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CN115591289A - Preparation method of multifunctional filter element for sample liquid separation, filter element and application thereof - Google Patents

Preparation method of multifunctional filter element for sample liquid separation, filter element and application thereof Download PDF

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Publication number
CN115591289A
CN115591289A CN202211219809.4A CN202211219809A CN115591289A CN 115591289 A CN115591289 A CN 115591289A CN 202211219809 A CN202211219809 A CN 202211219809A CN 115591289 A CN115591289 A CN 115591289A
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filler
filter element
packing
sample liquid
polymer
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张健
陈高明
胡玉梅
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Biocomma Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
    • B01D29/0093—Making filtering elements not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D36/00—Filter circuits or combinations of filters with other separating devices

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Abstract

The invention discloses a preparation method of a multifunctional filter element for sample liquid separation, and the filter element and application thereof. The preparation method comprises the following steps: (1) Mixing a first polymer and an adsorptive filler according to a formula ratio to form a pre-sintered mixed material; (2) uniformly mixing the pre-sintered mixed materials, and then vibrating and compressing to obtain a pre-sintered material; (3) sintering the pre-sintered material to obtain the filter element; and (4) coating a second polymer film on the surface of the filter element after the filter element is cooled. In the preparation method of the invention, the first polymer and the adsorptive filler are mixed and then are vibrated and compressed to uniformly disperse the first polymer and the adsorptive filler, so that the adsorptive filler in the prepared multifunctional filter element is better distributed according to the assumption. The second polymer film is coated on the surface of the sintered filter element, so that the adsorption filler positioned outside can be prevented from falling off to pollute sample liquid or cause poor experimental effect, and the speed of the sample liquid passing through the multifunctional filter element can be reduced, thereby realizing the full contact of the sample liquid in the multifunctional filter element and realizing the separation of a target object to improve the separation effect.

Description

用于样液分离的多功能滤芯的制备方法，及其滤芯和应用Preparation method of multifunctional filter element for sample liquid separation, filter element and application thereof

技术领域technical field

本发明涉及滤芯领域，尤其涉及一种用于样液分离的多功能滤芯的制备方法，及其滤芯和应用。The invention relates to the field of filter elements, in particular to a method for preparing a multifunctional filter element for sample liquid separation, and the filter element and its application.

背景技术Background technique

滤芯可广泛应用于生物医药、生命科学、临床诊断、化学分析、样本处理、气体过滤等领域。但目前的滤芯仅具有过滤的功能，功能较为单一。为了在过滤的同时实现吸附分离或萃取，方便装配等，需开发一种多功能滤芯，实现滤芯与吸附剂等的结合。Filter elements can be widely used in biomedicine, life sciences, clinical diagnosis, chemical analysis, sample processing, gas filtration and other fields. But the present filter element only has the function of filtering, and the function is comparatively single. In order to achieve adsorption separation or extraction while filtering, and facilitate assembly, etc., it is necessary to develop a multifunctional filter element to realize the combination of filter element and adsorbent.

目前，业界有于滤芯中增加吸附剂填料以同时实现吸附和过滤功能。但采用传统的滤芯烧结工艺，吸附剂在滤芯内不能很好地按照设想进行分布，因而并不能较好的实现两种功能的结合。同时，滤芯内增加吸附剂填料之后，会有部分吸附剂填料被烧结在成型滤芯的外表面，容易出现吸附剂填料脱落的问题，从而污染样液或导致实验效果变差。At present, the industry is adding adsorbent fillers to filter elements to achieve both adsorption and filtration functions. However, with the traditional filter element sintering process, the adsorbent cannot be well distributed in the filter element according to the assumption, so the combination of the two functions cannot be well realized. At the same time, after the adsorbent filler is added in the filter element, some of the adsorbent filler will be sintered on the outer surface of the formed filter element, which is prone to the problem of the adsorbent filler falling off, which will pollute the sample liquid or lead to poor experimental results.

发明内容Contents of the invention

鉴于上述问题，本发明的目的在于提供一种用于样液分离的多功能滤芯的制备方法，其既能实现吸附性填料于滤芯中较佳的分布，又能避免吸附剂填料的脱落，可制得一种兼顾吸附和过滤功能的多功能滤芯，可用于生物或医药类样液分离。In view of the above problems, the object of the present invention is to provide a method for preparing a multi-functional filter element for sample liquid separation, which can realize better distribution of the adsorptive filler in the filter element and avoid the falling off of the adsorbent filler, which can A multifunctional filter element with both adsorption and filtration functions is prepared, which can be used for separation of biological or pharmaceutical sample liquids.

为实现上述目的，本发明第一方面提供了用于样液分离的多功能滤芯的制备方法，包括步骤：In order to achieve the above object, the first aspect of the present invention provides a method for preparing a multifunctional filter element for sample liquid separation, comprising the steps of:

(1)按照配方比混合第一聚合物和吸附性填料成预烧混料；(1) Mixing the first polymer and the adsorptive filler according to the formula ratio to form a pre-calcined mixture;

(2)将预烧混料混匀后振动压缩得预烧料；(2) Vibrating and compressing the calcined mixture after mixing to obtain the calcined material;

(3)将预烧料进行烧结得滤芯；(3) Sintering the pre-fired material to obtain a filter element;

(4)滤芯冷却后于表面包覆第二聚合物膜。(4) The surface of the filter core is coated with a second polymer film after cooling.

