WO2023102752A1 - 紫外线消毒器用密封胶塞及其制备方法 - Google Patents

紫外线消毒器用密封胶塞及其制备方法 Download PDF

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WO2023102752A1
WO2023102752A1 PCT/CN2021/136201 CN2021136201W WO2023102752A1 WO 2023102752 A1 WO2023102752 A1 WO 2023102752A1 CN 2021136201 W CN2021136201 W CN 2021136201W WO 2023102752 A1 WO2023102752 A1 WO 2023102752A1
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titanium dioxide
deposition
preparation
rubber
solution
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French (fr)
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陆妹妹
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无锡诚源环境科技有限公司
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Priority to PCT/CN2021/136201 priority Critical patent/WO2023102752A1/zh
Priority to CN202180003850.5A priority patent/CN116783399A/zh
Publication of WO2023102752A1 publication Critical patent/WO2023102752A1/zh

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    • 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
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/08—Radiation
    • A61L2/10—Ultraviolet radiation
    • 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
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/18—Radiation
    • A61L9/20—Ultraviolet radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B21/00—Means for preventing relative axial movement of a pin, spigot, shaft or the like and a member surrounding it; Stud-and-socket releasable fastenings

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  • the invention relates to the technical field of disinfection and sterilization, in particular to a sealing rubber plug for an ultraviolet sterilizer and a preparation method thereof.
  • Ultraviolet sterilizer is a device that uses ultraviolet light to sterilize and sterilize. It is widely used in the field of water treatment due to its high efficiency of full physical sterilization and no secondary pollution.
  • the UV resistance of the sealant plug directly determines the service life of the UV sterilizer.
  • the sealant plug is generally made of rubber. Under long-term ultraviolet radiation, the rubber will cause the cracking of the molecular bonds of the rubber, causing it to age, and the tensile and elongation at break are both reduced, which eventually leads to a decrease in its sealing performance. Therefore, the current service life of the sealing rubber plug is less than one year, which in turn causes water leakage to occur after the UV sterilizer is installed underwater for a period of time and causes equipment damage.
  • the object of the present invention is to prolong the service life of the sealing rubber plug, and provide a sealing rubber plug for ultraviolet sterilizer and a preparation method thereof.
  • the present invention provides a sealing rubber plug for an ultraviolet sterilizer, comprising a rubber substrate, the outer surface of which is coated with a titanium dioxide coating.
  • titanium dioxide by coating the outer surface of the rubber substrate (that is, the traditional sealing rubber plug) with a titanium dioxide coating, the photocatalytic properties of titanium dioxide are used to enhance the UV aging resistance of the sealing rubber plug, thereby prolonging its service life .
  • titanium dioxide also has antibacterial properties, which can promote the catalytic oxidation of ultraviolet rays to kill bacteria and viruses in water, so that the ultraviolet sterilizer has the high-efficiency sterilization performance of photophysics-photocatalysis-photochemistry.
  • the present invention also provides the preparation method of above-mentioned sealing rubber plug, comprises the following steps:
  • the rubber substrate with the titanium dioxide coating formed on the outer surface is taken out and sent to a vacuum oven for heat treatment for a second time, and the sealing rubber plug is obtained after cooling to normal temperature.
  • the deposition solution is obtained by mixing (NH 4 ) 2 TiF 6 solution and H 3 BO 3 in proportion.
  • Mixing (NH 4 ) 2 TiF 6 solution with H 3 BO 3 makes it easier to form a titanium dioxide coating, and it can be carried out in a low temperature environment, which reduces the requirements for experimental conditions and can also ensure the performance of the rubber substrate.
  • TiO 2 nanocrystals with a particle size of nanometers are added to the deposition solution as a crystallization inducer, and the mass fraction of TiO 2 nanocrystals is 0.2-3%.
  • Adding TiO 2 nanocrystals as a crystallization inducer in the deposition solution can promote (NH 4 ) 2 TiF 6 solution and H 3 BO 3 to form a titanium dioxide coating more quickly, and accelerate the coating efficiency, that is, the preparation efficiency of the sealant plug.
  • the timing of adding the inducer can be added during the process of preparing the deposition solution, or can be added after the rubber substrate is placed in the deposition solution.
  • a stirrer is used to stir during the deposition process. Stirring during the deposition process can make the thickness of the titanium dioxide coating formed on the surface of the rubber substrate more uniform, and prevent the service life of the sealant plug from being reduced due to the unevenness of the titanium dioxide coating during use.
  • stirring and heating are performed during deposition. Simultaneous heating during stirring can further contribute to the synthesis of titanium dioxide and accelerate coating efficiency.
