A hydrophilically modified polyketone material and a method for its preparation

Abstract

The application relates to the technical field of high polymer composite materials, and particularly discloses a hydrophilic modified polyketone material and a preparation method thereof.A hydrophilic modified polyketone material is prepared from the following components by weight: 80-93 parts of polyketone resin, 2-5 parts of a compatilizer, 5-15 parts of a hydrophilic agent, 0.1-0.5 parts of an initiator, 0.2-0.5 parts of an antioxidant and 0.3-0.6 parts of a lubricant; the hydrophilic agent is methoxy polyethylene glycol methacrylate.The hydrophilic modified polyketone material prepared by the application has the advantages of excellent hydrophilicity, good hydrophilic durability and high mechanical property retention rate.

Description

Technical Field

[0001] This application relates to the field of polymer composite materials technology, and more specifically, to a hydrophilic modified polyketone material and its preparation method. Background Technology

[0002] Polyketone resin (POK) is a highly crystalline polymer, a novel green polymer material synthesized from carbon monoxide and olefins (ethylene, propylene). POK possesses excellent abrasion resistance, superior chemical resistance and hydrolysis resistance, as well as good gas barrier properties. However, the highly crystalline and non-polar nature of the POK molecular chain results in low surface energy and strong hydrophobicity. This characteristic severely limits its application in areas requiring good wettability, stain resistance, or biocompatibility, such as blood contact devices, filter membranes, and antistatic components.

[0003] The existing POK hydrophilic modification technology has the following limitations: (1) Physical blending of small molecule surfactants, such as glycerol monooleate (GMO) or ethoxylated amines, can reduce the contact angle in the short term, but the small molecule additives are very easy to migrate and precipitate during long-term use or washing, resulting in rapid loss of hydrophilicity and possible contamination of the contact medium. (2) Plasma or ultraviolet irradiation surface treatment can only change the properties of the surface layer of the material by a few nanometers. The effect is not lasting and requires expensive post-processing equipment, making it difficult to use for the overall modification of complex shaped products.

[0004] Patent application CN116510538A discloses a method for preparing an aliphatic polyketone filter membrane with fibrous pores, comprising the following steps: S1: 20 parts of POK, 3 parts of hydrophilic modifier F-127, and 77 parts of phthalic anhydride are added to a container and mixed, heated to 160°C, and after being fully dispersed and homogenized, vacuum degassing is performed; S2: The casting solution is used to prepare a flat sheet membrane on an automatic film coating machine; S3: The nascent flat sheet membrane is immediately placed in a pure water cooling bath, the water temperature of which is controlled at 45°C, and the curing time is 0.5 h; S4: The cured membrane is immersed in pure water at 60°C for 24 h, then immersed in a 20% glycerol aqueous solution for 24 h, and naturally air-dried to obtain an aliphatic polyketone flat sheet filter membrane with fibrous pores.

[0005] In this technical solution, POK is physically blended with the hydrophilic modifier F-127, and then a film is formed using a thermally induced phase separation method. The two molecules are "anchored" solely through intermolecular forces and physical entanglement. During film formation, F-127 can spontaneously migrate to the membrane-water interface due to its amphiphilic nature, giving the membrane a certain degree of hydrophilicity in its initial state. However, POK itself is a highly crystalline, low-surface-energy hydrophobic polymer with limited ability to bind hydrophilic PEO segments. Especially under fluid shearing, backwashing, or chemical cleaning, the poorly anchored F-127 molecules easily break free of their bonds and dissolve, leading to hydrophobicity of the membrane surface and a continuous increase in the water contact angle over time. Summary of the Invention

[0006] In order to improve the hydrophilicity of polyketone materials and overcome the technical defects of existing modification methods, such as easy migration and precipitation of hydrophilic components and insufficient hydrophilic durability, this application provides a hydrophilic modified polyketone material and its preparation method.