本发明的多功能滤芯的制备方法中，将第一聚合物和吸附性填料混合后进行振动压缩可使第一聚合物和吸附性填料分散均匀，可使制得的多功能滤芯中吸附性填料较好的按照设想进行分布。烧结的滤芯表面包覆第二聚合物膜，不仅可防止处于外部的吸附性填料脱落而污染样液或导致实验效果差，还可减缓样液通过多功能滤芯的速度，从而实现样液在多功能滤芯中充分接触而实现目标物的分离，以提升分离效果。In the preparation method of the multifunctional filter element of the present invention, after the first polymer and the adsorptive filler are mixed, vibration compression can make the first polymer and the adsorptive filler disperse evenly, and the adsorptive filler in the obtained multifunctional filter element can Better to distribute as envisaged. The surface of the sintered filter element is covered with a second polymer film, which can not only prevent the external adsorbent filler from falling off and contaminate the sample liquid or cause poor experimental results, but also slow down the speed of the sample liquid passing through the multi-functional filter element, so as to realize the sample liquid in multiple The functional filter element is fully contacted to achieve the separation of the target object, so as to improve the separation effect.

作为一实施例，吸附性填料占第一聚合物和吸附性填料总重量的比例大于等于0.05％小于等于60％。As an example, the ratio of the adsorptive filler to the total weight of the first polymer and the adsorptive filler is greater than or equal to 0.05% and less than or equal to 60%.

作为一实施例，吸附性填料为硅胶、活性铝、碳类吸附剂、分子筛、聚合物吸附剂或生物吸附剂。As an example, the adsorptive filler is silica gel, activated aluminum, carbon-based adsorbent, molecular sieve, polymer adsorbent or biosorbent.

作为一实施例，吸附性填料为

Figure BDA0003874565130000021
HLB填料、
Figure BDA0003874565130000022
WAX填料、
Figure BDA0003874565130000023
WCX填料、
Figure BDA0003874565130000024
MAX填料、
Figure BDA0003874565130000025
MCX填料、
Figure BDA0003874565130000026
C18填料、
Figure BDA0003874565130000027
C8填料、SPE C4硅胶填料、
Figure BDA0003874565130000028
Silica硅胶填料、
Figure BDA0003874565130000029
Diol填料、
Figure BDA00038745651300000210
CN填料、
Figure BDA00038745651300000211
Carb-GCB填料、
Figure BDA00038745651300000212
Florisil填料、
Figure BDA00038745651300000213
ALA填料、
Figure BDA00038745651300000214
ALN填料、
Figure BDA00038745651300000215
ALB填料、
Figure BDA00038745651300000216
SCX填料、
Figure BDA00038745651300000217
SAX填料、
Figure BDA00038745651300000218
NH2填料、
Figure BDA00038745651300000219
PSA填料和
Figure BDA00038745651300000220
PRS填料中的至少一种。As an example, the adsorptive filler is
Figure BDA0003874565130000021
HLB filler,
Figure BDA0003874565130000022
WAX filler,
Figure BDA0003874565130000023
WCX packing,
Figure BDA0003874565130000024
MAX packing,
Figure BDA0003874565130000025
MCX packing,
Figure BDA0003874565130000026
C18 packing,
Figure BDA0003874565130000027
C8 packing, SPE C4 silica gel packing,
Figure BDA0003874565130000028
Silica silica gel packing,
Figure BDA0003874565130000029
Diol filler,
Figure BDA00038745651300000210
CN filler,
Figure BDA00038745651300000211
Carb-GCB filler,
Figure BDA00038745651300000212
Florisil filler,
Figure BDA00038745651300000213
ALA filler,
Figure BDA00038745651300000214
ALN packing,
Figure BDA00038745651300000215
ALB packing,
Figure BDA00038745651300000216
SCX packing,
Figure BDA00038745651300000217
SAX filler,
Figure BDA00038745651300000218
NH 2 filler,
Figure BDA00038745651300000219
PSA filler and
Figure BDA00038745651300000220
At least one of the PRS fillers.

作为一实施例，第一聚合物选自聚对苯二甲酸乙二醇酯、聚丙烯和聚乙烯中的至少一种。As an embodiment, the first polymer is selected from at least one of polyethylene terephthalate, polypropylene and polyethylene.

作为一实施例，第二聚合物膜通过将第二聚合物溶解或分散于溶剂中得包覆液，再将包覆液设置于滤芯的表面干燥可得。As an example, the second polymer film can be obtained by dissolving or dispersing the second polymer in a solvent to obtain a coating solution, and then placing the coating solution on the surface of the filter element to dry.

作为一实施例，第二聚合物选自硝酸纤维素、醋酸纤维素、聚醚砜和聚偏氟乙烯中的至少一种。As an embodiment, the second polymer is at least one selected from nitrocellulose, cellulose acetate, polyethersulfone and polyvinylidene fluoride.