  • a layer of titanium dioxide coating is uniformly deposited on the surface of the rubber substrate by liquid deposition technology, and the anti-ultraviolet performance of the existing commercially available rubber is enhanced by virtue of the anti-ultraviolet and antibacterial properties of titanium dioxide. Extend the service life of the UV sterilizer and realize the completely reliable operation of the UV sterilizer.
  • Fig. 1 is the flowchart of the preparation method of fluorine rubber in the embodiment.
  • the sealing rubber plug provided in this embodiment includes a rubber substrate, and the outer surface of the rubber substrate is coated with a titanium dioxide coating.
  • the rubber substrate is preferably a fluororubber substrate, because fluororubber itself has stronger UV resistance than other rubbers.
  • Titanium dioxide has antibacterial and photocatalytic properties. Utilizing the antibacterial and photocatalytic properties of titanium dioxide can not only enhance the bactericidal properties of ultraviolet sterilizers, but also promote the catalytic oxidation of ultraviolet rays to kill bacteria and viruses in water, making ultraviolet sterilizers with photophysics-light Catalytic-photochemical three-effect integrated high-efficiency bactericidal performance. According to calculations, the sealing rubber plug coated with titanium dioxide coating can increase the sterilization and disinfection efficiency by 20-30%, and the anti-ultraviolet aging time of fluororubber can be increased by more than three times. That is to say, by coating the titanium dioxide coating on the outer surface of the rubber substrate, not only the service life of the sealant plug can be extended, but also the disinfection and sterilization performance can be enhanced.
  • the method for preparing above-mentioned ultraviolet sterilizer with sealant plug comprises the following steps:
  • Step 1 preparing a deposition solution capable of synthesizing titanium dioxide.
  • the deposition solution capable of synthesizing titanium dioxide generally refers to the formation of titanium dioxide after chemical reaction of two or more substances. In this embodiment, it is preferably obtained by mixing (NH 4 ) 2 TiF 6 solution and H 3 BO 3 in proportion.
  • the concentration of (NH 4 ) 2 TiF 6 solution can be 0.1-2mol/L, and the concentration of H 3 BO 3 can be It is 0.2-4mol/L, mixed according to the volume ratio of 0.5-3:1.
  • the low-temperature preparation method is preferred. It can be prepared from (NH 4 ) 2 TiF 6 solution and H 3 BO 3 at room temperature and dried at 80-120°C. Under this scheme, it not only adapts to the application scene of fluororubber, the temperature is generally lower than 120 °C, but also avoids the denaturation of fluororubber at a temperature higher than 250 °C, and ensures the fluororubber under the condition of reducing the preparation requirements. performance reliability.
  • nanoscale TiO2 nanocrystals can be added in the deposition solution as a crystallization inducer.
  • the mass fraction of TiO 2 nanocrystals can be 0.2-3%.
  • Step 2 immersing the rubber substrate in the deposition solution, so that after a period of time (first time) of deposition, a titanium dioxide coating is formed on the outer surface of the rubber substrate.
  • the surface of the rubber substrate needs to be cleaned before placing the rubber substrate in the deposition solution.
  • stirring may be performed during deposition, or heating may be performed while stirring.
  • Step 3 taking out the rubber substrate with the titanium dioxide coating formed on the outer surface and sending it to a vacuum oven for heat treatment for a period of time (second time), and cooling to normal temperature to obtain the sealing rubber plug.
  • the titanium dioxide coating is formed on the surface, it is baked in a vacuum oven to make the titanium dioxide coating more stable on the surface of the rubber substrate and not easy to fall off.
  • an aging test was also carried out. Specifically, the TiO2 - coated fluororubber was placed in an ultraviolet aging test box, and the ultraviolet aging test was carried out according to the standard GB/T16585-1996. The equivalent duration of the fluororubber prepared in each test example was not less than 3 years.
  • the fluorororubber prepared in this example can not only increase the service life, but also improve the sterilization effect when used in ultraviolet sterilization equipment. After testing, the sterilization and disinfection efficiency of the fluorine rubber prepared in each test example is increased by 20-30%. Specifically, the prepared fluororubber was irradiated under the same ultraviolet radiation dose (20mJ/cm 2 ), and it was found that the time for killing bacteria to reach the number (10 3 /L) stipulated in the first-level sewage standard was shortened by 20 -30%, so it is judged that the efficiency of sterilization and disinfection has increased by 20-30%.
  • the fluorine rubber prepared in Test Example 2 is irradiated under the environment of the same ultraviolet radiation dose (20mJ/cm 2 ), the inlet flow of sewage is 219m3/h, and the required sterilization time of the required ultraviolet lamp tube is usually 1.49s.
  • the use of fluorine rubber containing titanium dioxide coating shortens the time for killing bacteria to reach the number specified in the first-level sewage discharge standard (10 3 /L) to 1.12s, and the sterilization and disinfection efficiency increases by about 24.8%.

