent whitening agent CBS), 4,4-bis(5-methyl-2-benzoxazolyl)stilbene (fluorescent whitening agent KSN), and 2,2-(4,4'-stilbene-bisbenzoxazole (fluorescent whitening agent OB-1). The amount of fluorescent whitening agent used is not particularly limited, but is generally 0.002-0.03 wt%.

[0269] The matting agent, which diffusely reflects incident light upon the polymer surface, produces a low-gloss, matte, or matte appearance. The matting agent includes, but is not limited to, any one or more of the following: precipitated barium sulfate, silica, hydrated gypsum powder, talc, titanium dioxide, and polymethylurea resin. Silicon dioxide is preferred. The amount of matting agent used is not particularly limited, but is generally 2-5 wt%.

[0270] Among them, the flame retardant can increase the flame resistance of the material, which includes but is not limited to any one or more of the following flame retardants: phosphorus series, such as red phosphorus, tricresol phosphate, triphenyl phosphate, tricresyl phosphate, toluene diphenyl 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, perchlorocyclopentane decane; inorganic flame retardants, such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants, such as chlorohydric anhydride, bis (2,3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, etc.; among them, the flame retardants are preferably decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, toluene diphenyl phosphate, antimony trioxide. The amount of the flame retardant used is not particularly limited, and is generally 1-20 wt%.

[0271] In the present invention, the filler mainly plays the following roles in the material: ① reducing the shrinkage rate of the molded product, improving the dimensional stability, surface finish, smoothness, and matte or matte properties of the product; ② regulating the viscosity of the polymer; ③ meeting different performance requirements, such as improving the impact strength and compression strength, hardness, stiffness and modulus of the polymer material, improving wear resistance, increasing heat deformation temperature, improving electrical conductivity and thermal conductivity, etc.; ④ improving the coloring effect of the pigment; ⑤ imparting light stability and chemical corrosion resistance; ⑥ playing a volume-increasing role, which can reduce costs and improve the competitiveness of the product in the market.

[0272] The fillers include but are not limited to inorganic non-metal fillers, metal fillers, organic fillers, and organometallic compound fillers.

[0273] Among them, 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 nanotubes, molybdenum disulfide, silicon dioxide, zinc oxide, aluminum oxide, diatomaceous earth, 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 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), upconversion 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, whiskers, etc.

[0274] Among them, the metal filler includes metal compounds, including but not limited to any one or more of the following: metal powders, fibers, including but not limited to powders and fibers of copper, silver, nickel, iron, gold, etc. and their alloys; nanometal particles, including but not limited to nanogold particles, nanosilver particles, nanopalladium particles, nanoiron particles, nanocobalt particles, nanonickel particles, nanoCoPt3 particles, nanoFePt particles, nanoFePd particles, nickel-iron bimetallic magnetic nanoparticles and other nanometal particles that can generate heat under at least one of infrared, near-infrared, ultraviolet, and electromagnetic effects; liquid metals, including but not limited to mercury, gallium, gallium-indium liquid alloys, gallium-indium-tin liquid alloys, and other gallium-based liquid metal alloys.

[0275] The organic fillers include, but are not limited to, any one or more of the following: ① natural organic fillers; ② synthetic resin fillers; ③ synthetic rubber fillers; ④ synthetic fiber fillers; ⑤ foamable polymer particles; ⑥ conjugated polymers; and ⑦ organic functional dyes / pigments. Organic fillers with properties such as ultraviolet absorption, fluorescence, luminescence, and photothermal properties are of great significance to the present invention, as their multifunctionality can be fully utilized.

[0276] 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.

[0277] 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%.

[0278] In an embodiment of the present application, the dynamically migratable low surface energy polymer modifier can be blended into the base resin through conventional mixing means in a standard production process, and migrates to the material surface during processing, heat treatment and use, to achieve the effects of waterproofing, stain resistance, dust resistance, anti-clotting, anti-thrombosis, antibacterial, self-cleaning, etc.

[0279] In an embodiment of the present application, the mixing means used include but are not limited to solution stirring mixing, melting stirring 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 mode used includes but is not limited to extrusion molding, injection molding, compression molding, casting molding, calendering molding, casting molding.

[0280] In an embodiment of the present application, the low surface energy blended composition is used as a base component to prepare a coating or paint with a solvent.

[0281] 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 solvents.

[0282] Further, suitable substrates for coating include, but are not limited to, glass (e.g., windows, optical components, lenses, mirrors), ceramics (e.g., ceramic tiles), cement, stone, surfaces to be coated (e.g., body panels and boat surfaces), metals (e.g., architectural columns), paper (e.g., adhesive release liners), cardboard (e.g., food containers), thermosets and thermoplastics (e.g., polycarbonates, acrylics, polyolefins, polyurethanes, polyesters, polyamides, polyimides, phenolic resins, cellulose diacetate, cellulose triacetate, polystyrene, and styrene-acrylonitrile copolymers), and combinations thereof. The substrate can be in the form of a film, sheet, or some other form. The substrate can include a transparent or translucent display element, which optionally has a ceramer hardcoat thereon.

[0283] In a specific embodiment of the present invention, the low surface energy blend composition of the present invention can be applied to a substrate using conventional coating techniques, such as spray coating, knife coating, notch coating, reverse roll coating, gravure coating, dip coating, rod coating, flow coating, or spin coating. Any optional solvent is then typically at least partially removed (e.g., using a forced air oven), and the low surface energy blend composition is then at least partially cured to form a durable coating.

[0284] In a specific embodiment of the present invention, the prepared low surface energy blend composition can be selectively heat-treated by low-temperature heating, so that the modifier in the matrix resin can migrate to the surface more quickly without affecting the matrix resin, wherein the optional suitable heat treatment temperature range is 40-60°C, and the optional suitable heat treatment time is 12 hours to 7 days.

[0285] The present invention also discloses an application of the low surface energy blend composition in the fields of coatings, textiles, electronic products, automotive parts, and filtration membranes.

[0286] The present invention also discloses an application of the low surface energy blend composition in the field of medical products. The medical products include medical instruments, medical equipment, 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 circuits, 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.

[0287] The specific embodiments of the present invention are described in detail below. The described embodiments are exemplary and are intended to be used to explain the present invention, but are not to be construed as limiting the present invention. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in the art or in accordance with the product specifications were used. Where the raw materials, reagents, or instruments used are not specified by manufacturer, they are all conventional products that can be obtained commercially.

[0288] For the sake of simplicity, the following abbreviations are used in the examples to represent the raw materials or reagents used:

[0289] PEG: polyethylene glycol

[0290] PPG: Polypropylene glycol

[0291] PTMG: Polytetramethylene glycol

[0292] HTPB: Hydroxyl-terminated polybutadiene

[0293] HLBH: Hydroxyl-terminated hydrogenated polybutadiene

[0294] HHTPI: Hydroxyl-terminated hydrogenated polyisoprene

[0295] PDMS-COH: Hydroxyl-terminated silicone oil

[0296] PDMS-CNH2: amino-terminated hydrocarbon modified silicone oil

[0297] PCDL: Polycarbonate Diol

[0298] PEA: polyethylene adipate

[0299] PBA: polybutylene adipate

[0300] PCL: Polycaprolactone

[0301] PO3G: Polytrimethylene ether glycol

[0302] ATPE: polyoxypropylene diamine

[0303] HDI: Hexamethylene diisocyanate

[0304] IPDI: Isophorone diisocyanate

[0305] TMDI: Trimethyl-1,6-hexamethylene diisocyanate

[0306] HMDI: dicyclohexylmethane diisocyanate

[0307] CHDI: 1,4-cyclohexane diisocyanate

[0308] HXDI: 1,4-cyclohexanedimethyl diisocyanate

[0309] MDI: diphenylmethane diisocyanate

[0310] TEDA: triethylenediamine

[0311] DMCHA: N,N-dimethylcyclohexylamine

[0312] C4F6OH: Hexafluorobutanol (CAS: 382-31-0)

[0313] C4F7OH: 2,2,3,3,4,4,4-heptafluorobutanol (CAS: 375-01-9)

[0314] C5F8OH: 2,2,3,3,4,4,5,5-octafluoropentanol (CAS: 355-80-6)

[0315] C6F9OH: 1H,1H,2H,2H-perfluorohexanol (CAS: 2043-47-2)

[0316] C8F13OH: 1H,1H,2H,2H-perfluorooctanol (CAS: 647-42-7)

[0317] C10F17OH: 1H,1H,2H,2H-perfluorodecanol (CAS: 678-39-7)

[0318] DMAc: dimethylacetamide

[0319] THF: Tetrahydrofuran

[0320] MeOH: methanol

[0321] CHCl3: chloroform

[0322] IPA: Isopropyl alcohol

[0323] The infrared spectrum test was performed using the iS50 Fourier transform infrared spectrometer produced by Thermo Fisher Scientific, USA.

[0324] The hardness test is carried out using a Shore A or Shore D durometer at 23°C. The test method is: insert the Shore durometer into the material to be tested, and the value displayed on the dial is the hardness value.

[0325] Contact angle measurements were performed using an Attension Theta Lite optical contact angle meter from Bioline Technologies, Sweden. The droplets used in the experiment were deionized water and diiodomethane. The droplet volume was 5 μL, and the test was conducted at 25°C and 65% RH. By measuring the contact angles of water and diiodomethane on the product surface, the free energy contributions of the polar and dispersive components of the product's surface free energy were calculated. The surface free energy of the sample was calculated according to Fowkes theory (Fowkes FM. Attractive forces at interface [J]. Indust Eng Chem 1964, 56: 40-52.).