[0007] This application provides a hydrophilic modified polyketone material, comprising the following components in parts by weight: 80-93 parts polyketone resin, 2-5 parts compatibilizer, 5-15 parts hydrophilic agent, 0.1-0.5 parts initiator, 0.2-0.5 parts antioxidant, and 0.3-0.6 parts lubricant; The hydrophilic agent is methoxy polyethylene glycol methacrylate.

[0008] In this technical solution, during reactive extrusion, free radicals are generated in the compatibilizer backbone, which in turn initiates the graft polymerization of methoxy polyethylene glycol methacrylate monomers onto the compatibilizer backbone. This indirectly introduces hydrophilic polyethylene glycol segments into the polyketide matrix through chemical grafting, which helps reduce the tendency of hydrophilic components to migrate and precipitate during washing or long-term use, and improves the wettability and durability of the polyketide material surface. The methoxy group, as the end-capping group, ensures that the hydrophilic monomer contains only one reactive double bond, reducing the risk of crosslinking that may be caused by multifunctional monomers and helping to maintain the melt processability of the product. Furthermore, the compatibilizer can also improve the interfacial compatibility between the hydrophilic segments and the polyketide matrix.

[0009] Preferably, the antioxidant includes antioxidant 1098 and antioxidant 168.

[0010] Preferably, the lubricant is ethylene bis-stearamide.

[0011] Preferably, the compatibilizer is at least one of maleic anhydride-grafted polyolefin and maleic anhydride-grafted EMA.

[0012] More preferably, the compatibilizer is maleic anhydride-grafted polyethylene or maleic anhydride-grafted polypropylene, with a grafting rate of 0.8% to 2.5%.

[0013] In this technical solution, the nonpolar backbone of the compatibilizer exhibits excellent physical compatibility with the nonpolar polyketone matrix. It can be firmly embedded within the three-dimensional network of the polyketone matrix through deep entanglement between molecular chains, forming stable "anchor points." The maleic anhydride groups of the side chains form a tight physical association with the polyethylene glycol ether oxygen segments in the methoxy polyethylene glycol methacrylate monomer through hydrogen bonding and dipole-dipole interactions. Some compatibilizers also undergo graft copolymerization with the methoxy polyethylene glycol methacrylate monomer, indirectly connecting the hydrophilic segments to the polyketone matrix through covalent bonds.

[0014] Preferably, the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene.

[0015] Preferably, the hydrophilic agent includes high molecular weight methoxy polyethylene glycol methacrylate and low molecular weight methoxy polyethylene glycol methacrylate.

[0016] Preferably, the proportion of high molecular weight methoxy polyethylene glycol methacrylate in the hydrophilic agent is not less than 80%.

[0017] In this technical solution, the low molecular weight component diffuses rapidly and has high polymerization reactivity, enabling the rapid formation of a high-density hydrophilic network node. The high molecular weight component, after polymerization, provides longer polyethylene glycol extended segments that can effectively extend to the material surface. By gradient blending of methoxy polyethylene glycol methacrylates of different molecular weights, a multi-layered hydrophilic structure can be constructed, significantly improving the surface utilization rate of the hydrophilic segments, thereby enhancing the overall hydrophilicity and durability of the material.

[0018] Preferably, the number average molecular weight of the low molecular weight methoxy polyethylene glycol methacrylate is 600-1000.

[0019] Preferably, the number average molecular weight of the high molecular weight methoxy polyethylene glycol methacrylate is not less than 2000.

[0020] Preferably, the hydrophilic modified polyketone material further includes 0.5 to 2 parts by weight of sulfobetaine methacrylate.

[0021] In this technical solution, sulfobetaine methacrylate can undergo free radical copolymerization with methoxy polyethylene glycol methacrylate, introducing zwitterionic groups into the hydrophilic macromolecular chain. These zwitterionic groups can bind more water molecules through electrostatic interactions, forming a more stable bound water layer and significantly reducing the initial contact angle of the material.

[0022] Preferably, the hydrophilic modified polyketone material further includes octadecyl polyoxyethylene ether methacrylate, and the amount of octadecyl polyoxyethylene ether methacrylate is 5% to 8% of the mass of the hydrophilic agent.