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Abstract

一种紫外线消毒器用密封胶塞及其制备方法，该密封胶塞包括橡胶基材，所述橡胶基材的外表面涂覆有二氧化钛涂层。制备方法包括：制备能合成二氧化钛的沉积液；将橡胶基材浸没于所述沉积液中，使得沉积第一时间后，橡胶基材的外表面形成二氧化钛涂层；将外表面形成有二氧化钛涂层的橡胶基材取出送至真空烘箱中热处理第二时间，冷却至常温后即得所述密封胶塞。利用二氧化钛的抗菌和光催化特性，既可以增强紫外线消毒器的杀菌特性，也可以促进紫外线的催化氧化杀灭水体中的细菌和病毒，使得紫外线消毒器具备光物理-光催化-光化学三效一体的高效杀菌性能，杀菌消毒效率提升20-30％，氟橡胶抗紫外老化时长提升三倍以上。

Description

紫外线消毒器用密封胶塞及其制备方法 技术领域
本发明涉及消毒杀菌技术领域，特别涉及一种紫外线消毒器用密封胶塞及其制备方法。
背景技术
紫外线消毒器是利用紫外线进行消毒杀菌的装置，以其全物理杀菌的高效性和无二次污染等特点被广泛应用于水处理领域。然而，由于紫外灯管、套管需要经过防水密封后才能安装运行在水处理工程中，因此密封胶塞的抗紫外性能优劣直接决定了紫外线消毒器的使用寿命。密封胶塞一般采用的是橡胶，橡胶在紫外线的长期照射下，会引起橡胶分子键的裂解，致使其老化，拉伸与断裂伸长率均减小，最终导致其密封性能下降。因此，目前密封胶塞的使用寿命不足一年，继而导致紫外消毒器在水下安装后运行一段时间就会出现漏水而引起设备损坏。
发明内容
本发明的目的在于延长密封胶塞的使用寿命，提供一种紫外线消毒器用密封胶塞及其制备方法。
一方面，本发明提供了一种紫外线消毒器用密封胶塞，包括橡胶基材，所述橡胶基材的外表面涂覆有二氧化钛涂层。
上述方案中，通过在橡胶基材(也就是传统的密封胶塞)的外表面涂覆有二氧化钛涂层，利用二氧化钛的光催化特性，增强密封胶塞的抗紫外老化能力，继而延长其使用寿命。另外，二氧化钛还具有抗菌特性，可以促进紫外线的催 化氧化杀灭水体中的细菌和病毒，使得紫外线消毒器具备光物理-光催化-光化学三效一体的高效杀菌性能。
另一方面，本发明还提供了上述密封胶塞的制备方法，包括以下步骤：
制备能合成二氧化钛的沉积液；
将橡胶基材浸没于所述沉积液中，使得沉积第一时间后，橡胶基材的外表面形成二氧化钛涂层；
将外表面形成有二氧化钛涂层的橡胶基材取出送至真空烘箱中热处理第二时间，冷却至常温后即得所述密封胶塞。
优选地，所述沉积液由(NH 4) 2TiF 6溶液与H 3BO 3按照比例混合而得。采用(NH 4) 2TiF 6溶液与H 3BO 3混合，更容易形成二氧化钛涂层，且可以在低温环境下进行，降低对实验条件的要求，同时还可以保障橡胶基材的性能。
优选地，在所述沉积液中添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的质量分数为0.2-3％。沉积液中添加TiO 2纳米晶作为结晶诱导剂，可以促进(NH 4) 2TiF 6溶液与H 3BO 3更快速地形成二氧化钛涂层，加快涂覆效率，即加快密封胶塞的制备效率。诱导剂的添加时机，可以是在制备沉积液的过程中添加，也可以是在将橡胶基材置于沉积液之后再添加。
优选地，将橡胶基材浸没于所述沉积液中后，在沉积过程中使用搅拌器搅拌。沉积过程中进行搅拌，可以使得橡胶基材表面形成的二氧化钛涂层厚度更加均匀，避免密封胶塞在使用过程中由于二氧化钛涂层的不均匀性而降低使用寿命。
优选地，在沉积过程中进行搅拌并加热。搅拌过程中同时加热，可以进一 步有助于二氧化钛的合成，加快涂覆效率。
与现有技术相比，本发明方法及系统，具有以下技术优势：
通过在全橡胶塞表面复合抗紫外涂层，利用液相沉积技术在橡胶基材表面均匀沉积一层二氧化钛涂层，借助二氧化钛的抗紫外和抗菌特性，增强现有市售橡胶的抗紫外性能，延长紫外线消毒器的使用寿命，实现紫外线消毒器的完全可靠运行。
本发明所具有的其他优势将会在具体实施例中进行相应说明。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为实施例中氟橡胶制备方法的流程图。
具体实施方式
下面将结合本发明实施例中附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。因此，以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明的实施例，本领域技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
为了延长紫外线消毒器用密封胶塞的使用寿命，减缓被紫外线分解的速度，本实施例中提供的密封胶塞，包括橡胶基材，所述橡胶基材的外表面涂覆有二 氧化钛涂层。橡胶基材优选采用氟橡胶基材，因为氟橡胶本身抗紫外性能比其他橡胶更强。
