CN1772356A - A kind of chiral molecularly imprinted fiber composite membrane and its preparation method and application - Google Patents

Abstract

The present invention discloses composite fiber membrane with chiral molecular imprint and its preparation process and application. The composite fiber membrane with chiral molecular imprint has excellent identifying selectivity. For example, the composite fiber membrane with L-DBTA as template molecule has high identifying selectivity on L-DBTA only, low identifying selectivity on other compounds and separation factor on racemic L, D-DBTA solution up to 2.7. Altering the temperature molecules can obtain different composite fiber membrane for separating several kinds of racemic compounds.

Description

Translated fromChinese

一种手性分子印迹纤维复合膜及其制备方法和应用A kind of chiral molecularly imprinted fiber composite membrane and its preparation method and application

技术领域technical field

本发明涉及一种分子印迹复合膜的制备方法，具体地说，本发明涉及一种手性分子印迹复合膜的制备方法。The invention relates to a method for preparing a molecularly imprinted composite membrane, in particular to a method for preparing a chiral molecularly imprinted composite membrane.

背景技术Background technique

分子印迹技术(Molecular Imprinting Technique)是利用分子印迹聚合物对印迹分子立体结构与形状具有的“记忆”功能进行特定分子识别的一种技术，因此具有预定性和识别性，自1993年Mosbach等在《Nature》上发表了有关可以分离茶碱分子印迹聚合物报道以来，得到了迅速发展，成为化学、生物学、高分子材料、医学等学科的交叉领域，在色谱固定相、固相萃取、膜分离、免疫分析、抗体模拟、仿生物传感器、催化剂和合成酶等方面表现出良好的应用前景。Molecular Imprinting Technique (Molecular Imprinting Technique) is a technology that uses molecularly imprinted polymers to carry out specific molecular recognition on the "memory" function of the three-dimensional structure and shape of imprinted molecules. Therefore, it is predetermined and recognizable. Since 1993, Mosbach et al. Since the report on molecularly imprinted polymers that can separate theophylline was published in "Nature", it has developed rapidly and has become an interdisciplinary field of chemistry, biology, polymer materials, medicine and other disciplines. Separation, immunoassay, antibody simulation, imitation biosensor, catalyst and synthetic enzyme have shown good application prospects.

以手性化合物作为印迹分子的分子印迹技术是MIT的一个重要分支，称为手性分子印迹技术，它利用手性分子印迹聚合物对手性印迹分子的“记忆”功能进行手性识别，是近年来手性分离领域具有应用和开发价值的一种新技术。Molecular imprinting technology using chiral compounds as imprinted molecules is an important branch of MIT, called chiral molecular imprinted technology, which uses chiral molecularly imprinted polymers to perform chiral recognition of the "memory" function of chiral imprinted molecules. It is a new technology with application and development value in the field of chiral separation.

通过高分子聚合物膜表面化学接枝或改性的方法可以得到不同分离性能的膜材料。以微滤或超滤膜作为支撑体，将分子印迹聚合物接枝到膜的表面，可以获得对特定印迹分子具有识别作用的不对称复合膜。Nidal等通过光聚合的方法在溶剂中将3’，5’-环腺苷酸分子印迹聚合物接枝到聚偏氟乙烯超滤膜表面，制备出了对3’，5’-环腺苷酸分子具有识别特性的分子印迹复合膜。Membrane materials with different separation properties can be obtained by chemically grafting or modifying the surface of polymer membranes. Using microfiltration or ultrafiltration membranes as supports, molecularly imprinted polymers are grafted onto the surface of the membranes to obtain asymmetric composite membranes that can recognize specific imprinted molecules. Nidal et al. grafted 3', 5'-cyclic adenosine molecularly imprinted polymer onto the surface of polyvinylidene fluoride ultrafiltration membrane in a solvent by photopolymerization, and prepared 3', 5'-cyclic adenosine A molecularly imprinted composite membrane with recognition properties for acid molecules.

通常，分子印迹复合膜的制备步骤可分为三步：首先将印迹分子以及适量的功能单体溶解在溶剂中，使印迹分子和功能单体充分结合；其次通过一定的方法固定于基膜表面，再在一定温度或紫外光照条件下聚合形成表面印迹聚合物；最后洗脱印迹分子，形成具有基膜支撑的表面手性印迹聚合物膜。Generally, the preparation steps of molecularly imprinted composite membranes can be divided into three steps: first, dissolve the imprinted molecules and an appropriate amount of functional monomers in a solvent, so that the imprinted molecules and functional monomers are fully combined; secondly, fix them on the basement membrane surface by a certain method , and then polymerized at a certain temperature or under ultraviolet light to form a surface imprinted polymer; finally, the imprinted molecules were eluted to form a surface chiral imprinted polymer film supported by a basement membrane.