[0023] In this technical solution, octadecyl polyoxyethylene ether methacrylate, as a reactive surfactant, can reduce the interfacial tension between the hydrophilic monomer and the polyketide melt, refine the hydrophilic phase region, and improve interfacial compatibility. At the same time, its octadecyl long chain can form physical entanglement with the polyketide molecular chain, playing a dual anchoring role on the hydrophilic chain segment, further improving the hydrophilic durability of the material.

[0024] Preferably, the hydrophilic modified polyketone material further includes 1-2 parts by weight of silanized nano-SiO2.

[0025] Preferably, the silane coupling agent used in the silanized nano-SiO2 includes silane coupling agent KH-570 and 2-[methoxy(polyoxyethylene)propyl]trimethoxysilane.

[0026] Preferably, the method for preparing the silanized nano-SiO2 includes the following steps: Nano-SiO2 was dispersed in an aqueous ethanol solution, the pH was adjusted to 4.5-5.0, silane coupling agent KH-570 and 2-[methoxy(polyoxyethylene)propyl]trimethoxysilane were added and mixed evenly, the temperature was raised to 55-70℃, and the reaction was carried out for 4-6 hours. After solid-liquid separation, washing and drying were performed to obtain silanized nano-SiO2.

[0027] Preferably, the particle size distribution of the nano-SiO2 is 20~50nm.

[0028] In this technical solution, KH-570 introduces methacryloyl groups onto the surface of nano-SiO2, and 2-[methoxy(polyoxyethylene)propyl]trimethoxysilane introduces polyethylene glycol segments onto the surface of nano-SiO2. Silanized nano-SiO2 serves as a heterogeneous nucleation site for polyketide crystallization, refining the polyketide crystalline structure and improving the material's mechanical properties. Furthermore, its surface methacryloyl groups can participate in free radical grafting reactions, enhancing the bonding stability between nano-SiO2 and the polyketide matrix and hydrophilic segments. Its surface polyethylene glycol segments can act as hydrophilic enrichment nodes, promoting the exposure of hydrophilic segments on or near the material surface.

[0029] This application also provides a method for preparing a hydrophilic modified polyketone material, comprising the following steps: After the polyketone resin, compatibilizer, antioxidant, and lubricant are mixed evenly according to the formula, they are fed from the main feeder. After the hydrophilic agent and initiator are mixed, they are fed from the side feeder. The mixture is then extruded through a twin-screw extruder, cooled, granulated, dried, and injection molded to obtain the hydrophilic modified polyketone material.

[0030] Preferably, the temperature of each zone of the twin-screw extruder is set as follows: 145~155℃ for the first zone; 220~235℃ for the second to eleventh zones; and the main extruder speed is 200~300rpm.

[0031] In this technical solution, the hydrophilic agent and initiator are added via a side-feed method, which avoids premature decomposition of the initiator in the low-temperature zone and reduces the residence time of the hydrophilic agent in the high-temperature zone, thereby reducing its volatilization loss. Controlling the appropriate main unit speed and residence time ensures sufficient graft polymerization of the methoxy polyethylene glycol methacrylate monomer while preventing excessive thermal degradation of the polyketone resin.

[0032] Preferably, when adding the hydrophilic agent, the step further includes adding sulfobetaine methacrylate and / or octadecyl polyoxyethylene ether methacrylate.

[0033] Preferably, after adding the polyketone resin, the step of adding silanized nano-SiO2 is also included.

[0034] In summary, this application has the following beneficial effects: 1. This application uses methoxy polyethylene glycol methacrylate as a reactive hydrophilic agent. Under the action of an initiator and a compatibilizer, the hydrophilic segments of polyethylene glycol are introduced into the polyketide matrix in the form of grafting, which reduces the migration and precipitation of the hydrophilic agent during water washing and long-term use, and achieves a long-lasting hydrophilic modification effect.

[0035] 2. This application constructs a multi-layered hydrophilic structure by combining high- and low-molecular-weight methoxy polyethylene glycol methacrylates. The low-molecular-weight component rapidly forms dense hydrophilic nodes, while the high-molecular-weight component provides long chain extension, synergistically improving the surface coverage and wetting efficiency of the hydrophilic segments. Detailed Implementation

[0036] The present application will be further described in detail below with reference to the embodiments.

