WO2022247035A1 - 一种抗菌低粘附聚乙烯醇涂层 - Google Patents

一种抗菌低粘附聚乙烯醇涂层 Download PDF

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WO2022247035A1
WO2022247035A1 PCT/CN2021/115225 CN2021115225W WO2022247035A1 WO 2022247035 A1 WO2022247035 A1 WO 2022247035A1 CN 2021115225 W CN2021115225 W CN 2021115225W WO 2022247035 A1 WO2022247035 A1 WO 2022247035A1
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polyvinyl alcohol
low
antibacterial
adhesion
alcohol coating
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PCT/CN2021/115225
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English (en)
French (fr)
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吴旭
陈俊民
于丹凤
徐秀彬
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广州大学
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Publication of WO2022247035A1 publication Critical patent/WO2022247035A1/zh
Priority to US18/489,004 priority Critical patent/US20240052179A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention belongs to the field of novel polymer functional materials, and more specifically relates to an antibacterial low-adhesion polyvinyl alcohol coating.
  • low-adhesion coatings that do not stick to liquids have promising applications in the fields of antifouling self-cleaning, anti-icing, anti-fog, liquid transport, and drag reduction.
  • the low liquid adhesion properties of such materials are affected by the topography of the material surface as well as the surface chemical composition.
  • the preparation conditions of existing low-adhesion coatings are complex and have certain biological toxicity, which restricts the development and application of such materials. Therefore, it is urgent to propose a simple, efficient and biocompatible low-adhesion coating.
  • micro-nano rough surface structure on the surface of the bionic lotus leaf.
  • This type of material can be assembled with fluorine-containing silica, zinc oxide and other particles on the surface of the material. Formation imparts a micro-nanostructure to the surface of the material, however such materials are not wear-resistant.
  • anti-adhesive materials with smooth surface structures such as SLIPS, monolayers and polymer coatings. Since SLIPS and monolayers have problems such as lubricant loss and non-abrasion resistance, polymer coatings have more room for development.
  • polymer coatings it has been reported that high-density crosslinking can enhance the interaction within molecules and promote the formation of micro-nano holes on the surface, which improves the anti-adhesion performance of the material surface.
  • anti-adhesion properties can be achieved by physically mixing or chemically bonding low surface energy monomers to change the chemical composition of the material surface.
  • functional monomers will spontaneously enrich on the surface to form a low liquid adhesion layer.
  • the liquid-solid interface formed between the external liquid and the coating surface inhibits the reconstruction of functional molecular segments, which can realize the anti-sticking of liquid attached.
  • polymer coatings are prepared from film-forming monomers with poor biocompatibility and non-degradability, and the polymer coatings have insufficient anti-liquid adhesion properties.
  • the primary purpose of the present invention is to provide an antibacterial low adhesion polyvinyl alcohol coating.
  • Polyvinyl alcohol with good biocompatibility is selected, and polyvinyl alcohol is strongly cross-linked by multifunctional isocyanate, and a small amount of monohydroxy silicone oil is added to the system to give the coating good low adhesion performance; strong cross-linking
  • the combination imparts strength to the coating while enhancing the internal interaction force of the coating, inhibits the surface chemical reconstruction of functional monomers, and reduces the interaction with foreign substances at the coating interface, while low surface energy compounds are conducive to regulating the surface of the system.
  • the efficient coordination of energy, cross-linking, and surface energy regulation facilitates the coating to simultaneously exhibit low adhesion to aqueous and oily liquids and good anti-bacterial adhesion properties.
  • Another object of the present invention is to provide the preparation method of the above-mentioned antibacterial low-adhesion polyvinyl alcohol coating
  • Another object of the present invention is to provide the application of the antibacterial low-adhesion polyvinyl alcohol coating in the fields of antifouling self-cleaning, liquid transportation and animal body implant materials.
  • the invention provides an antibacterial low-adhesion polyvinyl alcohol coating, comprising the following raw materials in weight percentage:
  • the crosslinking agent is at least one selected from hexamethylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate trimer.