[0326] The molecular weight and molecular weight distribution of the product were determined by gel permeation chromatography (GPC) on a Waters-150C gel permeation chromatography instrument (Waters, USA). Polystyrene standards were used as the reference polymer, and relative molecular weight and elution time were calibrated. Tetrahydrofuran (chromatographic grade) was used as the mobile phase. The test temperature was 35°C, the test sample volume was 25 μL, and the flow rate was 0.8 mL / min. Before testing, the polymer solution was filtered through a 0.45 μm polytetrafluoroethylene (PTFE) porous filter.

[0327] Fluorine content is determined by the combustion method on an Elementar vario EL III elemental analyzer. The sample is burned in an oxygen stream, and the organic components are fully oxidized with an oxidant, resulting in the quantitative conversion of each element into its corresponding volatile oxide. These products are then passed through a silica gel column chromatography column, and their concentrations are measured using a thermal conductivity detector. The fluorine content is then calculated by titration with a thorium nitrate standard solution.

[0328] The tensile properties test was carried out using a CMT-6104 microcomputer series electronic universal testing machine produced by Shenzhen Xinsansi Metrology Technology Co., Ltd. The test standard was GB 1040-79.

[0329] The tearing performance test was carried out using a CMT-6104 microcomputer series electronic universal testing machine produced by Shenzhen Xinsansi Metrology Technology Co., Ltd. The test standard was GB / T529-2008.

[0330] The SEM test was carried out using a German Zeiss Sigma 300 scanning electron microscope, and the fluorine atomic percentage on the sample surface was analyzed by EDS mapping.

[0331] The durability test uses 1200 grit sandpaper to polish the sample surface. After polishing, the contact angle test is performed directly. Then the sample is placed at room temperature for 5 days and the contact angle test is performed again. After the test is completed, the sample is continued to be polished and then placed at room temperature for 7 days and the contact angle test is performed again. The experiment is repeated. When the water contact angle of the sample decreases by 15%, it is judged to have failed.

[0332] All tests in this embodiment, comparative example, application comparative example, and application embodiment were performed after the samples were prepared and placed for 1-2 weeks, during which time some samples were selectively subjected to low-temperature heat treatment.

[0333] Preparation of organic borate compounds:

[0334] Preparation of organic borate compound I:

[0335] 13.69 g of 3-aminophenylboronic acid (0.1 mol) was added to a reaction flask and dissolved in 50 ml of MeOH. Then 10 g of anhydrous magnesium sulfate was added, and 9.11 g of 3-amino-1,2-propanediol (0.1 mol) was dissolved in 25 ml of MeOH. The mixture was added dropwise to the reaction flask, stirred at room temperature for 24 h, allowed to stand to separate, and filtered under reduced pressure. The filtrate was rotary evaporated at 55 °C to remove MeOH, and then placed in a vacuum oven at 70 °C overnight to obtain a yellow-white solid powder.

[0336] Preparation of organic borate compound II:

[0337] 26.00 g of 1,6-hexanediol (0.22 mmol) was added to a reaction flask and dissolved in 50 ml of THF. 20 g of anhydrous magnesium sulfate was then added, and 5.97 g of methylboric acid (0.1 mol) was dissolved in 50 mL of THF and added dropwise. The mixture was heated to 50°C and reacted for 24 h. The mixture was allowed to stand for stratification and filtered under reduced pressure. The filtrate was washed with n-hexane. The solvent was removed from the filtrate by rotary evaporation at 60°C and finally placed in a vacuum oven at 70°C overnight to obtain a light yellow solid powder.

[0338] Preparation of organic borate compound III:

[0339] 13.69 g of 4-aminophenylboronic acid (0.1 mol) was added to a reaction flask and dissolved in 50 ml of MeOH. Then 10 g of anhydrous magnesium sulfate was added, and 15.32 g of dopamine (0.1 mol) was dissolved in 50 ml of MeOH. The mixture was added dropwise to the reaction flask, stirred at room temperature for 24 h, allowed to stand to separate, and filtered under reduced pressure. The filtrate was evaporated at 55 °C to remove MeOH, and then placed in a vacuum oven at 70 °C overnight to obtain a yellow solid powder.

[0340] Preparation of organic borate compound IV:

[0341] 27.59 g of 3-hydroxyphenylboronic acid (0.2 mol) was added to a reaction flask and dissolved in 100 ml of MeOH. Then 15 g of anhydrous magnesium sulfate was added, and 13.61 g of pentaerythritol (0.1 mol) was dissolved in 50 ml of MeOH. The mixture was added dropwise to the reaction flask, stirred at room temperature for 24 h, allowed to stand to separate, and filtered under reduced pressure. The filtrate was rotary evaporated at 55 °C to remove MeOH, and then placed in a vacuum oven at 70 °C overnight to obtain a white solid powder.

[0342] Preparation of organic borate compound V:

[0343] 17.80 g of 1-aminoethylboric acid (0.2 mol) was added to a reaction flask and dissolved in 80 ml of THF. Then 15 g of anhydrous magnesium sulfate was added, and 27.83 g of 5-amino-2-(hydroxymethyl)phenol (0.2 mol) was dissolved in 100 ml of THF. The mixture was added dropwise to the reaction flask, stirred at room temperature for 24 h, allowed to stand to separate, and filtered under reduced pressure. The filtrate was washed with n-hexane, and the solvent was removed by rotary evaporation at 60° C. The filtrate was finally placed in a vacuum oven at 70° C. overnight to obtain a light yellow solid powder.

[0344] Example 1

[0345] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 30 g of PEG (50 mmol, PETRONAS PEG-600, Mn=600) was added to a four-necked flask equipped with a stir bar. The flask containing the PEG was heated to 100°C and vacuum-dried for 3 h. 200 ml of anhydrous DMAc was added to the flask, and the PEG was dissolved by stirring in a 60°C oil bath with nitrogen. 19.68 g (75 mmol) of HMDI was added to the flask, and the mixture was stirred to dissolve. 25 mg (0.05 wt% based on the weight of the PEG) of bismuth carboxylate catalyst was then added. The mixture was stirred at 60°C with a continuous nitrogen flow for 2 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0346] 1.76 g (15 mmol) of N-tert-butylethanolamine was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 50°C and stirred for 3 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 9.10 g (25 mmol) of C8F13OH was then added and the reaction was continued at 60°C for 5 hours. 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 in distilled water and washed several times in methanol. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 8 hours to obtain a transparent, viscous liquid, designated as Modifier 1. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are listed in Table 1.

[0347] Example 2

[0348] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 60 g of PPG (20 mmol, Shandong Bluestar Dongda Chemical Co., Ltd., Mn = 3000, viscosity 460-600 mPa·s at 25°C) was added to a four-necked flask equipped with a stir bar. The flask containing the PPG was heated to 90°C and vacuum-dried for 3 h. 8.45 g (38 mmol) of IPDI was added to the flask, and the mixture was stirred at 90°C for 3 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0349] 1.09 g (8 mmol) of salicylaldehyde hydrazone was weighed and added to the flask containing the prepolymer. The resulting mixture was heated at 60°C and stirred for 10 minutes. 4.18 g (18 mmol) of C₅F₄OH was then added and stirred for 20 minutes. The mixture was poured into a mold and allowed to react in an 80°C forced air oven for 12 hours. After cooling, a gray, translucent elastomer was obtained, designated Modifier 2. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were measured and are listed in Table 1.

[0350] Example 3

[0351] All glassware used for the synthesis reaction was dried in an oven at 110°C for 2 h. 40 g of PPG (20 mmol, Shandong Bluestar Dongda Chemical Co., Ltd., Mn=2000) was added to a four-necked flask equipped with a stirring rod. The flask containing the PPG was heated to 100°C and vacuumed to remove water for 3 h. 150 ml of anhydrous DMAc was added to the flask, and the flask was placed in a 70°C oil bath and stirred with nitrogen to dissolve the PPG. 8.41 g (40 mmol) of TMDI was added to the flask, followed by 50 mL of anhydrous DMAc, and the mixture was stirred to dissolve. 32 mg (0.08 wt% based on the mass of the PPG) of an organotin catalyst was then added. The mixture was stirred and reacted at 90°C for 2 h under continuous nitrogen flow. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0352] 3.19 g (14 mmol) of organic borate compound I was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 55°C with stirring for 4 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 2.55 g (14 mmol) of C₄F₆OH was then added and the reaction was continued at 65°C for 6 hours. 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 in distilled water and washed several times in methanol. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 8 hours to obtain a light gray viscous liquid, designated as Modifier 3. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0353] Example 4

[0354] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. To a four-necked flask equipped with a stir bar was added 26 g of PTMG (40 mmol, Mitsubishi Chemical Corporation PTMG 650, Mn=650, viscosity 100-200 mPa·s at 40°C). The flask containing the PTMG was heated to 110°C and vacuum-dried for 2 h. 10.09 g (60 mmol) of HDI was added to the flask. The mixture was stirred at 100°C for 2 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0355] To the flask containing the prepolymer was added 1.87 g (16 mmol) of 3-hydroxy-3-methyl-2-butanone oxime and the resulting mixture was stirred at 80 °C for 30 min. Then, 3.71 g (8 mmol) of C10F17OH was added and the stirring was continued for another 30 min. The mixture was poured into a mold and the reaction was continued in a forced air oven at 80 °C for 48 h. After cooling, a translucent elastomer was obtained and was designated as Modifier 4. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1.

[0356] Example 5

[0357] 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 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn = 1000). 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 under a continuous flow of nitrogen for 2 h. The -NCO content of the system was determined to be stable using a potentiometric titrator and a prepolymer was obtained.