[0037] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application are all commercially available.

[0038] The polyketone resin is Hyosung M130F from South Korea; octadecyl polyoxyethylene ether methacrylate is a commercially available industrial product with a solid content of 60%. The amount of octadecyl polyoxyethylene ether methacrylate used in the following examples is based on its solid content.

[0039] Example 1 The hydrophilic modified polyketone material of this embodiment is made from the following components: Polyketone resin 1850g, compatibilizer 40g, hydrophilic agent 100g, initiator 2g, antioxidant 4g, lubricant 6g; The hydrophilic agent is methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000; the compatibilizer is maleic anhydride-grafted polyethylene; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidants are antioxidant 1098 and antioxidant 168 in a mass ratio of 1:1; and the lubricant is ethylene bis-stearamide.

[0040] The preparation method of the hydrophilic modified polyketone material in this embodiment includes the following steps: S1: Add polyketone resin, compatibilizer, antioxidant, and lubricant into a high-speed mixer and mix at 1200 rpm for 3 minutes to obtain the main feed; S2: Mix the hydrophilic agent and initiator evenly to obtain the side feed; S3: The main feed is added to the twin-screw extruder through the main feed port, and the side feed mixture is injected from the fifth zone side feed port of the twin-screw extruder through a metering pump. The extruded strip is cooled by circulating cooling water at 25°C, air-dried, pelletized, and dried at 80°C for 4 hours to obtain hydrophilic modified polyketone material.

[0041] The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1 is 145℃; Zones 2 to 11 are 220℃, and the main extruder speed is 200rpm.

[0042] Example 2 The difference between this embodiment and Embodiment 1 is that: 1790g of polyketone resin, 100g of compatibilizer, 100g of hydrophilic agent, 4g of initiator, 6g of antioxidant, and 8g of lubricant; Everything else is the same as in Example 1.

[0043] Example 3 The hydrophilic modified polyketone material of this embodiment is made from the following components: Polyketone resin 1690g, compatibilizer 100g, hydrophilic agent 200g, initiator 8g, antioxidant 10g, lubricant 12g; The hydrophilic agent is methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000; the compatibilizer is maleic anhydride-grafted polypropylene 80g and maleic anhydride-grafted EMA 20g; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidant is antioxidant 1098 and antioxidant 168 in a mass ratio of 1:1; and the lubricant is ethylene bis-stearamide.

[0044] The preparation method of the hydrophilic modified polyketone material in this embodiment includes the following steps: S1: Add polyketone resin, compatibilizer, antioxidant, and lubricant into a high-speed mixer and mix at 1200 rpm for 3 minutes to obtain the main feed; S2: Mix the hydrophilic agent and initiator evenly to obtain the side feed; S3: The main feed is added to the twin-screw extruder through the main feed port, and the side feed mixture is injected from the fifth zone side feed port of the twin-screw extruder through a metering pump. The extruded strip is cooled by circulating cooling water at 25°C, air-dried, pelletized, and dried at 80°C for 4 hours to obtain hydrophilic modified polyketone material.

[0045] The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1 is 155℃; Zones 2 to 11 are 235℃, and the main extruder speed is 300 rpm.

[0046] Example 4 The hydrophilic modified polyketone material of this embodiment is made from the following components: Polyketone resin 1590g, compatibilizer 100g, hydrophilic agent 300g, initiator 10g, antioxidant 10g, lubricant 12g; The hydrophilic agent is methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000; the compatibilizer is maleic anhydride-grafted polyethylene 80g and maleic anhydride-grafted EMA 20g; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidant is antioxidant 1098 and antioxidant 168 in a 1:1 mass ratio; and the lubricant is ethylene bis-stearamide.