二氧化钛具有抗菌和光催化特性，利用二氧化钛的抗菌和光催化特性，既可以增强紫外线消毒器的杀菌特性，也可以促进紫外线的催化氧化杀灭水体中的细菌和病毒，使得紫外线消毒器具备光物理-光催化-光化学三效一体的高效杀菌性能。经测算，涂覆有二氧化钛涂层的密封胶塞，杀菌消毒效率提升20-30％，氟橡胶抗紫外老化时长提升三倍以上。也就是说，通过在橡胶基材外表面涂覆二氧化钛涂层，不仅可以延长密封胶塞的使用寿命，而且还可以增强消毒杀菌性能。
请参阅图1，制备上述紫外线消毒器用密封胶塞的方法，包括以下步骤：
步骤1，制备能够合成二氧化钛的沉积液。
能够合成二氧化钛的沉积液一般是指两种或以上物质经过化学反应后生成二氧化钛。本实施例中优选由(NH 4) 2TiF 6溶液与H 3BO 3按照比例混合而得，(NH 4) 2TiF 6溶液的浓度可以是0.1-2mol/L，H 3BO 3的浓度可以是0.2-4mol/L，按照体积比0.5-3:1的比例混合。
(NH 4) 2TiF 6溶液与H 3BO 3生成TiO 2的反应式如下：
[TiF 6] 2-+6H 2O→[Ti(OH) 6] 2-+6HF
H 3BO 3+4HF→BF 4 -+H 3O ++2H 2O
[Ti(OH) 6] 2-+2H 3O +→TiO 2+6H 2O
(NH 4) 2TiF 6+2H 2O→TiO 2+2NH 4F+4HF
虽然制备二氧化钛的方法较多，但是优选采用低温制备法，由(NH 4) 2TiF 6溶 液与H 3BO 3可在室温下制备，在80-120℃温度环境下干燥。此种方案下，既适应了氟橡胶的应用场景，温度一般低于120℃，而且还避免了氟橡胶在温度高于250℃会变性的情况，在降低制备要求的情况下还保障了氟橡胶的性能可靠性。
为了加速反应，可以在沉积液中添加纳米级的TiO 2纳米晶作为结晶诱导剂。TiO 2纳米晶的质量分数可以为0.2-3％。
步骤2，将橡胶基材浸没于所述沉积液中，使得沉积一段时间(第一时间)后，橡胶基材的外表面形成二氧化钛涂层。
需要注意的是，为保障二氧化钛涂层在橡胶基材表面的稳定性，在将橡胶基材置于沉积液中之前，橡胶基材的表面需要事先清洗干净。
为了加速沉积，可以在沉积过程中进行搅拌，也可以在搅拌的同时进行加热。
步骤3，将外表面形成有二氧化钛涂层的橡胶基材取出送至真空烘箱中热处理一段时间(第二时间)，冷却至常温后即得所述密封胶塞。
表面形成二氧化钛涂层后，再利用真空烘烤箱进行烘烤，可以使得二氧化钛涂层在橡胶基材表面更稳定，不容易脱落。
为了更详细的对制备方法进行阐述，下面提供了部分试验例。
试验例1
将0.1mol/L的(NH 4) 2TiF 6溶液与0.2mol/L的H 3BO 3按照体积比2:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为1％，连续搅拌3小时(h)，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶 基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌并加热，沉积6h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在100℃左右环境下热处理24h，制备出具有TiO 2涂层的氟橡胶。
试验例2
将0.2mol/L的(NH 4) 2TiF 6溶液与0.4mol/L的H 3BO 3按照体积比2:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为1％，连续搅拌3小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌并加热，沉积6h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在100℃左右环境下热处理24h，制备出具有TiO 2涂层的氟橡胶。
试验例3
将0.2mol/L的(NH 4) 2TiF 6溶液与0.4mol/L的H 3BO 3按照体积比2:1的比例混合，连续搅拌3小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶基材可以完全浸没在沉积液中，沉积12h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在100℃左右环境下热处理24h，制备出具有TiO 2涂层的氟橡胶。
试验例4
将0.6mol/L的(NH 4) 2TiF 6溶液与1.0mol/L的H 3BO 3按照体积比2.5:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为0.2％，连续搅拌1小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶 基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌并加热，沉积6h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在120℃左右环境下热处理18h，制备出具有TiO 2涂层的氟橡胶。