  • the low surface energy compound is selected from organosilicon compounds, and further, the organosilicon compound is at least one of monohydroxyl-terminated silicone oils with an average molecular weight of 1000, 3000, 5000 and 10000.
  • the polyvinyl alcohol is formulated into a 0-10% mass fraction solution with a hydrophilic solvent, and the mass fraction solution is not 0; the mass fraction is further 4-6%.
  • the hydrophilic solvent is an amide solvent, specifically at least one of N,N-dimethylformamide and N,N-dimethylformamide.
  • the crosslinking agent, low surface energy compound and catalyst are dispersed in a compound solvent of ketone solvent and amide solvent;
  • the ketone solvent is preferably at least one ketone solvent such as acetone and butanone;
  • the The amide solvent is preferably at least one of N,N-dimethylformamide and N,N-dimethylformamide; the volume ratio of the amide solvent to the ketone solvent is (10-15):1.
  • the prepolymer solution formed from the raw materials of the antibacterial and low-adhesion polyvinyl alcohol coating has a solid content of 5% to 10%.
  • the present invention provides the preparation method of the cross-linked polyvinyl alcohol coating of above-mentioned antibacterial low adhesion, comprises the following steps:
  • the reaction time of the step (1) is 12 to 24 hours.
  • the substrate in step (3) is tinplate, glass sheet, PET, 316 stainless steel, etc.
  • the curing is heating at 100-140° C. for 2-8 hours.
  • the antibacterial low-adhesion polyvinyl alcohol coating has waterproof, oil-proof and anti-bacterial adhesion properties, and can be applied in the fields of anti-fouling self-cleaning, liquid transportation and animal body implant materials.
  • the antibacterial and low-adhesion polyvinyl alcohol coating prepared by the invention Compared with the prior art, the antibacterial and low-adhesion polyvinyl alcohol coating prepared by the invention. It has the following technical effects:
  • the preparation method of the antibacterial low-adhesion polyvinyl alcohol coating is simple, the energy consumption is low, and it is suitable for industrial production.
  • the antibacterial and low-adhesion cross-linked polyvinyl alcohol coating has strong cross-linking and good adhesion to the substrate.
  • the polyvinyl alcohol coating has excellent flexibility, which can be minimally affected by the deformation of the substrate.
  • the antibacterial low-adhesion polyvinyl alcohol coating has good transparency.
  • the antibacterial low-adhesion polyvinyl alcohol coating has excellent waterproof and oil-adherent performance, and has good anti-bacterial adhesion performance.
  • Figure 1 is a schematic diagram of the preparation process of an antibacterial and low-adhesion cross-linked polyvinyl alcohol coating.
  • Fig. 2 is a water sliding angle diagram of Examples 1-3.
  • Fig. 3 is the water-oil sliding angle diagram of embodiment 1.
  • Fig. 4 is the antibacterial performance figure of embodiment 1 ⁇ 3.
  • Fig. 5 is the antibacterial performance figure of embodiment 1.
  • the antibacterial low-adhesion polyvinyl alcohol coating of the present invention is made of polyvinyl alcohol, crosslinking agent, low surface energy compound, catalyst, specifically comprises the raw material of following percentage by weight:
  • Antibacterial low adhesion polyvinyl alcohol coating of the present invention is prepared as follows (seeing Fig. 1):
  • Disperse crosslinking agent preferably hexamethylene diisocyanate trimer (HDIT)
  • low surface energy compound preferably 5000 molecular weight monohydroxy silicone oil (PDMS-OH-5000)
  • dibutyltin dilaurate In a compound solvent [preferably acetone and N,N-dimethylacetamide (DMAc)], react for 12 to 24 hours;
  • a compound solvent preferably acetone and N,N-dimethylacetamide (DMAc)
  • Each raw material composition of Examples 1-3 corresponds to Table 1-3 respectively.
  • Fig. 2 is the water sliding angle test of the coatings composed of different raw materials in Examples 1-3.
  • Example 1 Through the comparison of Example 1 and Example 2, it can be seen that the increase of the silicone oil content has little effect on the performance, or even slightly decreases. This is due to the increase in the silicone oil content, which makes it easier to form macroscopic phase separation inside the coating system, and this phase separation is not conducive to the migration of silicone oil segments to the interface when the coating contacts with foreign substances, thereby reducing its Anti-adhesive properties.