[0047] The preparation method of the hydrophilic modified polyketone material in this embodiment includes the following steps: S1: Add polyketone resin, compatibilizer, antioxidant, and lubricant into a high-speed mixer and mix at 1200 rpm for 3 minutes to obtain the main feed; S2: Mix the hydrophilic agent and initiator evenly to obtain the side feed; S3: The main feed is added to the twin-screw extruder through the main feed port, and the side feed mixture is injected from the fifth zone side feed port of the twin-screw extruder through a metering pump. The extruded strip is cooled by circulating cooling water at 25°C, air-dried, pelletized, and dried at 80°C for 4 hours to obtain hydrophilic modified polyketone material.

[0048] The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1 is 150℃; Zones 2 to 11 are 230℃, and the main extruder speed is 280 rpm.

[0049] Example 5 The difference between this embodiment and embodiment 4 is that: The hydrophilic modified polyketone material of this embodiment is made from the following components: Polyketone resin 1590g, compatibilizer 100g, hydrophilic agent 300g, initiator 10g, antioxidant 10g, lubricant 12g; The product contains 240g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000 and 60g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 1000; the compatibilizer is 80g of maleic anhydride-grafted polyethylene and 20g of maleic anhydride-grafted EMA; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidants are antioxidant 1098 and antioxidant 168 in a 1:1 mass ratio; and the lubricant is ethylene bis-stearamide.

[0050] The rest is the same as in Example 4.

[0051] Example 6 The difference between this embodiment and embodiment 5 is as follows: The hydrophilic modified polyketone material of this embodiment is made from the following components: Polyketone resin 1590g, compatibilizer 100g, hydrophilic agent 300g, initiator 10g, antioxidant 10g, lubricant 12g; The hydrophilic agents are 240g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000, 40g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 1000, and 20g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 600; the compatibilizers are 80g of maleic anhydride-grafted polyethylene and 20g of maleic anhydride-grafted EMA; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidants are antioxidant 1098 and antioxidant 168 in a 1:1 mass ratio; and the lubricant is ethylene bis-stearamide.

[0052] The rest is the same as in Example 5.

[0053] Example 7 The hydrophilic modified polyketone material of this embodiment is made from the following components: Polyketone resin 1590g, compatibilizer 100g, hydrophilic agent 300g, initiator 10g, antioxidant 10g, lubricant 12g, sulfobetaine methacrylate 10g; The hydrophilic agents are 240g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000, 40g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 1000, and 20g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 600; the compatibilizers are 80g of maleic anhydride-grafted polyethylene and 20g of maleic anhydride-grafted EMA; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidants are antioxidant 1098 and antioxidant 168 in a 1:1 mass ratio; and the lubricant is ethylene bis-stearamide.

[0054] The preparation method of the hydrophilic modified polyketone material in this embodiment includes the following steps: S1: Add polyketone resin, compatibilizer, antioxidant, and lubricant into a high-speed mixer and mix at 1200 rpm for 3 minutes to obtain the main feed; S2: Mix the hydrophilic agent, sulfobetaine methacrylate and initiator evenly to obtain the side feed; S3: The main feed is added to the twin-screw extruder through the main feed port, and the side feed mixture is injected from the fifth zone side feed port of the twin-screw extruder through a metering pump. The extruded strip is cooled by circulating cooling water at 25°C, air-dried, pelletized, and dried at 80°C for 4 hours to obtain hydrophilic modified polyketone material.

[0055] The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1 is 150℃; Zones 2 to 11 are 230℃, and the main extruder speed is 280 rpm.

[0056] Example 8 The hydrophilic modified polyketone material of this embodiment is made from the following components: 1590g of polyketone resin, 100g of compatibilizer, 300g of hydrophilic agent, 10g of initiator, 10g of antioxidant, 12g of lubricant, 10g of sulfobetaine methacrylate, and 15g of octadecyl polyoxyethylene ether methacrylate. The hydrophilic agents are 240g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000, 40g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 1000, and 20g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 600; the compatibilizers are 80g of maleic anhydride-grafted polyethylene and 20g of maleic anhydride-grafted EMA; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidants are antioxidant 1098 and antioxidant 168 in a 1:1 mass ratio; and the lubricant is ethylene bis-stearamide.

