WO2020177065A1 - 一种通用型荧光流体光化学微反应器件及其3d打印制造方法 - Google Patents

一种通用型荧光流体光化学微反应器件及其3d打印制造方法 Download PDF

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WO2020177065A1
WO2020177065A1 PCT/CN2019/076906 CN2019076906W WO2020177065A1 WO 2020177065 A1 WO2020177065 A1 WO 2020177065A1 CN 2019076906 W CN2019076906 W CN 2019076906W WO 2020177065 A1 WO2020177065 A1 WO 2020177065A1
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reaction
channel
photochemical
fluorescent
light
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French (fr)
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张利静
陶胜洋
朱志刚
杨文博
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Dalian University of Technology
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Dalian University of Technology
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Priority to US17/054,051 priority patent/US11872556B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502715—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by interfacing components, e.g. fluidic, electrical, optical or mechanical interfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
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    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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    • B33Y10/00—Processes of additive manufacturing
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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00934—Electromagnetic waves
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    • B01L2300/0877—Flow chambers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01L2300/08—Geometry, shape and general structure
    • B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
    • B01L2300/0883—Serpentine channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
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    • B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/24—Coupling light guides
    • G02B6/42—Coupling light guides with opto-electronic elements

Definitions

  • the invention belongs to the technical field of photochemical reactor research, and relates to a 3D printing fluorescent fluid photochemical microreactor. Specifically, it relates to a method of using transparent light-curable resin 3D printing to manufacture microreactors with wavelength conversion function that can be applied to different photochemical reactions.
  • the photochemical microreactor is prepared by combining the light-transmitting microreactor and the external irradiating light source, which can effectively improve the conversion rate and selectivity of the photochemical reaction.
  • the progress of the reaction is directly related to the wavelength of the external radiation source (especially chemical reactions excited by visible light), so different photochemical reactions often require different irradiation light source.
  • light sources with special wavelengths are difficult to obtain or expensive, which greatly limits the application of photochemical microreactors.
  • Fluorescent dyes and quantum dots often have a wider absorption band and a narrower emission band. These substances can generate a strong emission light of a certain wavelength by collecting excitation light of different wavelengths, thereby playing the functions of light collection and wavelength conversion. Using this feature, people can use cheap LED light sources and even broad-spectrum light sources such as sunlight to initiate photochemical reactions.
  • fluorescent light-concentrating microreactors are widely used, that is, fluorescent materials are dispersed in a transparent medium, and then microchannels are constructed in the interior by the method of turning molds, and the microreactors are formed after curing. In this reactor, the fluorescent material absorbs light from an external light source and emits fluorescence of the desired wavelength.
  • This type of reactor solves the problem of wavelength matching in the photochemical reaction process.
  • this type of reactor has the following problems: First, because the fluorescent dye is doped into the reactor matrix from the beginning, it cannot be separated, so this type of reactor is only suitable for a specific light reaction; secondly, the fluorescent dye Replacement and recycling are difficult to achieve; finally, the process of preparing the reactor by the over-molding method is complicated and time-consuming, and it is difficult to design a more complicated space structure.
  • 3D printing is an emerging additive manufacturing technology that can construct objects with complex spatial structures through layer-by-layer printing, and has the characteristics of rapid prototyping. With the help of the powerful space construction capabilities of 3D printing technology, a continuous stream photochemical microreactor with a light collection channel and a reactant channel can be processed and manufactured to form a universal photochemical microreactor with replaceable fluorescent materials.
  • the purpose of the present invention is to provide a method for preparing a universal fluorescent fluid photochemical microreactor by using 3D printing technology combined with fluorescent materials.
  • a general-purpose fluorescent fluid photochemical micro-reaction device comprising an optical channel 2, a reaction channel 1, an optical channel outlet, an optical channel inlet, a reaction channel outlet, and a reaction channel inlet; the optical channel 2 is filled with fluorescent fluid and the two ports are sealed The reaction channel 1 enters the reaction liquid inside, and the optical channel 2 is located around the reaction channel 1 to ensure the progress of the photochemical reaction.
  • the reaction channel 1 and the light channel 2 are both serpentine square tubes, and the light channels 2 are two sets, respectively arranged on the upper and lower sides of the reaction channel 1 in parallel.
  • the reaction channel 1 is a linear square tube, and the light channel 2 is a spiral round tube, wound around the outer circumference of the reaction channel 1.
  • the material of the universal fluorescent fluid photochemical micro-reaction device is transparent photosensitive resin 3.
  • the fluorescent material in the fluorescent fluid is fluorescent dye, fluorescent quantum dot or nanocrystal, and the solvent is water, ethanol, isopropanol, acetonitrile, ethyl acetate, DMF, toluene or dichloromethane.
  • the characteristic size (ie tube diameter or cross-sectional side length) of light channel 2 and reaction channel 1 is 0.5-1mm, and the material is transparent photosensitive resin 3. .
  • Figure 2 is a schematic diagram of a spiral fluorescent fluid photochemical microreactor.
  • a method for preparing a universal fluorescent fluid photochemical microreactor using 3D printing technology the specific steps are as follows:
  • the fluorescent fluid photochemical micro-reaction device is placed in a cylindrical light-shielding tube wrapped with a blue LED strip to form the final photochemical reaction device.
  • the reactants diphenylanthracene and the photocatalyst methylene blue can be injected into the reaction channel separately, and the oxidation conversion rate of the diphenylanthracene under the action of the fluorescent fluid is three times that of pure blue light.
  • FITC fluorescent dye fluorescein isothiocyanate