[0358] To the flask containing the prepolymer was added 1.87 g (16 mmol) of 3-hydroxy-3-methyl-2-butanone oxime and the resulting mixture was stirred at 80 °C for 30 min. Then, 3.71 g (8 mmol) of C10F17OH was added and the stirring was continued for another 30 min. The mixture was poured into a mold and the reaction was continued in a forced air oven at 80 °C for 48 h. After cooling, a translucent elastomer was obtained and was designated as Modifier 4. 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

[0359] Example 6

[0360] ​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 (10 mmol, Mitsubishi Chemical Corporation PTMG 2000, Mn = 2000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 4.67 g (21 mmol) of IPDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst. The mixture was stirred at 90 °C under a constant stream of nitrogen for 2 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0361] A four necked flask equipped with a stir bar was charged with 20 g of PTMG (10 mmol, Mitsubishi Chemical Corporation PTMG 2000, Mn = 2000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 4.67 g (21 mmol) of IPDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst. The mixture was stirred at 90 °C under a constant stream of nitrogen for 2 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0362] Example 7

[0363] 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 (10 mmol, Mitsubishi Chemical Corporation PTMG 2000, Mn = 2000) and the flask containing the PTMG was heated to 110 °C and vacuumed for 2 h to remove water. To the flask was added 4.67 g (21 mmol) of IPDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst. The mixture was stirred at 90 °C under a constant stream of nitrogen for 2 h and the -NCO content of the system was determined to be stable using a potentiometric titrator to give a prepolymer.

[0364] 0.49 g (5 mmol) of 4-(hydroxymethyl)imidazole was weighed and added to the flask containing the prepolymer. 60 ml of anhydrous acetone was added to reduce viscosity. The resulting mixture was heated to 55°C with stirring for 6 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 2.20 g (11 mmol) of C₄F₇OH was then added, and the reaction was continued at 60°C for 4 hours. 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 repeatedly washed with a MeOH / water solution. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 12 hours to obtain a white solid, designated Modifier 7. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0365] Example 8

[0366] All glassware used for the synthesis reaction were dried in an oven at 110°C for 2h. 32g of HTPB (20mmol, Liming Chemical Research Institute V type, Mn=1600) was added to a four-necked flask equipped with a stirring rod, and the flask containing HTPB was heated to 110°C and vacuumed to remove water for 2h. 100ml of anhydrous toluene was added to the flask, and the HTPB was dissolved by nitrogen in an oil bath at 80°C. 5.32g (32mmol) of CHDI was added to the flask, followed by 100mL of anhydrous toluene, and the mixture was stirred to dissolve, and then 0.064g (0.2wt% based on the mass of HTPB) of bismuth carboxylate catalyst was added. The mixture was stirred and reacted at 110°C for 3h, and the -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0367] 1.15 g (8 mmol) of N,N'-diisopropylethylenediamine was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 70°C and stirred for 6 hours. The -NCO content in the system was determined using a potentiometric titrator to stabilize. 2.78 g (6 mmol) of C10F17OH was then added and the reaction continued at 70°C for 12 hours. The polymer solution was cooled to room temperature and precipitated in MeOH. The resulting precipitate was repeatedly washed with a THF / MeOH mixture and dried at room temperature for 12 hours. It was then dried in a vacuum oven at 110°C for 12 hours to obtain a light yellow elastomer, designated Modifier 8. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are listed in Table 1.

[0368] Example 9

[0369] All glassware used in the synthesis reaction was dried in an oven at 110°C for 2 h. 15 g of HLBH (10 mmol, Nisso PB GI-1000, Mn=1500, manufactured by Nippon Soda Co., Ltd.) was added to a four-necked flask equipped with a stir bar. The flask containing the HLBH was heated to 120°C and evacuated to remove water for 2 h. 100 ml of anhydrous toluene was added to the flask, and the HLBH was dissolved by stirring in an 80°C oil bath with nitrogen. 4.65 g (20 mmol) of IPDI was added to the flask, followed by 30 mL of anhydrous toluene. The mixture was stirred to dissolve, and 0.03 g (0.2 wt% based on the mass of the HLBH) of bismuth carboxylate catalyst was added. The mixture was stirred and reacted at 110°C for 2 h with continuous nitrogen flow. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0370] 0.16 g (5 mmol) of organic borate compound II was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 60°C and stirred for 4 hours. The -NCO content in the system was determined using a potentiometric titrator to stabilize. 4.01 g (11 mmol) of C8F13OH was then added and the reaction continued at 60°C for 4 hours. The polymer solution was cooled to room temperature and precipitated in MeOH. The resulting precipitate was repeatedly washed with a THF / MeOH mixed solvent, dried at room temperature for 12 hours, and then dried in a vacuum oven at 120°C for 12 hours to obtain a translucent elastomer, designated 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.

[0371] Example 10

[0372] All glassware used in the synthesis reaction was dried in a 110°C oven for 2 h. 30 g of HLBH (10 mmol, Nisso PB GI-3000, Mn=3000, manufactured by Nippon Soda Co., Ltd.) was added to a four-necked flask equipped with a stir bar. The flask containing the HLBH was heated to 120°C and vacuumed to remove water for 2 h. 100 ml of anhydrous toluene was added to the flask, which was then placed in an 80°C oil bath and stirred with nitrogen to dissolve the HLBH. 3.36 g (20 mmol) of HDI was added to the flask, stirred to mix, and then 0.06 g (0.2 wt% based on the mass of the HLBH) of TEDA catalyst was added. The mixture was stirred and reacted at 110°C for 2 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0373] Weigh 0.79 g (5 mmol) of 2,2,6,6-tetramethyl-4-piperidinol and add it to the flask containing the prepolymer. Heat the resulting mixture to 80°C and stir to react for 3 hours. Use a potentiometric titrator to determine the -NCO content in the system to reach stability, then add 1.82 g (10 mmol) of C4F6OH and continue to react at 80°C for 4 hours. Cool the polymer solution to room temperature, precipitate it in MeOH, dissolve the crude product in CHCl3, and pour it into a separatory funnel. Add deionized water, shake the funnel, separate the bottom layer containing the product, and wash it with water in a separatory funnel. Concentrate the separated CHCl3 layer by rotary evaporation to obtain the product. After drying it at room temperature for 6 hours, dry it in a vacuum oven at 60°C for 24 hours to obtain a yellow translucent elastomer, which is recorded as modifier 10. Its infrared spectrum is shown in the figure below. Figure 2 As shown, the weight average molecular weight (Mw), polydispersity and fluorine content of the modifier were measured, and the results are listed in Table 1.

[0374] Example 11

[0375] All glassware used in the synthesis reaction was dried in an oven at 110°C for 2 h. 20 g of HHTPI (10 mmol, Epol, Mn=2000, manufactured by Idemitsu Kosan Co., Ltd., Japan) was added to a four-necked flask equipped with a stirring rod. The flask containing HHTPI was heated to 120°C and vacuumed to remove water for 2 h. 100 ml of anhydrous CHCl₃ was added to the flask, and the HLBH was dissolved by stirring in a 60°C oil bath with nitrogen. 3.36 g (16 mmol) of TMDI was added to the flask, followed by 30 mL of anhydrous CHCl₃, and the mixture was stirred to dissolve. The mixture was stirred and reacted at 60°C with nitrogen for 6 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0376] 0.87 g (3 mmol) of the prepared organic borate compound III was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 60°C and stirred for 8 hours. The -NCO content in the system was determined using a potentiometric titrator until it stabilized. 2.32 g (5 mmol) of C10F17OH was then added and the reaction continued at 60°C for 12 hours. The polymer solution was cooled to room temperature and precipitated in MeOH. The resulting precipitate was repeatedly washed with a THF / MeOH mixed solvent, dried at room temperature for 12 hours, and then dried in a vacuum oven at 120°C for 12 hours to obtain a gray elastomer, designated Modifier 11. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are listed in Table 1.

[0377] Example 12

[0378] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 50 g of PDMS-COH (20 mmol, Dow Corning 3667, Mn=2400, viscosity 200-500 mPa·s at 25°C) was added to a four-necked flask equipped with a stir bar. The flask containing the PDMS-COH was heated to 80°C and vacuum-dried for 4 h. 7.06 g (42 mmol) of HDI was added to the flask. The mixture was stirred and reacted at 80°C for 4 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0379] 1.82 g (8 mmol) of organic borate compound I was weighed and added to the flask containing the prepolymer. The resulting mixture was stirred at 50°C for 120 minutes. 6.55 g (18 mmol) of C8F13OH was then added and stirred at 50°C for another 30 minutes. The mixture was poured into a mold and allowed to react in an 80°C forced air oven for 12 hours. After cooling, a light yellow viscous oil was obtained, designated Modifier 12. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0380] Example 13

[0381] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 50 g of PDMS-COH (20 mmol, Dow Corning 3667, Mn=2400, viscosity 200-500 mPa·s at 25°C) was added to a four-necked flask equipped with a stir bar. The flask containing the PDMS-COH was heated to 80°C and vacuum-dried for 4 h. 11.02 g (42 mmol) of HMDI was added to the flask. The mixture was stirred and reacted at 70°C for 6 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0382] 1.06 g (12 mmol) of glyoxime was weighed and added to the flask containing the prepolymer. The resulting mixture was stirred and reacted at 40°C for 120 minutes. 3.28 g (18 mmol) of C₄F₆OH was then added and stirred at 40°C for another 30 minutes. The mixture was poured into a mold and reacted in an 80°C forced air oven for another 12 hours. After cooling, a light yellow viscous oil was obtained, designated Modifier 13. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were measured and are listed in Table 1.