  • Example 1 the comparison of Example 1 and Example 3 can be found that the reduction of solid content leads to a significant increase in the water sliding angle, which is due to the smaller the solid content in the coating process, the smaller the film thickness and the The fewer functional monomers with low surface energy, the lower the lyophobic ability of the surface.
  • Fig. 3 is the water-oil sliding angle figure of embodiment 1, it can be clearly seen that the cross-linked polyvinyl alcohol coating has excellent waterproof and oil-proof adhesion properties, wherein the sliding angles of daily water, vegetable oil and pump oil are lower than 15°, while toluene, hexadecane and diiodomethane are even lower than 5°, indicating that the coating can be applied in the field of antifouling self-cleaning and liquid transportation materials.
  • Fig. 4 is the test results of Examples 1-3 and a blank glass substrate.
  • Four 1cm ⁇ 1cm samples were respectively inoculated with 1mL Escherichia coli bacteria solution (bacteria concentration: 10 6 cells/mL) in a test tube filled with PBS solution and cultured for four hours, then rinsed the residual bacteria solution on the surface of the inoculated sample with 2mL PBS solution .
  • Figure 5 is the test results of Example 1 and a blank glass substrate.
  • Two 1cm ⁇ 1cm samples were respectively inoculated with 50 ⁇ L of Escherichia coli bacteria solution (bacterial solution concentration: 10 8 cells/mL) in a test tube filled with nutrient broth solution (E. coli will proliferate to the peak value in nutrient broth) Fourteen hours later, rinse the residual bacterial liquid on the surface of the inoculated sample with 2mL PBS solution.
  • the comparison shows that after soaking in the bacterial solution for four hours in Examples 1 to 3 in Figure 4, compared with the blank glass substrate, the relative number of colonies is less, and the relative antibacterial rate is about 95%, indicating a low