Nidal等制备的复合膜是以非手性化合物为印迹分子制备的分子印迹复合膜，如果改用手性化合物作为印迹分子来制备手性分子印迹复合膜，则是一种新的制备方法，可以将膜分离技术的条件温和、操作简单、易于连续化等特点与手性分子印迹技术的手性识别性能结合起来，实现快速、便捷的手性化合物的分离。The composite membrane prepared by Nidal et al. is a molecularly imprinted composite membrane prepared with achiral compound as the imprinted molecule. If chiral compound is used as the imprinted molecule to prepare the chiral molecularly imprinted composite membrane, it is a new preparation method, which can Combining the characteristics of mild conditions, simple operation, and easy serialization of membrane separation technology with the chiral recognition performance of chiral molecular imprinting technology, rapid and convenient separation of chiral compounds can be achieved.

一般情况下，要得到理想的具有基膜支撑且具有手性选择性的膜是比较困难的，主要有如下因素的影响：1)基膜材料的选择；2)分子印迹聚合物的制备；3)复合条件的确定。In general, it is difficult to obtain an ideal membrane with basement membrane support and chiral selectivity, mainly due to the following factors: 1) selection of basement membrane material; 2) preparation of molecularly imprinted polymers; 3. ) Determination of composite conditions.

目前，手性拆分方法大多限于分析，用于工业生产的方法不多，而且具有很大的局限性。一般来说，一种特定的手性拆分方法只对某种手性化合物的拆分有效，而对其它手性化合物的拆分无效，共享性差，难以连续化操作，成本相对较高，拆分过程往往存在很大的盲目性(如对手性拆分配体试剂的选择)。At present, chiral resolution methods are mostly limited to analysis, and there are not many methods used in industrial production, and they have great limitations. Generally speaking, a specific chiral resolution method is only effective for the resolution of certain chiral compounds, but not for other chiral compounds. The sharing is poor, it is difficult to operate continuously, and the cost is relatively high. There is often a lot of blindness in the separation process (such as the choice of chiral separation ligand reagents).

手性分子印迹复合膜将对手性分子的识别性、特定性和膜的可连续化操作、通量大等特点结合起来，制备具有手性拆分性能的复合膜，是一种潜在的、高效的、新型的手性拆分手段，可以减少选择手性配体时的盲目性，使手性拆分连续化操作。另外，由于手性分子印迹复合膜的复合层具有特殊识别性能的“空腔结构”，因此其分离性能与其它表面改性所得到的复合膜完全不同，选择性更高。The chiral molecularly imprinted composite membrane combines the recognition and specificity of chiral molecules with the characteristics of continuous operation and large flux of the membrane to prepare a composite membrane with chiral resolution performance. It is a potential and efficient The new and new chiral resolution method can reduce the blindness in the selection of chiral ligands and make the chiral resolution continuous operation. In addition, because the composite layer of the chiral molecularly imprinted composite membrane has a "cavity structure" with special recognition properties, its separation performance is completely different from other composite membranes obtained by surface modification, and the selectivity is higher.

因此，研究开发一种手性分子印迹纤维复合膜的制备方法，将具有十分重要的意义。Therefore, it will be of great significance to research and develop a preparation method of chiral molecularly imprinted fiber composite membrane.

发明内容Contents of the invention

本发明需要解决的技术问题是公开一种手性分子印迹纤维复合膜及其制备方法和应用，以满足有关方面的需要。The technical problem to be solved in the present invention is to disclose a chiral molecularly imprinted fiber composite membrane and its preparation method and application, so as to meet the needs of related parties.