[0383] Example 14

[0384] All glassware used in the synthesis reaction was dried in a 110°C oven for 2 h. 50 g of PDMS-COH (20 mmol, Dow Corning 5562, Mn=2500) was added to a four-necked flask equipped with a stir bar. The flask containing the PDMS-COH was heated to 80°C and vacuum-dried for 4 h. 200 ml of anhydrous THF was added to the flask, and the PDMS-COH was dissolved by stirring in a 60°C oil bath with nitrogen. 6.98 g (42 mmol) of CHDI was added to the flask, followed by 50 mL of anhydrous THF. The mixture was stirred to dissolve, and 25 mg (0.05 wt% based on the mass of PDMS-COH) of triethylamine catalyst was added. The mixture was stirred and reacted at 60°C with nitrogen for 6 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0385] 1.02 g (10 mmol) of methylglyoxime was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 50°C and stirred for 6 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 10.21 g (22 mmol) of C10F17OH was then added and the reaction continued at 60°C for 10 hours. 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 hours and then dried in a vacuum oven at 60°C for 12 hours to obtain a light yellow elastomer, designated as modifier 14. Its infrared spectrum is shown in the figure below. Figure 3 As shown, the weight average molecular weight (Mw), polydispersity and fluorine content of the modifier were measured, and the results are listed in Table 1.

[0386] Example 15

[0387] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 40 g of PDMS-CNH2 (20 mmol, UC-2330, Mn=2000, manufactured by Jiaxing United Chemical Co., Ltd.) was added to a four-necked flask equipped with a stir bar. The flask containing the PDMS-CNH2 was heated to 80°C and evacuated for 3 h to remove water. 11.02 g (42 mmol) of HMDI was added to the flask, followed by 0.25 g (0.5 wt% based on the mass of the PDMS-CNH2) of bismuth carboxylate catalyst. The mixture was stirred and reacted at 70°C for 4 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0388] Example 15 1.88 g (16 mmol) of N-tert-butyl ethanolamine was weighed into a flask containing the prepolymer, 50 mL of anhydrous THF was added to reduce the viscosity, and the resulting mixture was heated to 45°C and stirred for 8 h. The -NCO content of the system was determined using a potentiometric titrator until it reached a stable value, and then 2.32 g (10 mmol) of C5F8OH was added. 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 obtain an amber viscous oil, which was designated as Modifier 15. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0389] Example 16

[0390] 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 Corporation CD210, Mn = 1000), and the flask containing the PCDL was heated to 100°C and vacuumed for 3 h to remove water. 100 mL of anhydrous DMAc was added to the flask, and the flask was placed in an oil bath at 70°C and stirred under a nitrogen atmosphere to dissolve the PCDL. 7.70 g (40 mmol) of HXDI was added to the flask, and 50 mL of anhydrous DMAc was added to dissolve the mixture. Then, 16 mg (0.08 wt% based on the mass of PCDL) of an organotin catalyst was added. The mixture was continuously stirred under a nitrogen atmosphere at 80°C for 4 h, and the -NCO content of the system was determined using a potentiometric titrator until it reached a stable value to obtain a prepolymer.

[0391] Example 15 1.88 g (16 mmol) of N-tert-butyl ethanolamine was weighed into a flask containing the prepolymer, 50 mL of anhydrous THF was added to reduce the viscosity, and the resulting mixture was heated to 45°C and stirred for 8 h. The -NCO content of the system was determined using a potentiometric titrator until it reached a stable value, and then 2.32 g (10 mmol) of C5F8OH was added. 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 obtain an amber viscous oil, which was designated as Modifier 15. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1. Figure 4

[0392] Example 17

[0393] ​All glassware used in the synthesis reaction was dried in an oven at 110°C for 2 h. 40 g of PCDL (20 mmol, Asahi Kasei Chemicals T5652, Mn=2000) was added to a four-necked flask equipped with a stirring rod. The flask containing PCDL was heated to 100°C and vacuum-dried for 3 h. 150 ml of anhydrous DMAc was added to the flask, and the flask was placed in a 70°C oil bath and stirred with nitrogen to dissolve the PCDL. 8.89 g (40 mmol) of IPDI was added to the flask, followed by 50 mL of anhydrous DMAc. The mixture was stirred to dissolve, and 40 mg (0.1 wt% based on the mass of PCDL) of bismuth carboxylate catalyst was added. The mixture was stirred and reacted at 80°C for 4 h under continuous nitrogen flow. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0394] 5.77 g (14 mmol) of organic borate compound IV was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 75°C with stirring for 3 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 3.70 g (14 mmol) of C6F9OH was then added and the reaction was continued at 80°C for 10 hours. 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 in distilled water and washed several times in an IPA solution, followed by another wash in IPA / n-hexane. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 120°C for 12 hours to obtain a white solid powder, designated as Modifier 17. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0395] Example 18

[0396] All glassware used in the synthesis reaction was dried in an oven at 110°C for 2 h. 10 g of PCDL (20 mmol, Daicel CD205PL, Mn=500) was added to a four-necked flask equipped with a stirring rod. The flask containing PCDL was heated to 100°C and vacuum-dried for 3 h. 50 ml of anhydrous DMAc was added to the flask, and the flask was placed in a 70°C oil bath with nitrogen and stirred to dissolve the PCDL. 3.99 g (24 mmol) of CHDI was added to the flask, followed by 0.02 g (0.2 wt% based on the mass of PCDL) of bismuth carboxylate catalyst. The mixture was stirred and reacted at 80°C with nitrogen for 5 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0397] 1.92 g (8 mmol) of azine salicylaldehyde was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 75°C with stirring for 3 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 2.18 g (6 mmol) of C8F13OH was then added and the reaction was continued at 80°C for 10 hours. 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 in distilled water and washed several times in an IPA solution, followed by another wash in IPA / n-hexane. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 120°C for 12 hours to obtain a white solid powder, designated as Modifier 18. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0398] Example 19

[0399] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 40 g of PCDL (20 mmol, Asahi Kasei Chemicals T5652, Mn=2000) was added to a four-necked flask equipped with a stir bar. The flask containing the PCDL was heated to 100°C and vacuum-dried for 3 h. 150 ml of anhydrous DMAc was added to the flask, and the flask was placed in a 70°C oil bath with nitrogen flow and stirred to dissolve the PCDL. 6.73 g (40 mmol) of HDI was added to the flask, followed by 50 mL of anhydrous DMAc. The mixture was stirred to dissolve, and 32 mg (0.08 wt% based on the mass of the PCDL) of an organotin catalyst was added. The mixture was stirred and reacted at 70°C with nitrogen flow for 6 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0400] 1.72 g (10 mmol) of N,N'-di-tert-butylethylenediamine was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 70°C with stirring for 3 hours. The -NCO content in the system was determined using a potentiometric titrator to stabilize. 4.75 g (18 mmol) of C6F9OH was then added and the reaction was continued at 80°C for 8 hours. 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 in distilled water and washed several times in an IPA solution, followed by another wash in IPA / n-hexane. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 120°C for 12 hours to obtain a white solid powder, designated as Modifier 19. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are listed in Table 1.

[0401] Example 20

[0402] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 40 g of PBA (20 mmol, Yantai Huada Chemical Industry CMA-44, Mn=2000) was added to a four-necked flask equipped with a stir bar. The flask containing PBA was heated to 90°C and evacuated for 3 h to remove water. 6.73 g (40 mmol) of HDI was added to the flask, followed by 16 mg (0.08 wt% based on the mass of PBA) of TEDA catalyst. The mixture was stirred and reacted at 80°C for 3 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0403] 1.39 g (12 mmol) of dimethylglyoxime was weighed and added to the flask containing the prepolymer. The resulting mixture was stirred at 40°C for 5 minutes. 5.10 g (14 mmol) of C8F13OH was then added and stirred for another 5 minutes. The mixture was poured into a mold and allowed to react in an 80°C forced air oven for 12 hours. After cooling, a white viscous liquid was obtained, 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.

[0404] Example 21

[0405] All glassware used in the synthesis reaction was dried in an oven at 110°C for 2 h. 40 g of PEA (40 mmol, Yantai Huada Chemical Industry CMA-1024, Mn = 1000, viscosity 100-200 mPa·s at 75°C) was added to a four-necked flask equipped with a stirring rod. The flask containing PEA was heated to 90°C and vacuum-dried for 3 h. 200 ml of anhydrous DMAc was added to the flask, and the flask was placed in a 70°C oil bath and stirred with nitrogen to dissolve the PEA. 19.94 g (76 mmol) of HMDI was added to the flask, followed by 32 mg (0.08 wt% based on the mass of PEA) of TEDA catalyst. The mixture was stirred and reacted at 80°C for 3 h under continuous nitrogen flow. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0406] 2.34 g (20 mmol) of N-tert-butylethanolamine was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 60°C and stirred for 3 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 8.35 g (36 mmol) of C5F8OH was then added and the reaction was continued at 65°C for 4 hours. 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 in distilled water and washed several times in ethanol. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 12 hours to obtain a white viscous liquid, designated as Modifier 21. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are listed in Table 1.