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Abstract

一种通用型荧光流体光化学微反应器件及其3D打印制造方法，属于光化学反应器研究技术领域。利用透明光敏树脂以及3D打印强大的空间构筑能力，制备了同时具有集光通道和反应通道的光化学微反应器件。将集光物质以流体形式引入到光通道中，既可以发挥集光和波长转换的作用，解决传统光化学反应器光源匹配的难题，又可以灵活更换集光物质以满足反应通道内不同光化学反应的需求，极大的扩展了反应器的应用范围。本发明光化学微反应器的制造简单、快速，可大规模生产，为研究反应的快速筛选、反应条件的优化以及反应机理等提供了便利。所用集光材料可回收再利用，降低了材料成本，且不污染环境。

Description

一种通用型荧光流体光化学微反应器件及其3D打印制造方法 技术领域
本发明属于光化学反应器研究技术领域，涉及到3D打印荧光流体光化学微反应器。具体涉及使用透明光固化树脂3D打印制造具有波长转换功能，可应用于不同光化学反应的微反应器的方法。
 背景技术
光化学反应是指在外界光源的照射下所发生的化学反应过程。光化学反应器作为光化学反应进行的场所, 其性能优劣对于光化学反应有十分重要的作用。光化学反应器中光源种类、反应器几何形状及反应器与光源间相互位置是直接影响光化学反应器性能的关键因素。近今年来微反应器由于反应体系的传质和传热过程获得极大改进，可使化学反应过程获得更高的转化率和收率而受到广泛关注。微反应器通常是指其内部流体通道或分散空间尺度在微米量级的微结构化学反应器。利用透光微反应器与外加辐照光源结合制备光化学微反应器，可以有效的提升光化学反应的转化率和选择性。然而在光化学反应中，由于受到量子力学基本原理的制约，反应的进行与否直接与外界辐照光源的波长有关（尤其是可见光激发的化学反应），因此针对不同光化学反应往往需要不同的辐照光源。而现实情况中，一些特殊波长的光源较难得到或是价格昂贵，这极大的限制了光化学微反应器的应用。
荧光染料和量子点往往具有较宽的吸收谱带和较窄的发射谱带。这些物质可以通过收集不同波长的激发光产生某一波长较强的发射光，从而起到集光和波长转换的功能。利用这一特征，人们可以利用廉价的LED光源甚至日光等广谱光源来引发光化学反应。目前应用较多的是荧光集光式微反应器，即将荧光材料分散到透明介质中，随后采用翻模的方法在其内部构筑微通道，经固化后形成微反应器。该反应器中，荧光材料吸收外加光源的光并发射所需波长的荧光。发射出来的荧光会在透明介质中以光波导的模式传输并聚焦到内置的微通道，从而促进微通道内的光化学反应的进行。这类反应器很好的解决了光化学反应过程中波长匹配的问题。但是这类反应器存在以下几个问题：首先，由于荧光染料一开始就掺杂到反应器基质中，无法分离，因此这类反应器只适用于某一特定的光反应；其次，荧光染料的更换和回收利用难以实现；最后，采用翻模法制备反应器过程繁杂，耗时长，且难以设计更加复杂的空间结构。这些因素到导致荧光集光式光化学微反应器制造成本高、普适性低，应用范围受到很大的限制。因此开发一种制备简单且多种光化学反应均能通用的集光式光化学微反应器就显得非常重要。
由于荧光材料采用掺杂方式进入反应器介质中而导致其被固定不能更换，若是将荧光材料以流体形式引入到微反应器内部，则有望解决上述问题。3D打印是一种新兴的增材制造技术，可通过逐层打印的方式来构造具有复杂空间结构的物体，且具有快速成型的特点。借助于3D打印技术强大的空间构筑能力，同时具有集光通道和反应物通道的连续流光化学微反应器可以被加工制造，形成荧光材料可更换的通用型光化学微反应器件。
 技术问题
本发明的目的是提供一种利用3D打印技术结合荧光材料制备通用型荧光流体光化学微反应器的方法。
 技术解决方案
本发明的技术方案：
一种通用型荧光流体光化学微反应器件，包括光通道2、反应通道1、光通道出口、光通道入口、反应通道出口和反应通道入口；所述的光通道2内部充满荧光流体，两端口密封；所述的反应通道1内部通入反应液，光通道2位于反应通道1周围，确保光化学反应的进行。