本发明的方法包括如下步骤：Method of the present invention comprises the steps:

(1)膜表面涂覆热引发剂：(1) The surface of the film is coated with a thermal initiator:

将高分子纤维膜与含有引发剂的溶液接触，然后晾干，获得膜表面涂覆有热引发剂的高分子纤维膜；The polymer fiber membrane is contacted with a solution containing an initiator, and then dried to obtain a polymer fiber membrane coated with a thermal initiator on the surface of the membrane;

所说的高分子纤维膜为中空纤维膜或平板超滤纤维膜，膜材料选自聚砜(PSF)、聚醚砜(PES)、聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚酰胺或纤维素或及衍生物等中的一种；The polymer fiber membrane is a hollow fiber membrane or a flat ultrafiltration fiber membrane, and the membrane material is selected from polysulfone (PSF), polyethersulfone (PES), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), One of polyamide or cellulose or its derivatives;

所说的中空纤维基膜最好具有如下的性能参数：   外径(μm)   1000～1400   壁厚(μm)   200～300   孔隙率，％   80～90   纯水通量，L/m².h   200～300Said hollow fiber base membrane preferably has the following performance parameters: Outer diameter (μm) 1000～1400 Wall thickness (μm) 200～300 Porosity,% 80～90 Pure water flux, L/m² .h 200～300

所说的含有引发剂的溶液中，引发剂的质量百分比含量为0.05～10％；In the solution containing the initiator, the mass percent content of the initiator is 0.05% to 10%;

所说的引发剂包括偶氮二异丁腈、苯甲酰过氧化物、苯甲基二甲基缩醛、偶氮二甲基戊腈、4，4-偶氮(4-腈基戊酸)或过硫酸铵等中的一种；Said initiator includes azobisisobutyronitrile, benzoyl peroxide, benzyl dimethyl acetal, azodimethylvaleronitrile, 4,4-azo (4-cyanovaleric acid ) or ammonium persulfate, etc.;

所说的溶剂包括乙腈或环己烷等中的一种或其混合物；Said solvent comprises one or its mixture in acetonitrile or hexanaphthene etc.;

(2)手性分子印迹复合膜的制备：(2) Preparation of chiral molecularly imprinted composite membrane:

将涂膜液涂覆于步骤(1)所得到的膜表面涂覆有热引发剂的高分子纤维膜表面，沥干，真空干燥，获得手性分子印迹复合膜前躯体；coating the coating solution on the surface of the polymer fiber membrane coated with a thermal initiator on the surface of the membrane obtained in step (1), draining, and drying in vacuum to obtain a chiral molecularly imprinted composite membrane precursor;

真空度为-0.09～-0.005MPa，温度为0～90℃，时间为4～72小时。The vacuum degree is -0.09～-0.005MPa, the temperature is 0～90°C, and the time is 4～72 hours.

涂膜液中，组分和质量百分比含量为：In the coating solution, the components and mass percentages are:

手性化合物                        0.25～10％Chiral compound 0.25～10%

功能单体                          1％～15％Functional monomer 1%～15%

交联剂                            5％～75％Cross-linking agent 5%～75%

溶剂                              10％～85％。Solvent 10%～85%.

所说的手性化合物选自二苯甲酰-L-酒石酸、D-色氨酸、左旋氧氟沙星、右旋氧氟沙星或其它手性化合物对映体中的一种；Said chiral compound is selected from dibenzoyl-L-tartaric acid, D-tryptophan, levofloxacin, dextroofloxacin or one of the enantiomers of other chiral compounds;

所说的功能单体选自丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸、丙烯酰胺、甲基丙烯酸、4-乙烯吡啶或苯乙烯等；The functional monomer is selected from ethyl acrylate, methyl methacrylate, acrylic acid, acrylamide, methacrylic acid, 4-vinylpyridine or styrene;

所说的交联剂选自乙二醇二甲基丙烯酸酯、四亚甲基二甲基丙烯酸酯、1，4-苯醚二丙烯酰胺、N，N-1，3-苯撑双(2-甲基-2-丙烯酰胺或三甲基丙烷三甲基丙烯酸酯等。Said cross-linking agent is selected from ethylene glycol dimethacrylate, tetramethylene dimethacrylate, 1,4-phenylene ether diacrylamide, N,N-1,3-phenylene bis(2 -Methyl-2-acrylamide or trimethylpropane trimethacrylate, etc.

所说的交联剂均可采用市售产品；Said linking agent can adopt commercially available product;

所说的溶剂选自乙腈、环己烷等或其混合物；Said solvent is selected from acetonitrile, hexanaphthene etc. or its mixture;

(3)模板分子的洗脱：(3) Elution of template molecules:

将步骤(2)的手性分子印迹复合膜前躯体置于洗脱剂中洗涤，直至手性化合物洗掉为止，获得本发明的具有手性识别分子印迹复合膜；Washing the chiral molecularly imprinted composite membrane precursor in step (2) in an eluent until the chiral compound is washed away to obtain the molecularly imprinted composite membrane with chiral recognition of the present invention;

所说的洗脱剂为体积百分比0.05～15％的醋酸/甲醇溶液。The eluent is 0.05-15% acetic acid/methanol solution by volume.