作为一实施例，溶剂为四氢呋喃、乙二醇二甲醚、正戊烷、正己烷、环己烷、甲苯、二甲苯、三甲苯、乙酸乙酯、甲酸甲酯、邻苯二甲酸二甲酯、乙腈、N甲基吡咯烷酮、N,N二甲基甲酰胺、二氯甲烷和1,2二氯乙烷中的至少一种。As an example, the solvent is tetrahydrofuran, ethylene glycol dimethyl ether, n-pentane, n-hexane, cyclohexane, toluene, xylene, trimethylbenzene, ethyl acetate, methyl formate, dimethyl phthalate , acetonitrile, N-methylpyrrolidone, N,N-dimethylformamide, dichloromethane and at least one of 1,2 dichloroethane.

作为一实施例，混匀采用的设备转速为5r/min至200r/min，转动时间为0.5h至10h。As an example, the rotating speed of the equipment used for mixing is 5r/min to 200r/min, and the rotation time is 0.5h to 10h.

作为一实施例，振动采用的频率为5Hz至200Hz，振动时间为3s至600s。As an embodiment, the vibration frequency is 5 Hz to 200 Hz, and the vibration time is 3 s to 600 s.

作为一实施例，烧结的温度为110℃至250℃，时间为1.5min至50min。As an example, the sintering temperature is 110° C. to 250° C., and the sintering time is 1.5 minutes to 50 minutes.

作为一实施例，冷却的温度为3℃至35℃，时间为1.5min至50minAs an example, the cooling temperature is 3°C to 35°C, and the time is 1.5min to 50min

本发明第二方面提供了多功能滤芯，包括由第一聚合物和吸附性填料混合烧结而成的芯核和包裹芯核的包覆层。The second aspect of the present invention provides a multifunctional filter element, comprising a core core formed by mixing and sintering a first polymer and an absorbent filler, and a cladding layer wrapping the core core.

本发明第三方面提供了用于样液分离的多功能滤芯的制备方法所制备的多功能滤芯于生物或医药类样液分离中的应用。The third aspect of the present invention provides the application of the multifunctional filter element prepared by the method for preparing the multifunctional filter element for sample liquid separation in biological or medical sample liquid separation.

附图说明Description of drawings

图1为本发明的用于样液分离的多功能滤芯的制备方法所制备的多功能滤芯的示意图。FIG. 1 is a schematic diagram of a multifunctional filter element prepared by the method for preparing a multifunctional filter element for sample liquid separation according to the present invention.

具体实施方式detailed description

本发明的多功能滤芯指具有多种功能的滤芯，包括但不限于过滤功能和吸附功能的结合。本发明的多功能滤芯尤其适用于生物或医药类样液的分离。The multifunctional filter element of the present invention refers to a filter element with multiple functions, including but not limited to the combination of filtering function and adsorption function. The multifunctional filter element of the invention is especially suitable for the separation of biological or medical sample liquids.

本发明的多功能滤芯100包括芯核10和包覆层30。芯核10由第一聚合物11和吸附性填料13混合烧结而成。原料中，吸附性填料占第一聚合物和吸附性填料总重量的比例大于等于0.05％小于等于60％。比例可但不限于为0.05％、0.1％、0.5％、1％、3％、5％、8％、10％、15％、20％、25％、30％、33％、35％、40％、45％、50％、55％、60％。作为示例，吸附性填料占第一聚合物和吸附性填料总重量的比例为33％。第一聚合物10选自聚丙烯、聚乙烯和聚对苯二甲酸乙二醇酯中的至少一种。作为示例，第一聚合物10选自聚丙烯。常温下第一聚合物10可为颗粒状。吸附性填料13为硅胶、活性铝、碳类吸附剂、分子筛、聚合物吸附剂或生物吸附剂。作为示例的，吸附性填料13可为