[0057] The preparation method of the hydrophilic modified polyketone material in this embodiment includes the following steps: S1: Add polyketone resin, compatibilizer, antioxidant, and lubricant into a high-speed mixer and mix at 1200 rpm for 3 minutes to obtain the main feed; S2: Mix the hydrophilic agent, sulfobetaine methacrylate, octadecyl polyoxyethylene ether methacrylate and initiator evenly to obtain the side feed; S3: The main feed is added to the twin-screw extruder through the main feed port, and the side feed mixture is injected from the fifth zone side feed port of the twin-screw extruder through a metering pump. The extruded strip is cooled by circulating cooling water at 25°C, air-dried, pelletized, and dried at 80°C for 4 hours to obtain hydrophilic modified polyketone material.

[0058] The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1 is 150℃; Zones 2 to 11 are 230℃, and the main extruder speed is 280 rpm.

[0059] Example 9 The difference between this embodiment and embodiment 8 is as follows: The hydrophilic modified polyketone material of this embodiment is made from the following components: 1590g of polyketone resin, 100g of compatibilizer, 300g of hydrophilic agent, 10g of initiator, 10g of antioxidant, 12g of lubricant, 40g of sulfobetaine methacrylate, and 24g of octadecyl polyoxyethylene ether methacrylate. The rest is the same as in Example 8.

[0060] Example 10 The hydrophilic modified polyketone material of this embodiment is made from the following components: 1590g polyketone resin, 100g compatibilizer, 300g hydrophilic agent, 10g initiator, 10g antioxidant, 12g lubricant, 10g sulfobetaine methacrylate, 20g silanized nano-SiO2. The hydrophilic agents are 240g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 2000, 40g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 1000, and 20g of methoxy polyethylene glycol methacrylate with a number average molecular weight of 600; the compatibilizers are 80g of maleic anhydride-grafted polyethylene and 20g of maleic anhydride-grafted EMA; the initiator is 1,3-bis(tert-butylperoxyisopropyl)benzene; the antioxidants are antioxidant 1098 and antioxidant 168 in a 1:1 mass ratio; and the lubricant is ethylene bis-stearamide.

[0061] The preparation method of the hydrophilic modified polyketone material in this embodiment includes the following steps: S1: Add polyketone resin, silanized nano-SiO2, compatibilizer, antioxidant, and lubricant into a high-speed mixer and mix at 1200 rpm for 3 minutes to obtain the main feed; S2: Mix the hydrophilic agent, sulfobetaine methacrylate and initiator evenly to obtain the side feed; S3: The main feed is added to the twin-screw extruder through the main feed port, and the side feed mixture is injected from the fifth zone side feed port of the twin-screw extruder through a metering pump. The extruded strip is cooled by circulating cooling water at 25°C, air-dried, pelletized, and dried at 80°C for 4 hours to obtain hydrophilic modified polyketone material.

[0062] The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1 is 150℃; Zones 2 to 11 are 230℃, and the main extruder speed is 280 rpm.

[0063] The preparation method of silanized nano-SiO2 includes the following steps: Nano-SiO2 was added to an ethanol-water solution (anhydrous ethanol and deionized water in a volume ratio of 9:1), with a solid-liquid ratio of 1g:10mL. The pH of the system was adjusted to 5.0 using 8% glacial acetic acid. 1.5% by mass of silane coupling agent KH-570 and 1.5% by mass of 2-[methoxy(polyoxyethylene)propyl]trimethoxysilane were added, and the mixture was stirred and mixed evenly. The mixture was heated to 55℃ and reacted for 6 hours. After centrifugation, the mixture was washed twice with deionized water and dried at 50℃ to constant weight to obtain silanized nano-SiO2.

[0064] The particle size distribution of nano-SiO2 is 20~50nm.