试验例5
将1.0mol/L的(NH 4) 2TiF 6溶液与2.0mol/L的H 3BO 3按照体积比1.2:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为0.5％，连续搅拌1小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌，沉积10h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在120℃环境下热处理18h，制备出具有TiO 2涂层的氟橡胶。
试验例6
将1.0mol/L的(NH 4) 2TiF 6溶液与2.0mol/L的H 3BO 3按照体积比1:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为2％，连续搅拌1小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌，沉积12h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在110℃环境下热处理18h，制备出具有TiO 2涂层的氟橡胶。
试验例7
将2mol/L的(NH 4) 2TiF 6溶液与3.2mol/L的H 3BO 3按照体积比3:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为1.5％，连续搅拌2小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌并加热，沉积8h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在80℃环境下热处理24h，制备出具有TiO 2涂层的氟橡胶。
试验例8
将2mol/L的(NH 4) 2TiF 6溶液与4mol/L的H 3BO 3按照体积比4:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的添加量为质量分数为3％，连续搅拌3小时，制备获得沉积液。
将氟橡胶基材用无水乙醇清洗至表面干净后，置于沉积液中，确保氟橡胶基材可以完全浸没在沉积液中，通过磁力搅拌器进行搅拌并加热，沉积8h后，将表面涂覆有二氧化钛涂层的氟橡胶基材取出送至真空烘箱中，在80℃环境下热处理24h，制备出具有TiO 2涂层的氟橡胶。
为了验证各个试验例制备出的具有TiO 2涂层的氟橡胶的抗紫外线老化性能，还进行了老化试验。具体是，将沉积好TiO 2涂层的氟橡胶置于紫外老化试验箱中，依据标准GB/T16585-1996进行紫外老化测试，各个试验例制备所得的氟橡胶等效时长不低于3年。
另外，本实施例制备的氟橡胶，不仅可以提高使用寿命，而且用于紫外杀菌设备中，还可以提高杀菌效果。经过测验，各个试验例制备所得的氟橡胶的杀菌消毒效率提升20-30％。具体是，将制备所得的氟橡胶在同等紫外辐射剂量(20mJ/cm 2)环境下进行照射，得出将细菌杀灭达到一级排污标准规定的数量(10 3个/L)的时间缩短20-30％，由此判定杀菌消毒效率提升20-30％。
例如将试验例2制备所得的氟橡胶在同等紫外辐射剂量(20mJ/cm 2)环境下 进行照射，污水的进口流量为219m3/h，通常所需紫外灯管的需求杀菌时间为1.49s，由于使用含有二氧化钛涂层的氟橡胶，使得将细菌杀灭达到一级排污标准规定的数量(10 3个/L)的时间缩短为1.12s,杀菌消毒效率提升约24.8％。
经过对各个试验例(包括本文中未提及的试验例)进行抗老化试验发现，将0.2mol/L的(NH 4) 2TiF 6溶液与0.4mol/L的H 3BO 3按照体积比2:1的比例混合，添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，且TiO 2纳米晶的添加量为质量分数为1％，连续搅拌3小时，制备获得沉积液，由该沉积液沉积所得的。二氧化钛涂层的氟橡胶效果最好。
理论分析，(NH 4) 2TiF 6溶液与H 3BO 3的体积比过大会导致钛源含量增多，使得沉积的二氧化钛薄膜较厚，容易出现团聚和孔隙，引起局部不均匀，减少使用，而且还存在钛源浪费问题；体积比过小又会导致H 3BO 3含量增多，使得沉积的二氧化钛薄膜较薄，在后期清洗和丝杠摩擦等流程中都会减少使用寿命。此外，TiO 2纳米晶作为诱导剂，添加的诱导剂质量分数过多会导致沉积二氧化钛的反应速率太快，不利于薄膜的均匀制备；过少或没有会导致反应速率慢，但是相对于薄膜不均匀性会降低氟橡胶的使用寿命而言，宁可牺牲反应时间来换取更长的使用寿命。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应所述以权利要求的保护范围为准。