所述的反应通道1与光通道2均为蛇形方管，光通道2为两套，分别平行设置于反应通道1的上下两侧。
所述的反应通道1为直线型方管，所述的光通道2为螺旋形圆管，缠绕于反应通道1外周。
所述的通用型荧光流体光化学微反应器件的材质为透明光敏树脂3。
所述的荧光流体中的荧光材料为荧光染料、荧光量子点或纳米晶，溶剂为水、乙醇、异丙醇、乙腈、乙酸乙酯、DMF、甲苯或二氯甲烷。
一种通用型荧光流体光化学微反应器件的3D打印制造方法，步骤如下：
（1）使用Solidworks软件设计出微反应器件的模型，用3D打印机进行打印，光通道2和反应通道1的特征尺寸（即管径或截面边长）为0.5-1mm，材质为透明光敏树脂3。
（2）利用紫外光固化3D打印机打印出微反应器件。
（3）用乙醇和异丙醇混合液清洗微反应器件，并确保通道中无树脂残留，随后置于紫外灯下固化2-10小时。
（4）将荧光材料溶于溶剂中，浓度在0.1-1000 ppm，随后使用注射器将其注入光通道2中，并将光通道2两端封紧。则制备得到通用型荧光流体光化学微反应器件。
所述的3D打印机选用的层打印精度为0.025-0.1mm。
 有益效果
本发明的有益效果：本发明采用3D打印技术制备通用型光化学微反应器，为光化学反应的研究提供了简单高效的设备装置。一、光化学微反器的制作十分简便、成本低。二、荧光染料以流体形式进入光通道，反应后可方便的回收利用，避免了荧光材料的浪费和环境污染，节约成本。三、根据反应通道内不同反应对光波长的需求，可灵活的更换光通道内荧光材料的种类，大大拓宽了反应器中发生的化学反应的类型，普适性更强。
 附图说明
图1是蛇形荧光流体光化学微反应器的示意图。
图2是螺旋形荧光流体光化学微反应器的示意图。
图中：1反应通道；2光通道；3透明光敏树脂。
 本发明的实施方式
具体实施方式
下面结合附图和技术方案，进一步对本发明进行详细的描述。
一种利用3D打印技术制备通用型荧光流体光化学微反应器的方法，具体步骤如下：
实施例1（蛇形微反应器）
（1）使用SolidWorks软件设计微反应器模型，光微通道和反应微通道均为蛇形方管，其管道边长尺寸为1mm，通道长度为105mm，反应器整体尺寸为长8.2 cm，宽3cm，高1.5 cm。
（2）利用紫外光固化3D打印机打印出微反应器，其材质为透明光敏树脂。
（3）打印完成后，将反应器从工作平台上取下，放入乙醇和异丙醇的混合溶液中进行清洗，尤其注意清洗微通道内部，保证无树脂残留。随后放置于紫外灯下固化4h。
（4）将荧光染料Lumogen F Red 305溶于乙醇溶液中，浓度为200 ppm，使用注射器将其注射到光通道中。
（5）将该荧光流体光化学微反应器件置于内部缠绕蓝光LED灯带的圆柱形遮光筒内，形成最终的光化学反应装置。对于反应二苯基蒽的催化氧化，可将反应物二苯基蒽和光催化剂亚甲基蓝分别注入到反应通道，在荧光流体的作用下二苯基蒽的氧化转化率是单纯蓝光下的3倍。
实施例2（螺旋形微反应器）
（1）使用SolidWorks软件设计微反应器模型。光微通道为螺旋形圆管，其管道直径为1mm，通道长度为105 mm。反应通道为直线型方管，管道边长为1密码，通道长度为56mm。反应器整体尺寸为长7cm，宽3.5cm，高1.5 cm。
（2）利用紫外光固化3D打印机打印出微反应器，其材质为透明光敏树脂。
（3）打印完成后，将反应器从工作平台上取下，放入乙醇和异丙醇的混合溶液中进行清洗，尤其注意清洗微通道内部，保证无树脂残留。随后放置于紫外灯下固化4h。
（4）将荧光染料异硫氰酸荧光素（FITC）溶于乙醇溶液中，浓度为400 ppm，使用注射器将其注射到光通道中。
（5）将该荧光流体光化学微反应器件置于内部缠绕蓝光LED灯带的圆柱形遮光筒内，形成最终的光化学反应装置。对于反应对甲基苯硫酚的氧化，可将反应物对甲基苯硫酚和光催化剂署红Y分别注入到反应通道，在荧光流体的作用下反应转化率是单纯蓝光下的1.8倍。