在上述制备方法中，基膜表面涂覆引发剂和涂覆涂膜液的先后顺序可以调换。基膜为聚合物高分子膜，在进行表面热聚合之前最好预先清洗处理，并烘干处理。In the above preparation method, the sequence of coating the initiator on the surface of the base film and coating the coating solution can be changed. The base film is a polymer film, and it is best to pre-clean and dry it before surface thermal polymerization.

采用上述方法所获得的手性分子印迹复合膜，基膜表面形态在表面聚合前后发生了较大的变化，未经表面聚合的基膜表面致密而且光滑，而经过表面聚合后，出现层叠交联状层；未经表面聚合的基膜皮层很薄，而经过表面聚合之后，皮层明显增厚。利用SEM可以测定手性分子印迹复合膜皮层厚度约3.0μm。从洗脱后的膜表面形态来看，明显出现许多尺寸在200nm以下的空穴，而且可以看出空穴之内还有空穴，具有三维的立体空穴网状结构。最大空穴直径也在200nm以下。孔隙率约为7×10⁶个/m²。The chiral molecularly imprinted composite membrane obtained by the above method has a large change in the surface morphology of the basement membrane before and after surface polymerization. The surface of the basement membrane without surface polymerization is dense and smooth, but after surface polymerization, lamination and crosslinking appear. The cortex of the basement membrane without surface polymerization is very thin, but after surface polymerization, the cortex thickens significantly. The skin thickness of the chiral molecularly imprinted composite membrane can be measured to be about 3.0 μm by SEM. From the surface morphology of the eluted membrane, there are obviously many holes with a size below 200nm, and it can be seen that there are holes inside the holes, with a three-dimensional hole network structure. The maximum hole diameter is also below 200nm. The porosity is about 7×10⁶ /m² .

利用本发明提供体系引发剂溶液及涂膜液配比及制膜工艺，通过改变模板分子，可制备出多种多样识别性能的分子印迹复合膜，可以用来拆分多种外消旋化合物。By utilizing the ratio of the system initiator solution and the coating solution and the film-making process provided by the invention, by changing the template molecules, molecularly imprinted composite films with various recognition properties can be prepared, which can be used to split various racemic compounds.

利用上述方法所获得的手性分子印迹复合膜，具有很好的识别选择性，如以L-DBTA为模板分子，只对L-DBTA，对其它化合物的识别选择性较小，对外消旋的L，D-DBTA溶液，其分离因子可达到2.7。The chiral molecularly imprinted composite membrane obtained by the above method has good recognition selectivity, such as using L-DBTA as a template molecule, only for L-DBTA, the recognition selectivity for other compounds is small, and for racemic L, D-DBTA solution, its separation factor can reach 2.7.

附图说明Description of drawings

图1为表面聚合前基膜外表面形态SEM电镜图。Figure 1 is the SEM electron micrograph of the outer surface morphology of the basement membrane before surface polymerization.

图2为表面聚合前基膜截面SEM电镜图。Fig. 2 is the SEM electron micrograph of the cross-section of the basement membrane before surface polymerization.

图3为手性分子印迹复合膜前躯体的表面形态SEM电镜图。Fig. 3 is the SEM electron micrograph of the surface morphology of the precursor of the chiral molecularly imprinted composite membrane.

图4为手性分子印迹复合膜前躯体的截面SEM电镜图。Fig. 4 is a cross-sectional SEM electron micrograph of the precursor of the chiral molecularly imprinted composite membrane.

图5为表面聚合前基膜表皮SEM电镜图。Fig. 5 is an SEM electron micrograph of the basement membrane epidermis before surface polymerization.

图6为手性分子印迹复合膜前躯体的表皮SEM电镜图。Fig. 6 is an SEM image of the epidermis of the precursor of the chiral molecularly imprinted composite membrane.

图7为手性分子印迹复合膜表面形态SEM电镜图。Figure 7 is the SEM electron micrograph of the surface morphology of the chiral molecularly imprinted composite membrane.