Figure BDA0003874565130000031
HLB填料、
Figure BDA0003874565130000032
WAX填料、
Figure BDA0003874565130000033
WCX填料、
Figure BDA0003874565130000034
MAX填料、
Figure BDA0003874565130000035
MCX填料、
Figure BDA0003874565130000041
C18填料、
Figure BDA0003874565130000042
C8填料、SPE C4硅胶填料、
Figure BDA0003874565130000043
Silica硅胶填料、
Figure BDA0003874565130000044
Diol填料、
Figure BDA0003874565130000045
CN填料、
Figure BDA0003874565130000046
Carb-GCB填料、
Figure BDA0003874565130000047
Florisil填料、
Figure BDA0003874565130000048
ALA填料、
Figure BDA0003874565130000049
ALN填料、
Figure BDA00038745651300000410
ALB填料、
Figure BDA00038745651300000411
SCX填料、
Figure BDA00038745651300000412
SAX填料、
Figure BDA00038745651300000413
NH2填料、
Figure BDA00038745651300000414
PSA填料和
Figure BDA00038745651300000415
PRS填料中的至少一种。The multifunctional filter element 100 of the present invention includes a core 10 and a cladding layer 30 . The core 10 is formed by mixing and sintering the first polymer 11 and the adsorptive filler 13 . In the raw material, the ratio of the adsorptive filler to the total weight of the first polymer and the adsorptive filler is greater than or equal to 0.05% and less than or equal to 60%. The ratio can be but not limited to 0.05%, 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 33%, 35%, 40% , 45%, 50%, 55%, 60%. As an example, the proportion of the adsorptive filler to the total weight of the first polymer and the adsorptive filler is 33%. The first polymer 10 is selected from at least one of polypropylene, polyethylene and polyethylene terephthalate. As an example, the first polymer 10 is selected from polypropylene. The first polymer 10 may be in granular form at normal temperature. Adsorptive filler 13 is silica gel, activated aluminum, carbon-based adsorbent, molecular sieve, polymer adsorbent or biosorbent. As an example, the adsorptive filler 13 can be
Figure BDA0003874565130000031
HLB filler,
Figure BDA0003874565130000032
WAX filler,
Figure BDA0003874565130000033
WCX packing,
Figure BDA0003874565130000034
MAX packing,
Figure BDA0003874565130000035
MCX packing,
Figure BDA0003874565130000041
C18 packing,
Figure BDA0003874565130000042
C8 packing, SPE C4 silica gel packing,
Figure BDA0003874565130000043
Silica silica gel packing,
Figure BDA0003874565130000044
Diol filler,
Figure BDA0003874565130000045
CN filler,
Figure BDA0003874565130000046
Carb-GCB filler,
Figure BDA0003874565130000047
Florisil filler,
Figure BDA0003874565130000048
ALA filler,
Figure BDA0003874565130000049
ALN packing,
Figure BDA00038745651300000410
ALB packing,
Figure BDA00038745651300000411
SCX packing,
Figure BDA00038745651300000412
SAX filler,
Figure BDA00038745651300000413
NH 2 filler,
Figure BDA00038745651300000414
PSA filler and
Figure BDA00038745651300000415
At least one of the PRS fillers.

其中，

Figure BDA00038745651300000416
HLB填料为亲水亲脂平衡填料，由共聚合技术制备而成。含有特定比例的亲水基和疏水基，其疏水性的二乙烯基苯结构保留非极性化合物，亲水性的N-乙烯基吡咯烷酮结构保留极性化合物。该填料具有良好的水润湿性，可通过水相调节亲水-亲脂平衡，从而获得理想的选择性填料。in,
Figure BDA00038745651300000416
HLB packing is hydrophilic-lipophilic balancing packing, prepared by copolymerization technology. Containing a specific ratio of hydrophilic and hydrophobic groups, its hydrophobic divinylbenzene structure retains non-polar compounds, and its hydrophilic N-vinylpyrrolidone structure retains polar compounds. The filler has good water wettability, and the hydrophilic-lipophilic balance can be adjusted through the water phase to obtain an ideal selective filler.

Figure BDA00038745651300000417
WAX填料为弱阴离子交换填料，是以大孔PS/DVB为基质，经三级胺基修饰的混合型弱阴离子交换吸附剂，其苯环具有较强的疏水相互作用，三级胺基提供了弱阴离子交换能力。
Figure BDA00038745651300000417
WAX packing is a weak anion exchange packing, which is a mixed weak anion exchange adsorbent modified by tertiary amine groups based on macroporous PS/DVB. The benzene ring has strong hydrophobic interaction, and the tertiary amine groups provide Weak anion exchange capacity.

Figure BDA00038745651300000418
WCX填料为弱阳离子交换填料，是以大孔PS/DVB为基质，经羧基修饰的混合型弱阳离子吸附剂，其苯环具有较强的疏水相互作用，羧基提供了弱阳离子交换能力。
Figure BDA00038745651300000418
WCX filler is a weak cation exchange filler, which is a mixed weak cation adsorbent modified by carboxyl groups based on macroporous PS/DVB. The benzene ring has strong hydrophobic interaction, and the carboxyl group provides weak cation exchange capacity.

Figure BDA00038745651300000419
MAX填料为混合型阴离子交换填料，是将季铵基键合到高度交联的PS/DVB表面得到的混合型强阴离子交换吸附剂，具有强阴离子交换和反相保留作用，适合酸性化合物的萃取。
Figure BDA00038745651300000419
MAX packing is a mixed-type anion-exchange filler, which is a mixed-type strong anion-exchange adsorbent obtained by bonding quaternary ammonium groups to the surface of highly cross-linked PS/DVB. It has strong anion-exchange and reverse-phase retention, and is suitable for the extraction of acidic compounds.

Figure BDA00038745651300000420
MCX填料为混合型阳离子交换填料，是将磺酸基键合在高度交联的PS/DVB表面得到的混合型强阳离子交换吸附剂，具有反相和阳离子交换双重保留性能，对碱性化合物有良好的保留能力。
Figure BDA00038745651300000420
MCX packing is a mixed cation exchange packing, which is a mixed strong cation exchange adsorbent obtained by bonding sulfonic acid groups on the surface of highly cross-linked PS/DVB. It has dual retention properties of reversed phase and cation exchange, and is effective for basic compounds Good retention.