Claims (8)

  1. 一种通用型荧光流体光化学微反应器件，其特征在于，包括光通道（2）、反应通道（1）、光通道出口、光通道入口、反应通道出口和反应通道入口；所述的光通道（2）内部充满荧光流体，两端口密封；所述的反应通道（1）内部通入反应液，光通道（2）位于反应通道（1）周围，确保光化学反应的进行。
  2. 根据权利要求1所述的一种通用型荧光流体光化学微反应器件，其特征在于，所述的反应通道（1）与光通道（2）均为蛇形方管，光通道（2）为两套，分别平行设置于反应通道（1）的上下两侧。
  3. 根据权利要求1所述的一种通用型荧光流体光化学微反应器件，其特征在于，所述的反应通道（1）为直线型方管，所述的光通道（2）为螺旋形圆管，缠绕于反应通道（1）外周。
  4. 根据权利要求1、2或3所述的一种通用型荧光流体光化学微反应器件，其特征在于，所述的通用型荧光流体光化学微反应器件的材质为透明光敏树脂（3）。
  5. 根据权利要求1、2或3所述的一种通用型荧光流体光化学微反应器件，其特征在于，所述的荧光流体中的荧光材料为荧光染料、荧光量子点或纳米晶，溶剂为水、乙醇、异丙醇、乙腈、乙酸乙酯、DMF、甲苯或二氯甲烷。
  6. 根据权利要求4所述的一种通用型荧光流体光化学微反应器件，其特征在于，所述的荧光流体中的荧光材料为荧光染料、荧光量子点或纳米晶，溶剂为水、乙醇、异丙醇、乙腈、乙酸乙酯、DMF、甲苯或二氯甲烷。
  7. 一种通用型荧光流体光化学微反应器件的3D打印制造方法，其特征在于，步骤如下：
    （1）使用Solidworks软件设计出微反应器件的模型，用3D打印机进行打印，光通道（2）和反应通道（1）的管径或截面边长为0.5-1mm，材质为透明光敏树脂（3）；
    （2）利用紫外光固化3D打印机打印出微反应器件；
    （3）用乙醇和异丙醇混合液清洗微反应器件，并确保通道中无树脂残留，随后置于紫外灯下固化2-10小时；
    （4）将荧光材料溶于溶剂中，浓度在0.1-1000 ppm，随后使用注射器将其注入光通道（2）中，并将光通道（2）两端封紧；则制备得到通用型荧光流体光化学微反应器件。
  8. 根据权利要求7所述的一种通用型荧光流体光化学微反应器件的3D打印制造方法，其特征在于，所述的3D打印机选用的层打印精度为0.025-0.1mm。
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