[0407] Example 22

[0408] All glassware used for the synthesis reaction were dried in an oven at 110°C for 2 h. 20 g of PCL (20 mmol, Daicel 210N, Mn = 1000) was added to a four-necked flask equipped with a stirring rod. The flask containing PCL was heated to 110°C and vacuumed to remove water for 2 h. 150 ml of anhydrous DMAc was added to the flask, and the flask was placed in a 70°C oil bath and stirred with nitrogen to dissolve the PCL. 5.78 g (26 mmol) of IPDI was added to the flask, followed by 10 mg (0.05 wt% based on the mass of PCL) of DMCHA catalyst. The mixture was stirred and reacted at 80°C for 3 h under continuous nitrogen flow. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0409] 0.91 g (4 mmol) of organic borate compound V was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 70°C with stirring for 4 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 0.53 g (4 mmol) of C6F9OH was then added and the reaction continued at 70°C for another 4 hours. 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 in distilled water and washed several times in ethanol. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 12 hours to obtain a light gray solid, designated as Modifier 22. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0410] Example 23

[0411] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 48 g of PO3G (20 mmol, Dupont Cerenol H2400, Mn=2400) was added to a four-necked flask equipped with a stir bar. The flask containing the PO3G was heated to 100°C and vacuum-dried for 2 h. 200 ml of anhydrous DMAc was added to the flask, and the PO3G was dissolved by stirring in a 70°C oil bath with nitrogen. 5.83 g (30 mmol) of HXDI was added to the flask, followed by 48 mg (0.1 wt% based on the mass of the PO3G) of DMCHA catalyst. The mixture was stirred at 80°C with a continuous nitrogen flow for 4 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0412] 2.46 g (6 mmol) of organic borate compound IV was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 60°C and stirred for 4 hours. The -NCO content in the system was determined using a potentiometric titrator until it stabilized. 4.64 g (10 mmol) of C10F17OH was then added and the reaction was continued at 70°C for 8 hours. 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 in distilled water and washed several times in ethanol. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 12 hours to obtain a translucent solid, designated as Modifier 23. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0413] Example 24

[0414] All glassware used for the synthesis reaction were dried in an oven at 110°C for 2h. 40g of ATPE (20mmol, AMD-2000, Yantai Minsheng Chemicals Co., Ltd., Mn=2000) was added to a four-necked flask equipped with a stirring rod, and the flask containing ATPE was heated to 110°C and vacuumed to remove water for 2h. 200ml of anhydrous toluene was added to the flask, and the ATPE was dissolved by stirring in a 70°C oil bath with nitrogen. 6.65g (40mmol) of CHDI was added to the flask, followed by 20mg (0.05wt% based on the mass of ATPE) of organotin catalyst. The mixture was stirred and reacted at 70°C for 2h with continuous nitrogen flow, and the -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0415] 1.37 g (10 mmol) of salicylaldehyde oxime was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 60°C and stirred for 3 hours. The -NCO content in the system was determined using a potentiometric titrator and stabilized. 5.28 g (20 mmol) of C6F9OH was then added and the reaction continued at 60°C for 4 hours. The polymer solution was cooled to room temperature and precipitated in MeOH. The crude product was dissolved in CHCl3 and poured into a separatory funnel. Deionized water was added, and the funnel was shaken to separate the bottom layer containing the product. The bottom layer was washed with water in a separatory funnel and the separated CHCl3 layer was concentrated by rotary evaporation to obtain the product. The product was dried at room temperature for 8 hours and then dried in a vacuum oven at 60°C for 24 hours to obtain a yellow solid, designated as Modifier 24. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and the results are listed in Table 1.

[0416] Comparative Example 1

[0417] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. To a four-necked flask equipped with a stir bar was added 60 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 3000, Mn=3000). The flask containing the PTMG was heated to 110°C and evacuated for 2 h to remove water. 6.65 g (40 mmol) of CHDI and 12 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst were added to the flask. The mixture was stirred and reacted at 90°C under a continuous nitrogen atmosphere for 2 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0418] 100 ml of anhydrous acetone was added to the flask containing the prepolymer to reduce the viscosity. 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. The crude product was dissolved in MeOH and repeatedly washed with a MeOH / water solution. After drying at room temperature for 12 h, the crude product was placed in a vacuum oven at 80°C and dried for 12 h to obtain a translucent solid, which was recorded as modifier 25. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were measured, and the results are listed in Table 1.

[0419] Comparative Example 2

[0420] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn=1000) was added to a four-necked flask equipped with a stir bar. The flask containing the PTMG was heated to 110°C and vacuum-dried for 2 h. 6.65 g (40 mmol) of CHDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst were added to the flask. The mixture was stirred and reacted at 90°C for 2 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0421] 0.90 g (10 mmol) of 1,4-butanediol was weighed and added to the flask containing the prepolymer, and 50 ml of anhydrous acetone was added to reduce the viscosity. The resulting mixture was heated at 70°C with stirring for 3 h. The -NCO content in the system was determined by potentiometric titrator to reach stability. 5.28 g (20 mmol) of C6F9OH was added, and the mixture was heated to 70°C and stirred for 4 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 repeatedly washed with MeOH / water solution. After drying at room temperature for 12 h, it was placed in a vacuum oven at 80°C and dried for 12 h to obtain a translucent elastomer, which was recorded 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.

[0422] Comparative Example 3

[0423] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn=1000) was added to a four-necked flask equipped with a stir bar. The flask containing the PTMG was heated to 110°C and vacuum-dried for 2 h. 6.65 g (40 mmol) of CHDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst were added to the flask. The mixture was stirred and reacted at 90°C for 2 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0424] 2.50 g (10 mmol) of bis(4-hydroxyphenyl) disulfide was weighed and added to the flask containing the prepolymer, and 50 ml of anhydrous acetone was added to reduce the viscosity. The resulting mixture was heated at 70°C with stirring for 3 h. The -NCO content in the system was determined by potentiometric titrator to reach stability. 5.28 g (20 mmol) of C6F9OH was then added, and the mixture was heated to 70°C and stirred for 4 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 repeatedly washed with a MeOH / water solution. After drying at room temperature for 12 h, it was placed in a vacuum oven at 80°C and dried for 12 h to obtain a light yellow elastomer, which was recorded as modifier 27. The weight average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined, and the results are listed in Table 1.

[0425] Comparative Example 4

[0426] All glassware used in the synthesis reaction was oven-dried at 110°C for 2 h. 20 g of PTMG (20 mmol, Mitsubishi Chemical Corporation PTMG 1000, Mn=1000) was added to a four-necked flask equipped with a stir bar. The flask containing the PTMG was heated to 110°C and vacuum-dried for 2 h. 6.65 g (40 mmol) of CHDI and 4 mg (0.02 wt% based on the mass of PTMG) of bismuth carboxylate catalyst were added to the flask. The mixture was stirred and reacted at 90°C for 2 h under a continuous nitrogen atmosphere. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0427] 1.56 g (10 mmol) of 2,2,6,6-tetramethylpiperidinamine was weighed and added to the flask containing the prepolymer. 50 ml of anhydrous acetone was added to reduce the viscosity. The resulting mixture was heated at 60°C with stirring for 4 h. The -NCO content in the system was determined by potentiometric titration to reach stability. 4.43 g (20 mmol) of silane coupling agent KH550 was then added, and 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 repeatedly washed with a MeOH / water solution. After drying at room temperature for 12 h, it was placed in a vacuum oven at 80°C and dried for 12 h to obtain a translucent elastomer, which was recorded as modifier 28. The weight average molecular weight (Mw) and polydispersity of the modifier were measured, and the results are listed in Table 1.

[0428] Comparative Example 5

[0429] All glassware used in the synthesis reaction was dried in an oven at 110°C for 2 h. 20 g of phthalic anhydride polyester diol (20 mmol, PD-110LV, Stepan, USA, Mn=1000) was added to a four-necked flask equipped with a stirring rod. The flask containing the phthalic anhydride polyester diol was heated to 100°C and vacuum-dried for 2 h. 200 ml of anhydrous DMAc was added to the flask, and the phthalic anhydride polyester diol was dissolved by stirring in a 70°C oil bath with nitrogen. 10.01 g (40 mmol) of MDI was added to the flask, and the mixture was stirred at 80°C with nitrogen for 3 h. The -NCO content in the system was determined to be stable using a potentiometric titrator to obtain a prepolymer.

[0430] 1.56 g (10 mmol) of 2,2,6,6-tetramethylpiperidinamine was weighed and added to the flask containing the prepolymer. The resulting mixture was heated to 60°C with stirring for 3 hours. The -NCO content in the system was determined to be stable using a potentiometric titrator. 5.28 g (20 mmol) of C6F9OH was then added and the reaction was continued at 60°C for 6 hours. 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 in distilled water and washed several times in ethanol. After drying at room temperature for 12 hours, it was dried in a vacuum oven at 80°C for 12 hours to obtain a white solid, designated as Modifier 29. The weight-average molecular weight (Mw), polydispersity, and fluorine content of the modifier were determined and are listed in Table 1.

[0431] Comparative Example 6

[0432] 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 26 g PTMG (40 mmol, Mitsubishi Chemical Corporation PTMG 650, Mn = 650, viscosity at 40 °C 100-200 mPa-s) and the flask with PTMG was heated to 110 °C and vacuumed for 2 h to remove water. The flask was charged with 13.29 g (80 mmol) CHDI and 52 mg (0.02 wt% based on the mass of PTMG) 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, giving a prepolymer.

[0433] The prepolymer containing flask was charged with 100 ml anhydrous acetone to reduce the viscosity and 21.13 g (80 mmol) C6F9OH was added. 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. The crude product was dissolved in MeOH and washed repeatedly with MeOH / water solution. The crude product was dried at room temperature for 12 h and then in a vacuum oven at 80 °C for 12 h to give a translucent liquid, which was designated as modifier 30. The weight average molecular weight (Mw), polydispersity and fluorine content of the modifier were determined and the results are shown in Table 1.