Figure BDA00038745651300000421
C18填料为封端十八烷基硅胶，是最常用的反相吸附剂，通过强疏水作用保留非极性化合物。该填料能保留大多数有机物，广泛用于环境、食品安全等领域。
Figure BDA00038745651300000421
C18 packing is capped octadecyl silica, which is the most commonly used reversed-phase adsorbent, and retains non-polar compounds through strong hydrophobic interaction. The filler can retain most of the organic matter and is widely used in the fields of environment and food safety.

Figure BDA00038745651300000422
C8填料为辛基硅胶，是中等疏水性的反相硅胶基质填料，通过疏水相互作用保留非极性化合物。与
Figure BDA00038745651300000423
C18填料相比，
Figure BDA00038745651300000424
C8填料的碳链较短，非极性疏水相互作用较弱。若使用
Figure BDA00038745651300000425
C18填料造成非极性目标物难以洗脱，可用
Figure BDA00038745651300000426
C8填料替代。
Figure BDA00038745651300000422
C8 packing is octyl silica gel, which is a reversed-phase silica gel matrix packing with medium hydrophobicity, and retains non-polar compounds through hydrophobic interaction. and
Figure BDA00038745651300000423
Compared to C18 packing,
Figure BDA00038745651300000424
C8 fillers have shorter carbon chains and weaker non-polar hydrophobic interactions. if use
Figure BDA00038745651300000425
C18 filler makes it difficult to elute non-polar targets, available
Figure BDA00038745651300000426
C8 filler replacement.

SPE C4硅胶填料表面的亲水性硅羟基通过硅烷化反应键合非极性4个碳的烷基作为反相固定相，利用被测物的碳氢键与固定相表面官能团产生非极性的范德华力或色散力，以富集非极性及弱极性物质。The hydrophilic silanol on the surface of the SPE C4 silica gel filler is bonded to a non-polar 4-carbon alkyl group through a silanization reaction as a reversed-phase stationary phase, using the carbon-hydrogen bond of the analyte and the functional group on the surface of the stationary phase to generate a non-polar phase. Van der Waals force or dispersion force to enrich non-polar and weakly polar substances.

Figure BDA0003874565130000051
Silica硅胶填料为未键合的硅胶填料，是极性最强的正相吸附剂，能保留样品中的极性化合物，特别是结构相似的极性化合物。
Figure BDA0003874565130000051
Silica silica gel filler is an unbonded silica gel filler, which is the most polar normal phase adsorbent and can retain polar compounds in the sample, especially polar compounds with similar structures.

Figure BDA0003874565130000052
Diol填料为二醇基类填料，具有类似硅胶的保留性能和较小的酸性，碳链提供了额外的疏水作用，因而可作为正相或反相吸附剂。若使用未键合硅胶填料，硅胶的酸性导致碱性杂质保留，可以换用
Figure BDA0003874565130000053
Diol填料。
Figure BDA0003874565130000052
Diol packing is a diol-based packing, which has similar retention properties to silica gel and less acidity. The carbon chain provides additional hydrophobicity, so it can be used as a normal phase or reverse phase adsorbent. If unbonded silica gel is used, the acidity of silica gel will cause the retention of basic impurities, which can be replaced
Figure BDA0003874565130000053
Diol filler.

Figure BDA0003874565130000054
CN填料为氰丙基类填料，是弱疏水性的硅胶基质填料，可作为正相或反相吸附剂使用。在反相条件下，从水溶液中萃取非极或弱极性的酸、中、碱性化合物。在正相条件下，从非极性有机溶液中萃取极性化合物。此外，氰丙基作为络合物配体，可富集水溶液中的某些金属离子。对在
Figure BDA0003874565130000055
C18填料上生产不可逆结合的强疏水物质，
Figure BDA0003874565130000056
CN填料是更合适的选择。
Figure BDA0003874565130000054
CN packing is cyanopropyl packing, which is weakly hydrophobic silica gel matrix packing and can be used as normal phase or reverse phase adsorbent. Under reversed-phase conditions, non-polar or weakly polar acidic, medium and basic compounds are extracted from aqueous solution. Under normal phase conditions, polar compounds are extracted from nonpolar organic solutions. In addition, cyanopropyl, as a complex ligand, can enrich certain metal ions in aqueous solution. yes
Figure BDA0003874565130000055
Produce irreversibly bound strong hydrophobic substances on C18 packing,
Figure BDA0003874565130000056
CN filler is a more suitable choice.

Figure BDA0003874565130000057
Carb-GCB填料为石墨化炭黑，由无孔片状分子组成，带有芳香性的正六元环结构，且呈正电性，具备反相和离子交换双重保留机制，既能保留非极性化合物(如有机氯杀虫剂)，也能保留强极性化合物(如表面活性剂)。
Figure BDA0003874565130000058
Carb-GCB为片状物质，无孔隙，因而萃取速度非常快，且吸附容量大于硅胶。
Figure BDA0003874565130000057
Carb-GCB filler is graphitized carbon black, composed of non-porous sheet-like molecules, with an aromatic positive six-membered ring structure, and is positively charged. It has dual retention mechanisms of reverse phase and ion exchange, and can retain non-polar compounds. (such as organochlorine pesticides), and can also retain highly polar compounds (such as surfactants).
Figure BDA0003874565130000058
Carb-GCB is a sheet-like substance without pores, so the extraction speed is very fast, and its adsorption capacity is greater than that of silica gel.