[0065] Example 11 The difference between this embodiment and embodiment 10 is as follows: The hydrophilic modified polyketone material of this embodiment is made from the following components: 1590g polyketone resin, 100g compatibilizer, 300g hydrophilic agent, 10g initiator, 10g antioxidant, 12g lubricant, 15g sulfobetaine methacrylate, 40g silanized nano-SiO2. The preparation method of silanized nano-SiO2 includes the following steps: Nano-SiO2 was added to an ethanol-water solution (anhydrous ethanol and deionized water in a volume ratio of 9:1), with a solid-liquid ratio of 1g:10mL. The pH of the system was adjusted to 4.5 using 8% glacial acetic acid. 2% by mass of silane coupling agent KH-570 and 2% by mass of 2-[methoxy(polyoxyethylene)propyl]trimethoxysilane were added, and the mixture was stirred until homogeneous. The mixture was heated to 70℃ and reacted for 4 hours. After centrifugation, the mixture was washed twice with deionized water and dried at 50℃ to constant weight to obtain silanized nano-SiO2.

[0066] The particle size distribution of nano-SiO2 is 20~50nm.

[0067] Everything else is the same as in Example 10.

[0068] Comparative Example 1 The difference between this comparative example and Example 1 is as follows: No compatibilizer was added, and the hydrophilic agent was polyethylene glycol with a number average molecular weight of 2000.

[0069] Everything else is the same as in Example 1.

[0070] Comparative Example 2 The difference between this comparative example and Example 1 is as follows: No compatibilizer was added; Everything else is the same as in Example 1.

[0071] Comparative Example 3 The difference between this comparative example and Example 1 is as follows: The hydrophilic agent is polyethylene glycol with a number average molecular weight of 2000.

[0072] Everything else is the same as in Example 1.

[0073] Comparative Example 4 The difference between this comparative example and Example 1 is as follows: No hydrophilic agents or compatibilizers were added; Everything else is the same as in Example 1.

[0074] Comparative Example 5 The difference between this comparative example and Example 1 is as follows: The hydrophilic agent is polyethylene glycol, the dosage is 300g, and the number average molecular weight is 2000; Everything else is the same as in Example 1.

[0075] Performance testing The hydrophilic modified polyketone materials obtained in the examples and comparative examples were injection molded into standard specimens on an injection molding machine. After being conditioned for 24 hours in an environment of 23±2℃ and 50±5% relative humidity, the following performance tests were conducted. The specific data are shown in Table 1: (1) Water contact angle test, the reference standard is GB / T 30693-2014; (2) Hydrophilic durability test: each sample was washed with water in a cycle. Each wash included 10 minutes of washing and 5 minutes of dehydration. After 50 washes, the sample was conditioned for 24 hours at 23±2℃ and 50±5% relative humidity. The water contact angle was measured according to GB / T 30693-2014 standard, and the change in contact angle before and after washing was calculated. (3) Tensile strength test, referring to GB / T 1040.1-2025 standard, the tensile rate is 50 mm / min; (4) Notched impact strength test, refer to GB / T 1843-2008 standard, V notch, cantilever beam method.

[0076] Table 1. Performance test data of hydrophilic modified polyketone materials prepared in Examples 1-11 and Comparative Examples 1-5

[0077] Note: "-" indicates that the initial contact angle of the sample is ≥65°. Such surfaces do not have significant hydrophilic application value, so durability testing was not conducted.

[0078] Based on the performance test data in Table 1, we can conclude that: In Examples 1-4, within the component range defined in this application, increasing the amount of compatibilizer simultaneously improved the hydrophilicity and interfacial mechanical properties of the materials, and all samples exhibited good hydrophilic durability. When the amount of hydrophilic agent increased from 10 parts to 15 parts, the decrease in contact angle became smaller, while the decrease in tensile strength slightly increased. However, even with a high amount of hydrophilic agent, the impact strength and tensile strength remained in a relatively good range compared to the physical blend in Comparative Example 5.

[0079] In Examples 4-6, by compounding methoxy polyethylene glycol methacrylates of different molecular weights, a multi-layered hydrophilic structure was constructed, which not only slightly reduced the contact angle but also slightly improved the mechanical properties while maintaining stable hydrophilic durability. This is because the gradient molecular weight helps to refine or stabilize the interface and reduce phase separation defects.