  • the adhered polyvinyl alcohol coating has good antimicrobial properties.
  • Fig. 5 further increases the concentration of bacteria solution and prolongs the soaking time.
  • the relative antibacterial rate is about 54%, and there is still a certain antibacterial performance. This is attributed to the existence of silicone oil molecular brushes on the coating surface, the surface has low surface energy, and it is difficult for the bacterial surface to interact with the strongly cross-linked polyvinyl alcohol surface, thereby reducing bacterial adhesion.

Abstract

一种抗菌低粘附的交联聚乙烯醇涂层，包括以下重量百分数的原料：聚乙烯醇25％～30％；交联剂65％～70％；低表面能化合物1％～5％；二月桂酸二丁基锡0～0.5％，不为0。一种该抗菌低粘附的交联聚乙烯醇涂层的制备方法及该涂层在防污自清洁、液体运输以及动物体植入材料领域中的应用。

Description

一种抗菌低粘附聚乙烯醇涂层
本发明属于新型高分子功能材料领域，更具体地，涉及一种抗菌低粘附聚乙烯醇涂层。
背景技术
近年来，不沾液体的低粘附涂层在防污自清洁、防冰、防雾、液体输送和减阻等领域具有广阔的应用前景。这类材料的低液体粘附性能受材料表面的形貌以及表面化学组成影响。目前，现有的低粘附涂层制备条件复杂且具有一定的生物毒性，制约着该类材料的发展和应用。因此提出一种简单高效且具有生物相容性的低粘附涂层，亟待解决。
关于表面的形貌对材料的低液体粘附性能影响，比较典型的有仿生荷叶表面的微纳粗糙表面结构，这类材料可通过在材料表面组装含氟的二氧化硅、氧化锌等颗粒形成赋予材料表面微纳结构，然而这类材料不耐磨。另外还有光滑表面结构的防粘附材料，如SLIPS、单分子层和聚合物涂层。由于SLIPS和单分子层分别存在润滑剂流失和不耐磨等问题，所以聚合物涂层更具发展空间。关于聚合物涂层，有报道曾指出高密度交联可增强分子内部的相互作用并促进表面形成微纳米孔洞，提高了材料表面的防粘附性能。另一方面，防粘附性能可以通过物理混合或化学键合低表面能单体改变材料表面的化学组成实现。涂层材料在固化过程中功能单体会自发地在表面富集形成低液体粘附层，同时，外来液体和涂层表面形成的液固界面处抑制功能分子链段重构，可实现液体的防粘附。但目前都是使用生物相容性差且不可降解的成膜单体来制备聚合物涂层，并且聚合物涂层防液体粘附性能不足。
发明内容
为解决现有低粘附材料制备复杂且不具生物相容性等问题。本发明首要目的在于提供一种抗菌低粘附聚乙烯醇涂层。选用具有良好的生物相容性的聚乙烯醇，通过多官能度的异氰酸酯对聚乙烯醇进行强交联，同时在体系中接入少量单羟基硅油赋予涂层良好的低粘附性能；强交联赋予涂层强度的同时增强涂层的内部的相互作用力，抑制功能单体的表面化学重构，减少涂层界面处与外来物的相互作用，而低表面能化合物有利于调控体系的表面能，交联和表面能调控的高效协调 促进涂层同时对水性和油性液体表现出低粘附性，并具有良好的防细菌粘附性能。
本发明另一目的在于提供是上述抗菌低粘附聚乙烯醇涂层的制备方法；
本发明再一目的在于提供上述抗菌低粘附聚乙烯醇涂层在防污自清洁、液体运输以及动物体植入材料领域中的应用。
本发明提供一种抗菌低粘附聚乙烯醇涂层，包括以下重量百分数的原料：
聚乙烯醇25％～30％；
交联剂65％～70％；
低表面能化合物1％～5％；
二月桂酸二丁基锡0～0.5％，不为0。
进一步，所述交联剂选自六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯三聚体至少一种。