Figure BDA0003874565130000059
Florisil填料为农残级弗罗里硅土，其经675℃活化，是一种强极性、高活性的多孔吸附剂，可吸附低极性和中等极性的目标化合物，如含氯、氮和磷的有机农药。在农药多残留检测中，Florisil柱效果好，成本低。
Figure BDA0003874565130000059
The Florisil filler is pesticide grade Florisil, which is activated at 675°C. It is a highly polar and highly active porous adsorbent that can adsorb low-polarity and medium-polarity target compounds, such as chlorine and nitrogen. and phosphorus organic pesticides. In the detection of multi-residue pesticides, the Florisil column has good effect and low cost.

Figure BDA00038745651300000510
ALA填料为酸性氧化铝，基于高活性多孔氧化铝，其表面电子可与芳香环形成pi-pi相互作用，具有很强的极性保留能力和Lewis酸特性。与未键合硅胶相比，氧化铝在高pH环境中更稳定，适合芳香胺类化合物的萃取。
Figure BDA00038745651300000511
ALA经过特殊处理，其pH值为4.0，呈酸性。
Figure BDA00038745651300000510
ALA filler is acidic alumina, based on highly active porous alumina. Its surface electrons can form pi-pi interactions with aromatic rings, and it has strong polar retention ability and Lewis acid characteristics. Compared with unbonded silica gel, alumina is more stable in a high pH environment and is suitable for the extraction of aromatic amines.
Figure BDA00038745651300000511
ALA is specially processed to have a pH of 4.0, which is acidic.

Figure BDA00038745651300000512
ALN填料为中性氧化铝，基于高活性多孔氧化铝，其表面电子可与芳香环形成pi-pi相互作用，具有很强的极性保留能力和Lewis酸特性。与未键合硅胶相比，氧化铝在高pH环境中更稳定，适合芳香胺类化合物的萃取。
Figure BDA0003874565130000061
ALN经过特殊处理，其pH值为7.0，呈中性。
Figure BDA00038745651300000512
ALN filler is neutral alumina, based on highly active porous alumina, whose surface electrons can form pi-pi interactions with aromatic rings, and has strong polarity retention and Lewis acid properties. Compared with unbonded silica gel, alumina is more stable in a high pH environment and is suitable for the extraction of aromatic amines.
Figure BDA0003874565130000061
After special treatment, ALN has a pH value of 7.0, which is neutral.

Figure BDA0003874565130000062
ALB填料为碱性氧化铝，基于高活性多孔氧化铝，其表面电子可与芳香环形成pi-pi相互作用，具有很强的极性保留能力和Lewis酸特性。与未键合硅胶相比，氧化铝在高pH环境中更稳定，适合芳香胺类化合物的萃取。
Figure BDA0003874565130000063
ALB经过特殊处理，其pH值为9.5，呈碱性。
Figure BDA0003874565130000062
ALB filler is basic alumina, based on highly active porous alumina, whose surface electrons can form pi-pi interactions with aromatic rings, with strong polarity retention and Lewis acid properties. Compared with unbonded silica gel, alumina is more stable in a high pH environment and is suitable for the extraction of aromatic amines.
Figure BDA0003874565130000063
ALB is specially processed to have an alkaline pH of 9.5.

Figure BDA0003874565130000064
SCX填料为强阳离子交换填料，其官能团为负电性的苯磺酸基，具有很强的阳离子交换能力，此外苯环有一定疏水保留作用。
Figure BDA0003874565130000065
SCX能萃取带正电荷的碱性化合物，如胺类化合物。
Figure BDA0003874565130000064
SCX packing is a strong cation exchange packing, and its functional group is negatively charged benzenesulfonic acid group, which has a strong cation exchange capacity. In addition, the benzene ring has a certain hydrophobic retention effect.
Figure BDA0003874565130000065
SCX can extract positively charged basic compounds such as amines.

Figure BDA0003874565130000066
SAX填料为强阴离子交换填料，是硅胶基质的季铵基键合相，在全pH范围皆带正电荷，具有很强的阴离子交换能力。SAX非常适合萃取弱酸性化合物，如羧酸。
Figure BDA0003874565130000066
SAX packing is a strong anion exchange packing, which is a quaternary ammonium-based bonded phase of silica gel matrix. It is positively charged in the whole pH range and has a strong anion exchange capacity. SAX is well suited for the extraction of weakly acidic compounds such as carboxylic acids.

Figure BDA0003874565130000067
NH2填料为氨丙基类填料，在非极性有机溶剂中具有强极性吸附，具有弱阴离子交换保留作用。
Figure BDA0003874565130000067
The NH 2 filler is an aminopropyl type filler, which has strong polar adsorption in non-polar organic solvents and weak anion exchange retention.