图8为手性分子印迹复合膜测试装置示意图。Fig. 8 is a schematic diagram of a chiral molecularly imprinted composite membrane testing device.

具体实施方式Detailed ways

以下举例对本发明技术进行说明，但专利技术并不仅限于所举实例。The following examples illustrate the technology of the present invention, but the patented technology is not limited to the examples given.

                        实施例1Example 1

首先按质量百分比称取原料，偶氮二异丁腈：6％，乙腈：94％，配制成引发剂溶液，其过程为：将AIBN加入到乙腈中，轻摇，使AIBN溶解。然后将溶液均匀涂于预先准备好的PSF中空纤维外表面，晾干。First, weigh raw materials according to mass percentage, azobisisobutyronitrile: 6%, acetonitrile: 94%, and prepare an initiator solution. The process is: add AIBN to acetonitrile and shake gently to dissolve AIBN. Then apply the solution evenly on the outer surface of the pre-prepared PSF hollow fiber, and let it dry.

然后按质量百分比称取原料，手性化合物二苯甲酰-L-酒石酸：2％；乙腈：60％；甲基丙烯酸甲酯：5％；乙二醇二甲基丙烯酸酯：32％配制成涂膜液，其过程为：先将L-DBTA加入到乙腈中，轻摇使其溶解，放置2小时，温度25℃，再加入甲基丙烯酸甲酯、乙二醇二甲基丙烯酸酯，摇匀，即为涂膜液。然后将涂膜液均匀涂于涂有引发剂的PSF中空纤维膜外表面，放置3小时后，将PSF中空纤维膜置于60℃的真空干燥箱中，真空度为-0.09～-0.005MPa，48小时。Then weigh raw materials by mass percentage, chiral compound dibenzoyl-L-tartaric acid: 2%; Acetonitrile: 60%; Methyl methacrylate: 5%; Ethylene glycol dimethacrylate: 32% to prepare Coating solution, the process is: first add L-DBTA to acetonitrile, shake it gently to dissolve it, let it stand for 2 hours at a temperature of 25°C, then add methyl methacrylate and ethylene glycol dimethacrylate, shake it Evenly, it is the coating solution. Then apply the coating solution evenly on the outer surface of the PSF hollow fiber membrane coated with the initiator, and after standing for 3 hours, place the PSF hollow fiber membrane in a vacuum drying oven at 60°C with a vacuum degree of -0.09～-0.005MPa. 48 hours.

最后将处理好的PSF膜置于10％醋酸/甲醇(体积比)溶液中洗脱模板分子，反复洗脱，直至模板分子洗掉为止。然后用甲醇冲洗，晾干，即制得手性分子印迹复合膜。可在干态时组装成手性分子印迹复合膜组件，对外消旋的二苯甲酰酒石酸溶液的分离因子可达到2.8。Finally, the treated PSF membrane is placed in 10% acetic acid/methanol (volume ratio) solution to elute the template molecules, and the elution is repeated until the template molecules are washed away. Then rinse with methanol and dry in the air to prepare the chiral molecular imprinted composite membrane. It can be assembled into a chiral molecular imprinted composite membrane module in a dry state, and the separation factor of racemic dibenzoyl tartaric acid solution can reach 2.8.

PSF中空纤维基膜具有如下的性能参数：   外径(μm)   1200   壁厚(μm)   234   孔隙率，％   87.8   纯水通量，L/m².h   267PSF hollow fiber base membrane has the following performance parameters: Outer diameter (μm) 1200 Wall thickness (μm) 234 Porosity,% 87.8 Pure water flux, L/m² .h 267

表面聚合前基膜外表面形态见图1，表面聚合前基膜截面见图2。手性分子印迹复合膜前躯体见图3。手性分子印迹复合膜前躯体的截面见图4。表面聚合前基膜表皮见图5。手性分子印迹复合膜前躯体的表皮见图6。手性分子印迹复合膜表面见图7。The morphology of the outer surface of the basement membrane before surface polymerization is shown in Figure 1, and the cross-section of the basement membrane before surface polymerization is shown in Figure 2. The precursor of the chiral molecularly imprinted composite membrane is shown in Figure 3. The cross-section of the precursor of the chiral molecularly imprinted composite membrane is shown in Fig. 4 . The basement membrane epidermis before surface polymerization is shown in Figure 5. The epidermis of the precursor of the chiral molecularly imprinted composite membrane is shown in Fig. 6 . The surface of the chiral molecularly imprinted composite membrane is shown in Figure 7.