[0080] In Examples 6-9, the introduction of sulfobetaine methacrylate significantly reduced the initial contact angle, and octadecyl polyoxyethylene ether methacrylate optimized the hydrophilic durability of the material. The synergistic use of the two can maintain the relative stability of the material's mechanical properties while optimizing surface hydrophilicity and durability.

[0081] In Examples 9-11, the introduction of silanized nano-SiO2 resulted in a sustained and significant improvement in tensile strength while maintaining good hydrophilicity and hydrophilic durability.

[0082] Of the Comparative Examples 1-5, Comparative Example 4, a pure polyketone resin, exhibited strong hydrophobicity, and its rigidity and toughness were at a high level. Comparative Examples 1-2 showed that regardless of whether the hydrophilic agent was reactive or non-reactive, without a compatibilizer to provide interfacial anchoring, the hydrophilic component could not form a strong bond with the matrix and would quickly precipitate and be lost under dynamic water washing; even with the addition of a compatibilizer, the durability of the non-reactive PEG was still insufficient. Conversely, in Comparative Example 5, although the hydrophilicity was significantly enhanced after a substantial increase in the amount of non-reactive polyethylene glycol, both tensile strength and notched impact strength showed a significant deterioration, indicating that relying solely on physical blending and adding a large amount of non-reactive hydrophilic agent would severely sacrifice the mechanical properties of the material.

Claims

1. A hydrophilic modified polyketone material, characterized in that, It is made from the following components in parts by weight: 80-93 parts polyketone resin, 2-5 parts compatibilizer, 5-15 parts hydrophilic agent, 0.1-0.5 parts initiator, 0.2-0.5 parts antioxidant, and 0.3-0.6 parts lubricant; The hydrophilic agent is methoxy polyethylene glycol methacrylate.

2. The hydrophilic modified polyketone material according to claim 1, characterized in that, The compatibilizer is at least one of maleic anhydride-grafted polyolefin and maleic anhydride-grafted EMA.

3. The hydrophilic modified polyketone material according to claim 1, characterized in that, The hydrophilic agent includes high molecular weight methoxy polyethylene glycol methacrylate and low molecular weight methoxy polyethylene glycol methacrylate.

4. The hydrophilic modified polyketone material according to claim 3, characterized in that, The low molecular weight methoxy polyethylene glycol methacrylate has a number average molecular weight of 600-1000.

5. The hydrophilic modified polyketone material according to claim 1, characterized in that, The hydrophilic modified polyketone material also includes 0.5 to 2 parts by weight of sulfobetaine methacrylate.

6. The hydrophilic modified polyketone material according to claim 1, characterized in that, The hydrophilic modified polyketone material also includes octadecyl polyoxyethylene ether methacrylate, and the amount of octadecyl polyoxyethylene ether methacrylate is 5% to 8% of the mass of the hydrophilic agent.

7. The hydrophilic modified polyketone material according to claim 1, characterized in that, The hydrophilic modified polyketone material also includes 1-2 parts by weight of silanized nano-SiO2, which is prepared by co-modification with silane coupling agent KH-570 and 2-[methoxy(polyoxyethylene)propyl]trimethoxysilane.

8. A method for preparing the hydrophilic modified polyketone material as described in claim 1, characterized in that, The process includes the following steps: After mixing polyketone resin, compatibilizer, antioxidant, and lubricant evenly according to the formula, the mixture is fed from the main feeder. After mixing hydrophilic agent and initiator, the mixture is fed from the side feeder. The mixture is then extruded through a twin-screw extruder, cooled, granulated, dried, and injection molded to obtain hydrophilic modified polyketone material.

9. The method for preparing the hydrophilic modified polyketone material according to claim 8, characterized in that, When adding a hydrophilic agent, the steps also include adding sulfobetaine methacrylate and / or octadecyl polyoxyethylene ether methacrylate.

10. The method for preparing the hydrophilic modified polyketone material according to claim 8, characterized in that, The process includes adding silanized nano-SiO2 after the addition of polyketone resin.

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