[0434] Comparative Example 1

[0435] A mixture of 100 parts by weight of LDPE (Dow Chemicals DFDA-1648NT) as base resin, 2 parts by weight of polyethylene wax, 0.4 parts by weight of antioxidant 1010, 0.8 parts by weight of antioxidant 168 and 0.5 parts by weight of dibutyltin dilaurate was mixed uniformly and then fed into an extruder for mixing and melting. The temperature of each zone of the extruder was set to 140-180 °C and the screw rotation speed was 500 rpm. The mixture was pelletized by a pelletizer and then dried to obtain a mixed pellet. The mixed pellet was injected into a mold by an injection molding machine. The temperature of each zone of the injection molding machine was set to 140-200 °C. The obtained sample was tested for hardness, water contact angle and mechanical properties. The results are shown in Table 2. The water contact angle of the sample is shown in Figure 1. Figure 10

[0436] Working Example 1.1

[0437] ​100 parts by weight of LDPE (Dow DFDA-1648NT, USA) was used as the base resin, 4 parts by weight of modifier 1, 2 parts by weight of polyethylene wax, 0.4 parts by weight of antioxidant 1010, 0.8 parts by weight of antioxidant 168, and 0.5 parts by weight of di-n-butyltin dilaurate were added and mixed uniformly. The mixture was added to an extruder for mixing. The temperature of each zone of the extruder was set to 140-180°C and the screw speed was 500 rpm. Granulation was carried out using a granulator. After drying, mixed pellets were obtained. The mixed pellets were injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 140-200°C to obtain test samples. The hardness, water contact angle, mechanical properties, and surface fluorine content of the samples were tested. The results are listed in Table 2.

[0438] Application Example 1.2

[0439] The 4 parts by weight of modifier 1 in application example 1.1 was replaced by 8 parts by weight of modifier 2, 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. The results are listed in Table 2. The water contact angle test diagram of the sample is shown in FIG. Figure 10 shown.

[0440] Application Example 1.3

[0441] The 4 parts by weight of modifier 1 in application example 1.1 was replaced by 8 parts by weight of modifier 3, while 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 listed in Table 2.

[0442] Application Comparative Example 2

[0443] 100 parts by weight of TPU (Wanhua Chemical M885) 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 dioctyltin dilaurate were added and mixed evenly. 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 speed was 500 rpm, and granulation was performed using a granulator. After drying, a mixed pellet was obtained. The mixed pellet was injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 170-220°C. A test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested. The results are listed in Table 2. The SEM image of the sample surface morphology is shown in Table 2. Figure 6 As shown in (A), the hydrophobicity of the sample is demonstrated as Figure 7 (A) shows the tensile stress-strain curve of the sample. Figure 8 As shown, the tear strength of the sample is Figure 9 As shown in the water contact angle test diagram of the sample Figure 12 shown.

[0444] Application Example 2.1

[0445] 100 parts by weight of TPU (Wanhua Chemical M885) was used as the base resin, 4 parts by weight of modifier 4, 0.2 parts by weight of antioxidant 168, 0.1 parts by weight of antioxidant 1010, and 0.3 parts by weight of dioctyltin dilaurate were added and mixed evenly. 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 speed was 500 rpm, and granulation was performed using a granulator. After drying, a mixed pellet was obtained. The mixed pellet was injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 170-220°C to obtain a test sample. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested. The results are listed in Table 2. The tensile stress-strain curve of the sample is shown in Table 2. Figure 8 As shown, the tear strength of the sample is Figure 9 shown.

[0446] Application Example 2.2

[0447] The 4 parts by weight of modifier 4 in application example 2.1 was replaced by 5 parts by weight of modifier 5, 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. The results are listed in Table 2. The EDS fluorine element mapping surface spectrum of the sample surface is shown in Figure 2. Figure 5 The SEM images of the sample surface morphology are shown in Figure 6 As shown in (B), the hydrophobicity of the sample is demonstrated as Figure 7 (B) shows the tensile stress-strain curve of the sample. Figure 8 As shown, the tear strength of the sample is Figure 9 As shown in the water contact angle test diagram of the sample Figure 12 shown.

[0448] Application Example 2.3

[0449] The 4 parts by weight of modifier 4 in application example 2.1 was replaced by 5 parts by weight of modifier 6, 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. The results are listed in Table 2. The tensile stress-strain curve of the sample is shown in FIG. Figure 8 As shown, the tear strength of the sample is Figure 9 shown.

[0450] Application Comparative Example 3

[0451] 100 parts by weight of TPE (German TPE K TF9AAC) was used 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, and 0.5 parts by weight of zinc stearate were added and mixed evenly. The mixture was added to an extruder for mixing. The temperature of each zone of the extruder was set to 160-210°C and the screw speed was 500 rpm. Granulation was performed using a granulator. After drying, a mixed pellet was obtained. The mixed pellet was injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 170-220°C. A test sample was obtained. The hardness, water contact angle, and mechanical properties of the sample were tested. The results are listed in Table 2. The water contact angle test diagram of the sample is shown in FIG. Figure 10 shown.

[0452] Application Example 3.1

[0453] 100 parts by weight of TPE (German TPE K TF9AAC) was used as the base resin, 8 parts by weight of modifier 8, 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, and 0.5 parts by weight of zinc stearate were added and mixed evenly. The mixture was added to an extruder for mixing. The temperature of each zone of the extruder was set to 160-210°C and the screw speed was 500 rpm. Granulation was performed using a granulator. After drying, mixed pellets were obtained. The mixed pellets were injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 170-220°C to obtain test samples. The hardness, water contact angle, mechanical properties, and surface fluorine content of the samples were tested. The results are listed in Table 2.

[0454] Application Example 3.2

[0455] The 8 parts by weight of modifier 8 in application example 3.1 was replaced by 6 parts by weight of modifier 9, 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. The results are listed in Table 2. The water contact angle test graph of the sample is shown in FIG. Figure 10 shown.

[0456] Application Example 3.3

[0457] The 8 parts by weight of modifier 8 in application example 3.1 were replaced by 10 parts by weight of modifier 11, while 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 listed in Table 2.

[0458] Comparative Application Example 4

[0459] 100 parts by weight of silicone rubber (GA-1081, Shenzhen Jiahaixin Silicone Rubber Co., Ltd.) was used 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. The temperature of the vulcanizer was set to 150°C, and the sample was placed in a mold for preheating. The mixed sample was then placed in the mold and vulcanized at 15 MPa for 15 minutes. The hot mold was removed from the mold to obtain a test sample. The hardness, water contact angle, and mechanical properties of the sample were tested. The results are listed in Table 2. The water contact angle test diagram of the sample is shown in Figure 2. Figure 10 shown.

[0460] Application Example 4.1

[0461] 100 parts by weight of silicone rubber (GA-1081, Shenzhen Jiahaixin Silicone Rubber Co., Ltd.) was used as the base resin, 6 parts by weight of modifier 12, 1 part by weight of vulcanizer 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 kneaded at room temperature using an open mill. The temperature of the vulcanizer was set to 150°C, and the sample was placed in a mold for preheating. The mixed sample was then placed in the mold and vulcanized at 15 MPa for 15 min. The sample was removed from the hot mold to obtain a test sample. The hardness, water contact angle, mechanical properties, and surface fluorine content of the sample were tested. The results are listed in Table 2.

[0462] Application Example 4.2

[0463] The 6 parts by weight of modifier 12 in application example 4.1 was replaced by 6 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. The results are listed in Table 2. The water contact angle test graph of the sample is shown in FIG. Figure 10 shown.

[0464] Application Example 4.3

[0465] The 6 parts by weight of modifier 12 in application example 4.1 was replaced by 8 parts by weight of modifier 15, while 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 listed in Table 2.

[0466] Application Comparative Example 5

[0467] 100 parts by weight of polycarbonate (Taiwan Province Formosa Chemical Corporation Idemitsu PC IR2200 CB) was used as the matrix 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 dioctyltin dilaurate were added and mixed evenly. 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 granulation was performed using a granulator. After drying, mixed pellets were obtained. The mixed pellets were injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 240-280°C to obtain test samples. The hardness, water contact angle, mechanical properties, and surface fluorine content of the samples were tested. The results are listed in Table 2. The water contact angle test diagram of the sample is shown in Figure 2. Figure 11 shown.

[0468] Application Example 5.1

[0469] 100 parts by weight of polycarbonate (Taiwan Province Formosa Chemical Corporation Idemitsu PC IR2200 CB) was used as the base resin, 2 parts by weight of modifier 16, 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 dioctyltin dilaurate were added and mixed evenly. The mixture was added to an extruder for mixing. The temperature of each zone of the extruder was set to 220-260°C and the screw speed was 500 rpm. Granulation was performed using a granulator. After drying, mixed pellets were obtained. The mixed pellets were injection molded by an injection molding machine. The temperature range of each zone of the injection molding machine was 240-280°C to obtain test samples. The hardness, water contact angle, mechanical properties, and surface fluorine content of the samples were tested. The results are listed in Table 2. The water contact angle test diagram of the sample is shown in Figure 2. Figure 11 shown.

[0470] Application Example 5.2

[0471] The 2 parts by weight of modifier 16 in application example 5.1 were replaced by 5 parts by weight of modifier 18, while 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 listed in Table 2.

[0472] Application Example 5.3

[0473] The 2 parts by weight of modifier 16 in application example 5.1 were replaced by 5 parts by weight of modifier 19, while 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 listed in Table 2.

[0474] Application Comparative Example 6

[0475] 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, and 30 parts by weight of deionized water were ultrasonically dispersed uniformly, 0.3 mm zirconium oxide beads were added, and the mixture was ball-milled 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, and 3 parts by weight of initiator benzoyl peroxide were mixed uniformly at 1200 r / min to obtain an acrylate coating, which was applied to a stainless steel surface, baked in an oven at 80° C. for 15 min, and irradiated under ultraviolet light for 5 min to obtain a 50 μm thick acrylate coating. The water contact angle and surface fluorine content of the coating were tested. The results are listed in Table 2. The sample water contact angle test diagram is shown in FIG. Figure 11 shown.