                            实施例2Example 2

按实施例1所述制备条件和过程，采用材料为聚醚砜(PES)的中空纤维超滤膜作为支撑体，其它与施例1相同，重复施例1的过程制，也可制得手性分子印迹复合膜，并组装成膜组件，对外消旋的L，D-DBTA溶液的分离因子可达到2.0。According to the preparation conditions and process described in Example 1, the material is a hollow fiber ultrafiltration membrane of polyethersulfone (PES) as a support, and the others are the same as in Example 1. Repeat the process of Example 1 to obtain chiral The molecularly imprinted composite membrane is assembled into a membrane module, and the separation factor of the racemic L, D-DBTA solution can reach 2.0.

                            实施例3Example 3

按实施例1所述制备条件和过程，采用左旋氧氟沙星作为模板分子，其它与施例1相同，重复施例1的过程制得左旋氧氟沙星手性分子印迹复合膜，并组装成膜组件，对外消旋的氧氟沙星溶液的分离因子可达到1.7。According to the preparation conditions and process described in Example 1, levofloxacin is used as the template molecule, and the others are the same as in Example 1, and the process of Example 1 is repeated to prepare the levofloxacin chiral molecularly imprinted composite film, and assemble Membrane-forming components, the separation factor of the racemic ofloxacin solution can reach 1.7.

                            实施例4Example 4

按实施例1所述制备条件、材料和过程，改变涂覆顺序，先以手性化合物为模板分子，加入功能单体，超声溶解，静置使其充分作用，加入溶剂和交联剂摇匀配制成涂膜液。According to the preparation conditions, materials and process described in Example 1, change the coating sequence, first use the chiral compound as the template molecule, add the functional monomer, ultrasonically dissolve, let it stand for full effect, add the solvent and crosslinking agent and shake well Prepared as a coating solution.

其中手性化合物的质量百分比含量为5.5％，功能单体的质量百分比含量为10％，交联剂42.5％，溶剂的质量百分比含量为42％。Wherein the mass percentage content of chiral compound is 5.5%, the mass percentage content of functional monomer is 10%, the crosslinking agent is 42.5%, and the mass percentage content of solvent is 42%.

将上述涂膜液涂覆于第一步膜的表面，阴干。然后将引发剂按比例溶于溶剂中，配制成引发剂的质量百分比含量为5％的溶液，将晾干的膜从中经过，然后晾干。最后将膜置于真空干燥箱中，在-0.07MPa真空度下热处理，热处理温度为60℃，处理时间为72小时。其它与施例1相同，可制得手性分子印迹复合膜，并组装成膜组件，对外消旋的L，D-DBTA溶液的分离因子可达到2.2。Apply the above-mentioned coating solution to the surface of the first step membrane and dry in the shade. Then, the initiator is dissolved in the solvent in proportion to prepare a solution with a mass percent content of the initiator of 5%, and the dried film is passed through it, and then dried. Finally, the film was placed in a vacuum drying oven, and heat-treated at a vacuum degree of -0.07 MPa, the heat-treatment temperature was 60° C., and the treatment time was 72 hours. Others are the same as in Example 1, a chiral molecularly imprinted composite membrane can be prepared and assembled into a membrane module, and the separation factor of the racemic L, D-DBTA solution can reach 2.2.

                            实施例5Example 5

按实施例1所述制备条件和过程，首先按质量百分比称取原料，偶氮二异丁腈：2％，乙腈：98％，配制成引发剂溶液，其它与施例1相同，重复施例1的过程制得手性分子印迹复合膜，并组装成膜组件，对外消旋的二苯甲酰酒石酸溶液的分离因子可达到1.7。According to the preparation conditions and process described in Example 1, first weigh the raw materials according to the mass percentage, azobisisobutyronitrile: 2%, acetonitrile: 98%, and prepare an initiator solution. Others are the same as in Example 1, and repeat the example 1 to prepare a chiral molecularly imprinted composite membrane and assemble it into a membrane module. The separation factor of the racemic dibenzoyl tartaric acid solution can reach 1.7.