Claims (10)

  1. 一种紫外线消毒器用密封胶塞，其特征在于，包括橡胶基材，所述橡胶基材的外表面涂覆有二氧化钛涂层。
  2. 根据权利要求1所述的紫外线消毒器用密封胶塞，其特征在于，所述橡胶基材为氟橡胶基材。
  3. 权利要求1所述的紫外线消毒器用密封胶塞的制备方法，其特征在于，包括以下步骤：
    制备能合成二氧化钛的沉积液；
    将橡胶基材浸没于所述沉积液中，使得沉积第一时间后，橡胶基材的外表面形成二氧化钛涂层；
    将外表面形成有二氧化钛涂层的橡胶基材取出送至真空烘箱中热处理第二时间，冷却至常温后即得所述密封胶塞。
  4. 根据权利要求3所述的制备方法，其特征在于，所述沉积液由(NH 4) 2TiF 6溶液与H 3BO 3按照比例混合而得。
  5. 根据权利要求4所述的制备方法，其特征在于，所述沉积液由0.1-2mol/L的(NH 4) 2TiF 6溶液与0.2-4mol/L的H 3BO 3，按照体积比1.2-4:1的比例混合。
  6. 根据权利要求5所述的制备方法，其特征在于，在所述沉积液中添加粒度在纳米级的TiO 2纳米晶作为结晶诱导剂，TiO 2纳米晶的质量分数为0.2-3％。
  7. 根据权利要求3所述的制备方法，其特征在于，将橡胶基材浸没于所述沉积液中后，在沉积过程中使用搅拌器搅拌。
  8. 根据权利要求7所述的制备方法，其特征在于，在沉积过程中进行搅拌并加热。
  9. 根据权利要求3所述的制备方法，其特征在于，外表面形成有二氧化钛涂层的橡胶基材在80-120℃环境下热处理。
  10. 根据权利要求3所述的制备方法，其特征在于，所述第一时间为6-12小时，和/或，所述第二时间为24-48小时。
PCT/CN2021/136201 2021-12-07 2021-12-07 紫外线消毒器用密封胶塞及其制备方法 WO2023102752A1 (zh)

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CN202165604U (zh) * 2011-07-26 2012-03-14 浙江吉利汽车研究院有限公司 一种车用密封条
CN202624885U (zh) * 2012-05-04 2012-12-26 江苏润德医用材料有限公司 橡胶瓶塞
CN104390005A (zh) * 2014-11-19 2015-03-04 苏州北开生化设备有限公司 一种用于制药设备的密封圈
CN210736891U (zh) * 2018-07-16 2020-06-12 海南大学 一种橡胶表面的抗紫外耐磨复合膜
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JP2002306595A (ja) * 2001-04-13 2002-10-22 Fine Rubber Kenkyusho:Kk 医薬品、医療用具品用ゴム栓
CN1663684A (zh) * 2004-03-02 2005-09-07 方侃 纳米二氧化钛薄膜的制备方法
CN202165604U (zh) * 2011-07-26 2012-03-14 浙江吉利汽车研究院有限公司 一种车用密封条
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