[0476] Application Example 6.1

[0477] 30 parts by weight of modifier 20, 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, and 30 parts by weight of deionized water were ultrasonically dispersed uniformly, 0.3 mm zirconium oxide beads were added, and the mixture was ball-milled 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, and 3 parts by weight of initiator benzoyl peroxide were mixed uniformly at 1200 r / min to obtain an acrylate coating, which was applied to a stainless steel surface, baked in an oven at 80°C for 15 min, and irradiated under ultraviolet light for 5 min to obtain a 50 μm thick acrylate coating. The water contact angle and surface fluorine content of the coating were tested, and the results are listed in Table 2.

[0478] Application Example 6.2

[0479] The 30 parts by weight of modifier 20 in application example 6.1 was replaced by 30 parts by weight of modifier 21, and the rest remained unchanged to obtain a 50 μm thick acrylate coating. The water contact angle and surface fluorine content of the coating were tested. The results are listed in Table 2. The water contact angle test graph of the sample is shown in FIG. Figure 11 shown.

[0480] Application Comparative Example 7

[0481] 20 parts by weight of polysulfone (US Solvay P1700) was used as the matrix resin, 100 parts by weight of DMAc solvent was added, and the mixture was heated to 70°C and stirred to dissolve for 8 hours. After stirring, the mixture was continued to be heated and allowed to stand for degassing. After degassing, the mixture was allowed to stand for one night. The mixture was then coated on a glass plate using a four-sided preparation device to form a film. After drying at room temperature for 12 hours, the film was placed in a vacuum oven at 50°C and dried for 12 hours to obtain a 400 μm thick test sample. The water contact angle, mechanical properties, and surface fluorine content of the sample were tested. The results are listed in Table 2. The sample water contact angle test diagram is shown in FIG. Figure 11shown.

[0482] Application Example 7.1

[0483] 20 parts by weight of polysulfone (US Solvay P1700) was used as the base resin, 1.2 parts by weight of modifier 23 and 100 parts by weight of DMAc solvent were added, and the mixture was heated to 70°C and stirred to dissolve for 8 hours. After stirring, the mixture was continued to be heated and allowed to stand for degassing. After degassing, the mixture was allowed to stand for one night. The mixture was then coated on a glass plate using a four-sided preparation device to form a film. After drying at room temperature for 12 hours, the film was placed in a vacuum oven at 50°C and dried for 12 hours to obtain a 400 μm thick test sample. The contact angle, mechanical properties, and surface fluorine content of the sample were tested. The results are listed in Table 2. The water contact angle test diagram of the sample is shown in Figure 2. Figure 11 shown.

[0484] Comparative Application Example 8

[0485] The 5 parts by weight of modifier 5 in application example 2.2 was replaced by 5 parts by weight of modifier 25, 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. The results are listed in Table 3. The water contact angle test diagram of the sample is shown in FIG. Figure 12 shown.

[0486] Comparative Application Example 9

[0487] The 5 parts by weight of modifier 5 in application example 2.2 was replaced by 5 parts by weight of modifier 26, 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. The results are listed in Table 3. The water contact angle test graph of the sample is shown in FIG. Figure 12 shown.

[0488] Comparative Application Example 10

[0489] The 5 parts by weight of modifier 5 in application example 2.2 was replaced by 5 parts by weight of modifier 27, 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. The results are listed in Table 3. The water contact angle test graph of the sample is shown in FIG. Figure 12 shown.

[0490] Comparative Application Example 11

[0491] The 5 parts by weight of modifier 5 in application example 2.2 was replaced by 5 parts by weight of modifier 28, 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. The results are listed in Table 3. The water contact angle test graph of the sample is shown in FIG. Figure 12 shown.

[0492] Comparative Application Example 12

[0493] Replace 5 parts by weight of modifier 5 in application example 2.2 with 5 parts by weight of modifier 29, and the rest remains unchanged to obtain a test sample, test the contact angle, surface energy, mechanical properties, 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 shown in Figure 12 .

[0494] Application comparative example 13

[0495] Replace 5 parts by weight of modifier 5 in application example 2.2 with 5 parts by weight of modifier 30, and the rest remains unchanged to obtain a test sample, test the contact angle, surface energy, mechanical properties, 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 shown in Figure 12 .

[0496] Table 1. Performance test table of the modifier prepared in the embodiment of the present application

[0497]

[0498]

[0499] Table 2. Performance test table of application comparative examples and application examples of the present application

[0500]

[0501]

[0502] From the comparison data of each application comparative example and application example in Table 2, it can be seen that for different base resins (polyolefin, polyurethane, thermoplastic elastomer, silicone rubber, polycarbonate, acrylic resin, and polysulfone), the low surface energy polymer modifier in the present application can achieve a significant hydrophobic and antifouling effect. After adding the modifier to the base resin, the water contact angle is increased by more than 50-65°, and the improvement effect is obvious. After adding the modifier in the present application, the percentage of fluorine atoms on the surface of the sample is much higher than the theoretical value, indicating that the distribution content of the modifier on the surface of the resin is much higher than that in the resin, and it has a tendency to accumulate on the surface of the resin. It also shows that the modifier itself achieves a hydrophobic effect by migrating to the surface of the resin. In addition, from the test data, it can be seen that the addition of the low surface energy polymer modifier in the present application has no effect on the hardness of the base resin, and the tensile strength, elongation at break (toughness), and tear strength of the base resin are also improved, which has very outstanding application value. The modifier in the present application itself has a certain molecular weight, and more is migrated to the surface of the base resin to work, and different base resins are used with good compatibility with the modifier polymer segment. The modifier itself not only can be well dispersed and migrated in the base resin, but also can have good bonding degree with the base after migration.

[0503] Table 3. Performance comparison table of the application examples and application examples of the present invention

[0504]

[0505] From the comparative data of each application comparative example and application example in Table 3, it can be seen that when the molecular weight of the modifier is similar (weight average molecular weight M w ≈5000g / mol), without introducing a temperature-sensitive dynamic structure into the modifier molecular chain (Application Comparative Example 8, Application Comparative Example 9), a modifier containing only a fluorinated structure is directly prepared, and the water contact angle of the TPU sample modified by it is increased by about 30°, and the surface energy is reduced by about 70%. The TPU sample modified by the low surface energy polymer modifier of the present invention (Application Example 2.2) has a significant increase in the percentage of fluorine atoms on its surface, and its water contact angle is increased by as much as 56°, achieving a super-hydrophobic effect comparable to that of lotus leaves in nature (water contact angle>150°), and a surface energy reduction of up to 97%, which has a very efficient and significant surface energy reduction effect. Figure 7It can also be seen from the hydrophobicity demonstration diagram of the samples that for the unmodified sample (A, application comparative example 2), when dyed ink is dripped onto the sample surface, the water droplets stay on the sample and cannot roll off; for the modified sample (B, application example 2.2), all the ink dripped onto the sample surface rolls off the paper surface and cannot stay on the sample. When ordinary dynamic structures (disulfide bonds) are introduced into the molecular chains of the modifier (application comparative example 10), the water contact angle enhancement effect and low surface energy reduction effect of the obtained sample cannot reach the effect of the modifier in the present invention, and the fluorine atomic percentage on the sample surface is also significantly lower than that in application example 2.2, indicating that only ordinary dynamic structures are used. Due to their high dynamic equilibrium reaction temperature, their migration ability is limited during short-time processing, low-temperature heat treatment (high-temperature heat treatment of ordinary dynamic structures will affect the base resin), and room temperature storage, and the low surface energy improvement effect is limited; while the modifier in the present invention, due to the introduction of temperature-sensitive dynamic structures, has limited low surface energy improvement effect during processing, heat treatment and use. During the use process, the thermosensitive dynamic structure in the polymer chain can dissociate under relatively low temperature conditions, thereby reducing the molecular weight of the modifier, thereby having good migration ability, being able to be well dispersed in the matrix, and efficiently completing the aggregation from the inside of the matrix to the surface, and the thermosensitive dynamic structure in the system can recombine into a dynamic covalent bond during the migration completion and cooling process, so that the modifier returns to its original molecular weight, enhances its binding force with the matrix, achieves stability on the surface of the matrix, and effectively reduces the risk of modifier elution and loss; and the migration ability of the modifier directly affects the fluorine enrichment of the matrix surface, thereby affecting the hydrophobic anti-fouling ability of the matrix. After the fluorinated structure of the modifier in the present invention is replaced by a siloxane structure (application comparative example 11), its water contact angle and surface energy improvement effect are significantly reduced, indicating that the fluorinated structure used in the modifier of the present invention has an excellent hydrophobic effect. In addition, the present invention uses a flexible aliphatic polymer diol / diamine and an aliphatic diisocyanate with strong chain motion ability as raw materials, so that the modifier polymer chain structure has high migration ability, achieves high surface fluorine enrichment in the matrix resin, and realizes super-hydrophobicity. In contrast, the modifier prepared by using aromatic polymer diol and aromatic diisocyanate (Application Comparative Example 12) 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 2.2. As can be seen from the application comparative example 13 data, the modifier molecular weight is too low, and although its migration ability is strong, its binding force with the matrix resin deteriorates, which will have a significant impact on the mechanical properties of the matrix resin itself.

[0506] Table 4. Water contact angle data of the durability test of the comparative examples and application examples of the present invention

[0507]

[0508] It can be seen from the durability experimental data of the application comparison examples and application examples in Table 4 that the water contact angles of the samples dropped significantly when tested directly after the first polishing, indicating that the fluorine-containing layer on the surface of the samples was damaged. Polishing with 1200 mesh sandpaper can destroy the surface layer of the samples. After the polished samples were placed at room temperature for 7 days, the hydrophobic effects on the sample surfaces were restored to varying degrees, indicating that the modifiers migrated back to the sample surface. However, due to the different migration abilities of the various modifiers, the samples maintained different hydrophobic effects during multiple polishing processes. Among them, the sample in application example 2.2 of the present invention still maintained a good hydrophobic effect after 6 polishings without failure, while the other application comparison examples all failed to varying degrees. The results show that the low surface energy modifier in the present invention can achieve long-term maintenance of the low surface energy effect through its dynamic migration ability, and has good durability.