Figure BDA0003874565130000068
PSA填料为乙二胺-N-丙基类填料，其与NH2类似，具有弱阴离子交换和正相保留作用。PSA的两个氨基(pKa分别为10.1和10.9)，提供了更大的离子交换容量，并能通过氢键萃取极性化合物。此外，PSA与金属离子形成络合物，可保留某些金属离子。
Figure BDA0003874565130000068
PSA packing is ethylenediamine-N-propyl type packing, which is similar to NH 2 and has weak anion exchange and normal phase retention. The two amino groups of PSA (pKa are 10.1 and 10.9, respectively), provide greater ion exchange capacity and can extract polar compounds through hydrogen bonding. In addition, PSA forms complexes with metal ions, which can retain some metal ions.

Figure BDA0003874565130000069
PRS填料为丙磺酸类填料，是以丙磺酸键合硅胶为填料的强阳离子交换型萃取柱，对弱碱性化合物具有良好的保留能力。
Figure BDA00038745651300000610
PRS中不存在非极性次级作用，因而具有独特的选择性。如使用SCX，样品基质中的非极性成分产生干扰时，可用
Figure BDA00038745651300000611
PRS填料进行萃取。
Figure BDA0003874565130000069
PRS filler is propanesulfonic acid filler, which is a strong cation exchange extraction column with propanesulfonic acid bonded silica gel as filler, and has good retention capacity for weakly basic compounds.
Figure BDA00038745651300000610
There is no non-polar secondary effect in PRS, so it has unique selectivity. When using SCX, when non-polar components in the sample matrix interfere, use
Figure BDA00038745651300000611
PRS packing for extraction.

包覆层30通过将第二聚合物溶解或分散于溶剂中得包覆液，再将包覆液设置于芯核10的表面干燥可得。溶剂为四氢呋喃、乙二醇二甲醚、正戊烷、正己烷、环己烷、甲苯、二甲苯、三甲苯、乙酸乙酯、甲酸甲酯、邻苯二甲酸二甲酯、乙腈、N甲基吡咯烷酮、N,N二甲基甲酰胺、二氯甲烷和1,2二氯乙烷中的至少一种。包覆液可涂覆于芯核10的表面再进行干燥，或者将芯核10浸渍于包覆液中再拿出进行干燥从而于芯核10的表面形成包覆层30。The coating layer 30 can be obtained by dissolving or dispersing the second polymer in a solvent to obtain a coating solution, and then placing the coating solution on the surface of the core 10 to dry. The solvent is tetrahydrofuran, ethylene glycol dimethyl ether, n-pentane, n-hexane, cyclohexane, toluene, xylene, trimethylbenzene, ethyl acetate, methyl formate, dimethyl phthalate, acetonitrile, N-methyl at least one of ylpyrrolidone, N,N dimethylformamide, dichloromethane and 1,2 dichloroethane. The coating solution can be coated on the surface of the core 10 and then dried, or the core 10 can be immersed in the coating solution and then taken out and dried to form the coating layer 30 on the surface of the core 10 .

第二聚合物选自硝酸纤维素、醋酸纤维素、聚醚砜和聚偏氟乙烯中的至少一种。The second polymer is at least one selected from nitrocellulose, cellulose acetate, polyethersulfone and polyvinylidene fluoride.

其中，硝酸纤维素可制成硝酸纤维素膜(nitrocellulose filter membrane，简称NC膜)，通常在胶体金试纸中用做C/T线的承载体，同时也是免疫反应的发生处。NC膜是生物学试验中最重要的耗材之一。Among them, nitrocellulose can be made into nitrocellulose filter membrane (NC membrane for short), which is usually used as the carrier of C/T line in colloidal gold test paper, and also where the immune reaction occurs. NC membrane is one of the most important consumables in biological experiments.

醋酸纤维素可制成醋酸纤维素膜(CA)，其是由二醋酸纤维素和三醋酸纤维素的铸膜液及二者混合物浇铸而成。随着乙酰基含量的增加，盐截留率与化学稳定性增加而水通量下降。Cellulose acetate can be made into cellulose acetate film (CA), which is cast from the casting solution of cellulose diacetate and cellulose triacetate and the mixture of the two. With the increase of acetyl group content, the salt rejection and chemical stability increased while the water flux decreased.

聚醚砜可制成聚醚砜微孔滤膜(PES)，其具有天然的亲水性能，与其他膜品种相比较，PES膜具有非常好的水湿润性，因此PES膜具备较高的水通量。PES膜表现出非常低的蛋白吸附能力，被广泛应用于食品、医药等领域的过滤和澄清。聚醚砜性能优异，能够耐受pH为1～14的溶液，耐有机溶剂性能良好，且耐温能达150℃，是目前制药行业应用最为广泛的亲水性膜材，常用于液体除菌和除支原体过滤。Polyethersulfone can be made into polyethersulfone microporous membrane (PES), which has natural hydrophilic properties. Compared with other membrane varieties, PES membrane has very good water wettability, so PES membrane has higher water flux. PES membranes exhibit very low protein adsorption capacity and are widely used in filtration and clarification in food, medicine and other fields. Polyethersulfone has excellent performance, can tolerate solutions with a pH of 1 to 14, has good resistance to organic solvents, and can withstand temperatures up to 150°C. It is the most widely used hydrophilic membrane material in the pharmaceutical industry and is often used for liquid sterilization. and filter for mycoplasma removal.