                            实施例6Example 6

按实施例1所述制备条件和过程，手性化合物二苯甲酰-L-酒石酸加入量：4％；乙腈：58％；甲基丙烯酸甲酯：5％；乙二醇二甲基丙烯酸酯：32％配制成涂膜液，其它与施例1相同，重复施例1的过程制得手性分子印迹复合膜，并组装成膜组件，对外消旋的L，D-DBTA溶液的分离因子可达到2.0。According to the preparation conditions and process described in Example 1, the chiral compound dibenzoyl-L-tartaric acid addition: 4%; acetonitrile: 58%; methyl methacrylate: 5%; ethylene glycol dimethacrylate : 32% is prepared as coating liquid, other is identical with embodiment 1, repeats the process of embodiment 1 and makes chiral molecularly imprinted composite film, and assembles into membrane assembly, the separation factor of the racemic L, D-DBTA solution can be Reach 2.0.

                            实施例7Example 7

按实施例1所述制备条件和过程，将涂好的中空纤维膜于50℃的真空干燥箱中，在-0.09MPa真空度下热处理，热处理48小时。其它与施例1相同，重复施例1的过程制得手性分子印迹复合膜，并组装成膜组件，对外消旋的二苯甲酰酒石酸溶液的分离因子可达到1.4。According to the preparation conditions and process described in Example 1, the coated hollow fiber membrane was heat-treated in a vacuum oven at 50° C. at a vacuum degree of -0.09 MPa for 48 hours. Others are the same as in Example 1. Repeat the process of Example 1 to prepare a chiral molecularly imprinted composite membrane and assemble it into a membrane module. The separation factor of the racemic dibenzoyl tartaric acid solution can reach 1.4.

                            实施例8Example 8

按实施例1所述制备条件和过程，将涂好的中空纤维膜于60℃的真空干燥箱中，在-0.09MPa真空度下热处理，热处理12小时。其它与施例1相同，重复施例1的过程制得手性分子印迹复合膜，并组装成膜组件，对外消旋的二苯甲酰酒石酸溶液的分离因子可达到1.5。According to the preparation conditions and process described in Example 1, the coated hollow fiber membrane was heat-treated in a vacuum oven at 60° C. at a vacuum degree of -0.09 MPa for 12 hours. Others are the same as in Example 1. Repeat the process of Example 1 to prepare a chiral molecularly imprinted composite membrane and assemble it into a membrane module. The separation factor of the racemic dibenzoyl tartaric acid solution can reach 1.5.

                            实施例9Example 9

按实施例1所述制备条件和过程，然后将涂膜液均匀涂于涂有引发剂的PSF中空纤维膜外表面，只放置阴干1小时，其它与施例1相同，重复施例1的过程制得手性分子印迹复合膜，并组装成膜组件，对外消旋的二苯甲酰酒石酸溶液的分离因子可达到1.4。Preparation conditions and process described in Example 1, then the coating solution is evenly coated on the outer surface of the PSF hollow fiber membrane coated with initiator, only placed to dry in the shade for 1 hour, other is the same as Example 1, repeat the process of Example 1 The chiral molecularly imprinted composite membrane was prepared and assembled into a membrane module. The separation factor of racemic dibenzoyl tartaric acid solution could reach 1.4.

                            实施例10Example 10

将实施例1～9制得的手性分子印迹复合膜5根，装入φ6×230mm不锈钢管中，两端用环氧树脂胶密封，分别组装成小型膜组件，在图8所示的装置装置上测定其分离因子。具体方法为：分别将一定浓度的左右旋的手性化合物溶液放入原液槽1中，用泵5输送至膜组件6，利用流量计4和压力表3控制手性化合物溶液流量和压力，经过手性分子印迹纤维复合膜分离后，浓缩液经循环槽2进入原液槽1循环，透过液进行分析。分配系数和分离因子采用式(1)和式(2)进行计算。Put five chiral molecularly imprinted composite membranes prepared in Examples 1 to 9 into φ6×230mm stainless steel tubes, seal both ends with epoxy resin, and assemble them into small membrane modules respectively. The device shown in Figure 8 The separation factor was measured on the device. The specific method is: respectively put a certain concentration of right-handed chiral compound solution into the stock solution tank 1, transport it to the membrane module 6 with the pump 5, use theflow meter 4 and the pressure gauge 3 to control the flow rate and pressure of the chiral compound solution, and pass through After the chiral molecularly imprinted fiber composite membrane is separated, the concentrated solution enters the original solution tank 1 through the circulation tank 2 for circulation, and the permeate is analyzed. The distribution coefficient and separation factor are calculated using formula (1) and formula (2).