[0509] The modifiers in the above embodiments and the modified products in the application embodiments can play the role of waterproof, anti-fouling, dustproof, anti-coagulation, anti-thrombosis, antibacterial, self-cleaning and other effects. According to actual needs, they can be used in the field of coatings (for example, as waterproof and anti-fouling polyurethane / acrylate / silicone coatings, waterproof and anti-fouling polyurethane / acrylate / silicone coatings), textiles (for example, as textile surface coatings, or as surface modifiers for chemical fibers such as polyester, nylon, acrylic, vinylon, polypropylene, chlorofiber, spandex, etc.), electronic products (for example, as watches, smart phones, telephones, televisions, DVD players, video recorders, camcorders, radios, tape recorders, combination speakers, laser players, computers, Surface dust and dirt prevention and self-cleaning treatment of the surface, internal parts, mainboard chips and other components of equipment such as game consoles and mobile communication products), automotive parts products field (for example, as body parts, car cover films, bumpers, doors, fenders, windshields, pillars, seats, center consoles, engine covers, trunk lids, sunroofs, roofs, door locks, armrests, floors, door sills and other surface dust and dirt prevention treatment), filter membrane field (for example, sewage filter membranes, water purification membranes, seawater desalination membranes, hemodialysis membranes, membranes for medical and pharmaceutical fields, membranes for food and beverage manufacturing, membranes for municipal water treatment, industrial Membranes for the electronics industry, membranes for material concentration and purification, etc., which play the role of antifouling, antibacterial, self-cleaning, etc.), medical products field (for example, used in medical instruments, medical equipment, surgical instruments, drug delivery devices, drug release devices, transplants, stents, pacemakers, implantable cardioverter-defibrillators, heart 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, 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, scaffolds, suture materials, needles, hernia repair meshes, tension-free vaginal slings and vaginal slings, prosthetic nerve devices and ear tubes, medical dressings, medical bandages, medical gauze, medical tapes, medical pads, medical sponges, blood oxygenators, ventilators, contraceptive devices, female 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., which have waterproof, anti-fouling, dust-proof, anti-coagulation, anti-thrombotic, antibacterial, self-cleaning and other effects).

[0510] It should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the patent scope of the present invention. For example, other compound raw materials for synthesizing the dynamically migratable low surface energy polymer modifier, the modifier structure, the applicable base resin, the applicable preparation method, and the application field, those skilled in the art can modify, replace, and expand the technical solutions described in the aforementioned embodiments in accordance with the protection scope and spirit of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention, or directly or indirectly applied in other related technical fields, should be included in the protection scope of the present invention.

Claims

1. A low surface energy polymer modifier capable of dynamic migration, characterized in that: The polymer main chain includes a temperature-sensitive dynamic structure, and the polymer chain end group is a fluorinated structure; it is prepared using at least the following raw materials in parts by weight: The temperature-sensitive dynamic structure can undergo dynamic dissociation and generation-conversion based on dynamic covalent bonds at a temperature of at least 50-80°C, and contains at least one of the following structures: Class I, organic borate ester structure: The boron atom B is connected to a carbon atom via a boron-carbon bond, and at least one organic group is connected to the boron atom via the boron-carbon bond; K is selected from a substituted form of 1,2-ethylene, a substituted form of 1,3-propylene, a substituted form of an o-disubstituted phenyl, and a substituted form of an o-disubstituted benzyl; X1 and X2 are each independently selected from a carbon atom and a silicon atom; Class II, imine structure: Wherein, R is a substituent; G is selected from an organic linking group, an oxygen atom linking group, a nitrogen atom linking group, and an amide group; Class III, large hindered urea bond structure: Among them, R b It is a steric group directly connected to the nitrogen atom; is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring, and n represents the number of links connected to the ring atoms of the cyclic structure; 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 dynamically migratable low surface energy polymer modifier according to claim 1, characterized in that The structure of the low surface energy polymer modifier is shown below: Among them, P, I, D, F t , m, and n 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 300-3000 Da; I are each independently a unit formed by polymerization of at least one aliphatic diisocyanate; D is independently a unit formed by polymerization of at least one temperature-sensitive dynamic compound raw material; F t Each independently is a unit formed by polymerization of at least one monohydroxy fluoroalcohol compound; m and n are the number of repeating units, each independently an integer from 1 to 5; The low surface energy polymer modifier has a weight average molecular weight Mw of 2000-20000 and a fluorine content of 1-10%.

3. The dynamically migratable low surface energy polymer modifier 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 dynamically migratable low surface energy polymer modifier 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 dynamically migratable low surface energy polymer modifier according to claim 1, characterized in that: 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 dynamically migratable low surface energy polymer modifier according to claim 1, characterized in that The temperature-sensitive dynamic compound raw material contains two reactive groups, which are selected from at least one of the following structures: E1-DCB-E2, E3-L1-E4, Among them, DCB is a temperature-sensitive dynamic structure, E3-L1-E4 is a temperature-sensitive dynamic structure precursor, L1 is an organic linker; E1, E2, E3, E4 are reactive groups, E1, E2 are each independently selected from -OH, -NH2, -SH, E3 are each independently selected from -NH-R b 、 E4 are each independently selected from -OH, -NH2, -SH, -NH-R b 、 Among them, R b is a steric hindering group directly connected to the nitrogen atom, is a nitrogen-containing aliphatic ring or a nitrogen-containing aromatic ring; n represents the number of links connected to the ring atoms of the cyclic structure.

7. The dynamically migratable low surface energy polymer modifier according to claim 6, characterized in that: The temperature-sensitive dynamic compound raw material is selected from organic borate diol, organic borate silicon ester diol, 1,3-bis(hydroxyimino)propan-2-one, azine salicylaldehyde, 4-(hydroxyiminomethyl)benzylamine oxime, 3-(hydroxyiminomethyl)benzylamine oxime, glyoxime, methylglyoxime, dimethylglyoxime, dimethylglyoxime, 3-hydroxy-3-methyl-2-butanone oxime, 5-hydroxyvaleraldehyde oxime, 4-hydroxybenzaldehyde oxime, 4'-hydroxyacetophenone oxime, 3-aminobenzylamine oxime, 3'-aminoacetophenone oxime, 4-aminoacetophenone oxime, 2-amino-1-p-tolueneacetophenone oxime, salicylaldehyde oxime, salicylaldehyde hydrazone, salicylaldehyde carbonyl hydrazone, levulinic acid semicarbazide Hydrazone, N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, N-tert-butylethanolamine, N,N'-di-tert-butylethylenediamine, tert-butylhydrazine, (2-amino-2-methylpropyl)(tert-butyl)amine, 2,2,6,6-tetramethylpiperidinamine, 2,2,6,6-tetramethyl-4-piperidinol, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, N-(sec-butyl)-2,2,6,6-tetramethylpiperidin-4-amine, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, 4-(hydroxymethyl)imidazole, 4-hydroxyethylimidazole, 2-(3-hydroxypropyl)benzimidazole, 4-hydroxybenzimidazole.

8. The dynamically migratable low surface energy polymer modifier according to claim 1, characterized in that: The monohydroxy fluoroalcohol compound has the following structure: Wherein, L2 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 dynamically migratable low surface energy polymer modifier 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 low surface energy polymer modifier capable of dynamic migration 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 content in the system reaches a stable level to obtain a prepolymer; S3. Add the temperature-sensitive dynamic compound raw material to the S2 prepolymer, control the reaction temperature at 40-80°C, continue heating and stirring with nitrogen for 2-8 hours, and then add the monohydroxy fluoroalcohol compound and continue 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, temperature-sensitive dynamic compound raw material, and monohydroxy fluoroalcohol compound is 1:1.2-2.1:0.2-0.8:0.1-1.

1.

11. A solvent-free preparation method of the low surface energy polymer modifier capable of dynamic migration according to claim 1, characterized in that: It uses low-viscosity aliphatic polymer diol as the reaction raw material, and does not use solvents during the entire reaction process. The preparation steps are as follows: S1: Heat the low-viscosity aliphatic polymer diol to 80-120°C and remove water in a vacuum for 2-4 hours; S2. A fixed molar amount of a low-viscosity aliphatic polymer diol and an aliphatic diisocyanate are heated to 60-110° C. under nitrogen and stirred for reaction for 2-6 hours until the -NCO groups in the system are stabilized to obtain a prepolymer; S3, adding the temperature-sensitive dynamic compound raw material to the S2 prepolymer, mechanically stirring and reacting at 40-90° C. for 5-120 minutes, then adding the monohydroxy fluoroalcohol compound and continuing to stir and react for 5-30 minutes, pouring the mixture into a mold and continuing to react in a forced air oven at 80-100° C. for 12-48 hours to obtain a low surface energy polymer modifier; The low-viscosity aliphatic polymeric diol has a number average molecular weight selected from 300-2000 Da, and its viscosity satisfies at least one of the following conditions: viscosity ≤ 1000 mPa·s at 25°C, viscosity ≤ 500 mPa·s at 40°C, and viscosity ≤ 200 mPa·s at 75°C; The molar ratio of the low-viscosity aliphatic polymer diol, aliphatic diisocyanate, temperature-sensitive dynamic compound raw material, and monohydroxy fluoroalcohol compound is 1:1.9-2.1:0.4-0.6:0.9-1.

1.

12. A low surface energy blend composition, characterized in that: The invention comprises 80-100 parts by weight of a base resin, 2-10 parts by weight of a dynamically migratable low surface energy polymer modifier according to 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.

13. An application of the low surface energy blend composition according to claim 12 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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