进一步，所述低表面能化合物选自有机硅化合物，更进一步所述有机硅化合物为平均分子量1000，3000，5000和10000的单羟基封端硅油中的至少一种。
进一步，所述聚乙烯醇应用亲水性溶剂配成0～10％质量分数溶液，质量分数溶液不为0；质量分数更进一步为4～6％。更进一步，所述亲水性溶剂为酰胺类溶剂，具体为N,N-二甲基甲酰胺、N,N-二甲基甲酰胺至少一种。
进一步，所述交联剂、低表面能化合物和催化剂选用酮类溶剂和酰胺类溶剂的复配溶剂进行分散；所述酮类溶剂优选为丙酮和丁酮等至少一种酮类溶剂；所述酰胺类溶剂优选为N,N-二甲基甲酰胺、N,N-二甲基甲酰胺至少一种；所述酰胺类溶剂和酮类溶剂体积比为(10～15):1。
进一步，所述抗菌低粘附聚乙烯醇涂层的原料形成的预聚体溶液，固含量为5％～10％。
本发明提供上述抗菌低粘附的交联聚乙烯醇涂层的制备方法，包括以下步骤:
(1)将交联剂、低表面能化合物、催化剂、分散于复配溶剂中，进行反应；
(2)随后继续加入聚乙烯醇溶液，将固含调至5％～10％搅拌均匀后得到预聚体溶液；
(3)最后取预聚体溶液在基体表面进行涂膜，固化后得到抗菌低粘附的交联聚乙烯醇涂层。
步骤(1)所述反应的时间为12～24h。
步骤(3)所述基体为马口铁、玻璃片、PET、316不锈钢等。所述固化为在100～140℃下加热2～8h。
所述抗菌低粘附聚乙烯醇涂层具有防水、防油、防细菌粘附性能,可在防污自清洁、液体运输以及动物体植入材料领域中应用。
有益效果：
与现有技术相比，本发明制备的抗菌低粘附聚乙烯醇涂层。具有如下技术效果：
(1)抗菌低粘附聚乙烯醇涂层制备方法简单，能耗低，适用于工业化生产。
(2)抗菌低粘附的交联聚乙烯醇涂层具有强交联，与基材具有良好的附着性。
(3)聚乙烯醇涂层具有优异的柔韧性，其能受基材形变的影响极小。
(4)抗菌低粘附聚乙烯醇涂层具有良好的透明度。
(5)抗菌低粘附聚乙烯醇涂层具有优异的防水油粘附的性能，并具有良好的防细菌粘附性能。
附图说明
图1为抗菌低粘附的交联聚乙烯醇涂层制备流程简图。
图2为实施例1～3水滑动角图。
图3为实施例1的水油滑动角图。
图4为实施例1～3的抗菌性能图。
图5为实施例1的抗菌性能图。
具体实施方式
以下是本发明的具体实施例，并结合实施例对本发明的技术方案作进一步的描述，但本发明并不限于这些实施例。
本发明的抗菌低粘附聚乙烯醇涂层由聚乙烯醇、交联剂、低表面能化合物、催化剂制成，具体包括以下重量百分数的原料：
聚乙烯醇20％～25％；
交联剂65％～70％；
低表面能化合物1％～4.5％；
催化剂0～0.5％。
各原料所用具体物质以及用量详见表1～3。
本发明的抗菌低粘附聚乙烯醇涂层制备如下(见图1)：
(1)将交联剂[优选六亚甲基二异氰酸酯三聚体(HDIT)]、低表面能化合物[优选5000分子量单羟基硅油(PDMS-OH-5000)]、二月桂酸二丁基锡、分散于复配溶剂[优选丙酮和N,N-二甲基乙酰胺(DMAc)]中，反应12～24h；
将交联剂、低表面能化合物、催化剂、溶剂加入三口烧瓶，混合均匀。将反应体系温度升至60～80℃，优选60℃，恒温反应12h形成反应前体。
(2)随后继续加入质量分数0～10％聚乙烯醇溶液，优选5％，将固含量调至5％～10％搅拌均匀后得到预聚体溶液。
(3)最后取预聚体溶液在马口铁、玻璃片、PET、316不锈钢进行涂布，并在120℃下烘干4h得到抗菌低粘附的交联聚乙烯醇涂层。
实施例1-3
实施例1-3各原料组成分别对应表1-3。
表1.实施例1抗菌低粘附聚乙烯醇涂层原料组成
Figure PCTCN2021115225-appb-000001
表2.实施例2抗菌低粘附聚乙烯醇涂层原料组成
Figure PCTCN2021115225-appb-000002
Figure PCTCN2021115225-appb-000003
表3.实施例3抗菌低粘附聚乙烯醇涂层原料组成
Figure PCTCN2021115225-appb-000004
检测结果
1.抗菌低粘附聚乙烯醇涂层水滑动角测试
图2为实例1～3不同原料组成的涂层的水滑动角测试。通过实施例1和实施例2对比，可以看出，硅油含量的增加对性能影响不大，甚至略有降低。这是归因于硅油含量变多，在涂层体系内部更容易形成宏观分相，而这种分相则不利于涂层和外源物接触时硅油链段往界面处的迁移，从而降低其防粘附性能。
其次，实施例1和实施例3的对比可以发现，固含的降低，其水滑动角有明显的增大，这是归因于涂膜过程中固含越小，其成膜厚度变小以及低表面能功能单体越少，从而降低了表面的疏液能力。