分离因子的测定方法如下：The separation factor was determined as follows:

分配系数(K_L)：$K_L=\frac{C_0-C}{C_0}\×100\%---\left(1\right)$Partition coefficient (K_L ):$K_L=\frac{C_0-C}{C_0}\×100\%---\left(1\right)$

分离因子(α)：α＝K_L/K_D                         (2)Separation factor (α): α=K_L /K_D (2)

式中：K_L表示手性分子印迹复合膜对左旋手性化合物的分配系数，C表示透过液的浓度，C₀表示底物初始浓度，K_D表示手性化合物手性分子印迹复合膜对右旋化合物的分配系数。分离因子α表示手性分子印迹膜对模板分子的选择性。In the formula: K_L represents the partition coefficient of the chiral molecularly imprinted composite membrane to the left-handed chiral compound, C represents the concentration of the permeate, C₀ represents the initial concentration of the substrate, and K_D represents the chiral molecularly imprinted composite membrane pair of chiral compound Partition coefficients of dextrorotatory compounds. Separation factor α represents the selectivity of chiral molecularly imprinted membranes to template molecules.

Claims (7)

1. the preparation method of a composite fiber membrane with chiral molecular imprint is characterized in that, comprises the steps:

(1) the macromolecular fibre film is contacted with the solution that contains initator, dry then, obtain the macromolecular fibre film that the film surface-coated has thermal initiator;

In the said solution that contains initator, the mass percentage content of initator is 0.05～10%;

Said initator comprises azodiisobutyronitrile, benzoyl peroxide, benzyl dimethyl acetal, azo methyl pentane nitrile, 4, a kind of in 4-azo (4-itrile group valeric acid) or the ammonium persulfate;

(2) coating liquid is coated on the macromolecular fibre film surface that the resulting film surface-coated of step (1) has thermal initiator, drains, vacuum drying obtains chiral molecular imprinting composite membrane precursor;

In the coating liquid, component and mass percentage content are:

Chipal compounds 0.25～10%

Function monomer 1%～15%

Crosslinking agent 5%～75%

Solvent 10%～85%

Said chipal compounds is selected from a kind of in dibenzoyl-L-tartaric acid, D-tryptophan, lefofloxacin, dextrorotation Ofloxacin or other chiral compound enantiomer;

Said function monomer is selected from ethyl acrylate, methyl methacrylate, acrylic acid, acrylamide, methacrylic acid, 4-vinylpyridine or styrene etc.;

Said crosslinking agent is selected from ethylene glycol dimethacrylate, tetramethylene dimethylacrylate, 1,4-phenylate diacrylamine, N, N-1,3-penylene two (2-methyl-2-acrylamide or trimethyl propane trimethyl acrylic esters etc.;

(3) the chiral molecular imprinting composite membrane precursor with step (2) places eluant, eluent to wash, and till chipal compounds is washed off, obtains the chiral Recognition molecular engram composite membrane that has of the present invention;

Said eluant, eluent is the acetic acid/methanol solution of percent by volume 0.05～15%.

2. method according to claim 1 is characterized in that, the solvent of step (1) is a kind of or its mixture in acetonitrile or the cyclohexane etc., and the solvent of step (2) is acetonitrile, cyclohexane etc. or its mixture.

3. method according to claim 1, it is characterized in that, said macromolecular fibre film is hollow-fibre membrane or dull and stereotyped ultrafiltration tunica fibrosa, membrane material be selected from polysulfones (PSF), polyether sulfone (PES), Kynoar (PVDF), polyvinyl chloride (PVC), polyamide or cellulose or and derivative etc. in a kind of.

4. method according to claim 1 is characterized in that, said doughnut basement membrane has following performance parameter: external diameter: 1000～1400 μ m, wall thickness 200～300 μ m, porosity 80～90%, pure water flux 200～300L/m².h.

5. method according to claim 1 is characterized in that, coating liquid is coated on the macromolecular fibre film surface that the resulting film surface-coated of step (1) has thermal initiator, drains, and vacuum drying obtains chiral molecular imprinting composite membrane precursor; Vacuum is-0.09～-0.005MPa, temperature is 0～90 ℃, the time is 4～72 hours.

6. according to the composite fiber membrane with chiral molecular imprint of each described method preparation of claim 1～6.

7. according to the application of the composite fiber membrane with chiral molecular imprint of each described method preparation of claim 1～6, it is characterized in that, be used for the resolution of racemic compound.

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