2.抗菌低粘附聚乙烯醇涂层油滑动角测试
图3为实施例1的水油滑动角图，可以清晰看到交联聚乙烯醇涂层具有优异的防水和防油粘附的性能，其中日常的水、植物油和泵油的滑动角低于15°，而甲苯、十六烷和二碘甲烷更是低于5°，表明该涂层可在防污自清洁以及液体运输材料领域中应用。
3.抗菌低粘附聚乙烯醇涂层抗菌测试
图4为实施例1～3和空白玻璃基材的测试结果。四个1cm×1cm的样品分别用1mL大肠杆菌菌液(菌液浓度：10 6个/mL)在装有PBS溶液的试管接种培养四 小时后，用2mL PBS溶液冲洗已接种样品表面残余菌液。在40kHz下超声10分钟，在40kHz下超声10分钟，将超声后的PBS溶液定量稀释后，取0.1mL，在培养基中恒温37℃培养，以探究样品的抗细菌粘附能力。
图5为实施例1和空白玻璃基材的测试结果。两个1cm×1cm的样品分别用50μL大肠杆菌菌液(菌液浓度：10 8个/mL)在装有营养肉汤溶液(大肠杆菌在营养肉汤中会增值至峰值)的试管接种培养二十四小时后，用2mLPBS溶液冲洗已接种样品表面残余菌液。然后将样品放入1mL无菌PBS中，在40kHz下超声10分钟，将超声后的PBS溶液定量稀释后，取0.1mL，在培养基中恒温37℃培养，以进一步探究样品的抗细菌粘附能力。
通过统计培养基表面大肠杆菌数，对比可知，图4中实施例1～3在浸泡四小时菌液后，相比空白玻璃基材相对菌落数较少，相对抗菌率约为95％，表明低粘附的聚乙烯醇涂层具有良好的抗菌性能。图5相对于图4进一步提高菌液浓度并延长浸泡时间，浸泡二十四小时后，相对抗菌率约为54％，仍有一定的抗菌性能。这是归因于涂层表面硅油分子刷的存在，表面具有低表面能，细菌表面难以和强交联的聚乙烯醇表面发生相互作用，从而降低细菌粘附。

Claims (10)

  1. 一种抗菌低粘附的交联聚乙烯醇涂层，其特征在于:包括以下重量百分数的原料：
    聚乙烯醇25％～30％；
    交联剂65％～70％；
    低表面能化合物1％～5％；
    二月桂酸二丁基锡0～0.5％，不为0。
  2. 根据权利要求1所述抗菌低粘附的交联聚乙烯醇涂层，其特征在于：所述交联剂选自六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯三聚体至少一种。
  3. 根据权利要求1所述抗菌低粘附的交联聚乙烯醇涂层，其特征在于：所述低表面能化合物选自有机硅化合物。
  4. 根据权利要求3所述抗菌低粘附的交联聚乙烯醇涂层，其特征在于：所述有机硅化合物为平均分子量1000，3000，5000和10000的单羟基封端硅油中的至少一种。
  5. 根据权利要求1所述抗菌低粘附的交联聚乙烯醇涂层，其特征在于：聚乙烯醇应用亲水性溶剂配成0～10％质量分数溶液，质量分数不为0；所述亲水性溶剂为酰胺类溶剂，具体为N,N-二甲基甲酰胺、N,N-二甲基甲酰胺至少一种；
    所述交联剂、低表面能化合物和催化剂选用酮类溶剂和酰胺类溶剂的复配溶剂进行分散。
  6. 根据权利要求5所述抗菌低粘附的交联聚乙烯醇涂层，其特征在于：
    所述酮类溶剂为丙酮和丁酮至少一种；所述酰胺类溶剂为N,N-二甲基甲酰胺、N,N-二甲基甲酰胺至少一种；所述酰胺类溶剂和酮类溶剂体积比为(10～15):1。
  7. 根据权利要求1所述抗菌低粘附的交联聚乙烯醇涂层，其特征在于：所述抗菌低粘附的交联聚乙烯醇涂层的原料形成的预聚体溶液，固含量为5％～10％。
  8. 一种制备权利要求1～7任一项所述抗菌低粘附的交联聚乙烯醇涂层的方法，其特征在于包括以下步骤：
    (1)将交联剂、低表面能化合物、催化剂、分散于复配溶剂中，进行反应；
    (2)随后继续加入聚乙烯醇溶液，将固含调至5％～10％搅拌均匀后得到预聚体溶液；
    (3)最后取预聚体溶液在基体表面进行涂膜，固化后得到抗菌低粘附的交联聚乙烯醇涂层。
  9. 根据权利要求8所述的方法，其特征在于：步骤(1)所述反应的时间为12～24h；步骤(3)所述基体为马口铁、玻璃片、PET或316不锈钢；所述固化为在100～140℃下加热2～8h。
  10. 根据权利要求1～7任一项所述抗菌低粘附的交联聚乙烯醇涂层在防污自清洁、液体运输以及动物体植入材料领域中的应用。
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