聚偏氟乙烯可制成聚偏氟乙烯膜(polyvinylidene fluoride)，是蛋白质印迹法中常用的一种固相支持物。PVDF膜是疏水性的，膜孔径有大有小，随着膜孔径的不断减小，膜对低分子量的蛋白结合就越牢固。Polyvinylidene fluoride can be made into polyvinylidene fluoride membrane (polyvinylidene fluoride), which is a solid phase support commonly used in Western blotting. PVDF membrane is hydrophobic, and the membrane pore size varies. As the membrane pore size decreases, the membrane binds to low-molecular-weight proteins more firmly.

本发明的制备方法可包括步骤：包括步骤：The preparation method of the present invention may comprise the steps of: comprising the steps of:

(1)按照配方比混合第一聚合物和吸附性填料成预烧混料；(1) Mixing the first polymer and the adsorptive filler according to the formula ratio to form a pre-calcined mixture;

(2)将预烧混料混匀后振动压缩得预烧料；(2) Vibrating and compressing the calcined mixture after mixing to obtain the calcined material;

(3)将预烧料进行烧结得滤芯；(3) Sintering the pre-fired material to obtain a filter element;

(4)滤芯冷却后于表面包覆第二聚合物膜。(4) The surface of the filter core is coated with a second polymer film after cooling.

其中，步骤(1)中，吸附性填料占第一聚合物和吸附性填料总重量的比例大于等于0.05％小于等于60％。作为示例，比例可为0.05％、0.1％、0.5％、1％、3％、5％、8％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％。作为示例，吸附性填料占第一聚合物和吸附性填料总重量的比例为33％。第一聚合物10选自聚丙烯、聚乙烯和聚对苯二甲酸乙二醇酯中的至少一种。作为示例，第一聚合物10选自聚丙烯。常温下第一聚合物10可为颗粒状。吸附性填料13为硅胶、活性铝、碳类吸附剂、分子筛、聚合物吸附剂或生物吸附剂。作为示例的，吸附性填料13可为

Figure BDA0003874565130000081
HLB填料、
Figure BDA0003874565130000082
WAX填料、
Figure BDA0003874565130000083
WCX填料、
Figure BDA0003874565130000084
MAX填料、
Figure BDA0003874565130000085
MCX填料、
Figure BDA0003874565130000086
C18填料、
Figure BDA0003874565130000087
C8填料、SPE C4硅胶填料、
Figure BDA0003874565130000088
Silica硅胶填料、
Figure BDA0003874565130000089
Diol填料、
Figure BDA00038745651300000810
CN填料、
Figure BDA00038745651300000811
Carb-GCB填料、
Figure BDA00038745651300000812
Florisil填料、
Figure BDA00038745651300000813
ALA填料、
Figure BDA00038745651300000814
ALN填料、
Figure BDA00038745651300000815
ALB填料、
Figure BDA00038745651300000816
SCX填料、
Figure BDA00038745651300000817
SAX填料、
Figure BDA00038745651300000818
NH2填料、
Figure BDA00038745651300000819
PSA填料和
Figure BDA00038745651300000820
PRS填料中的至少一种。Wherein, in step (1), the ratio of the adsorptive filler to the total weight of the first polymer and the adsorptive filler is greater than or equal to 0.05% and less than or equal to 60%. As an example, the ratio can be 0.05%, 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% , 50%, 55%, 60%. As an example, the proportion of the adsorptive filler to the total weight of the first polymer and the adsorptive filler is 33%. The first polymer 10 is selected from at least one of polypropylene, polyethylene and polyethylene terephthalate. As an example, the first polymer 10 is selected from polypropylene. The first polymer 10 may be in granular form at normal temperature. Adsorptive filler 13 is silica gel, activated aluminum, carbon-based adsorbent, molecular sieve, polymer adsorbent or biosorbent. As an example, the adsorptive filler 13 can be
Figure BDA0003874565130000081
HLB filler,
Figure BDA0003874565130000082
WAX filler,
Figure BDA0003874565130000083
WCX packing,
Figure BDA0003874565130000084
MAX packing,
Figure BDA0003874565130000085
MCX packing,
Figure BDA0003874565130000086
C18 packing,
Figure BDA0003874565130000087
C8 packing, SPE C4 silica gel packing,
Figure BDA0003874565130000088
Silica silica gel packing,
Figure BDA0003874565130000089
Diol filler,
Figure BDA00038745651300000810
CN filler,
Figure BDA00038745651300000811
Carb-GCB filler,
Figure BDA00038745651300000812
Florisil filler,
Figure BDA00038745651300000813
ALA filler,
Figure BDA00038745651300000814
ALN packing,
Figure BDA00038745651300000815
ALB packing,
Figure BDA00038745651300000816
SCX packing,
Figure BDA00038745651300000817
SAX filler,
Figure BDA00038745651300000818
NH 2 filler,
Figure BDA00038745651300000819
PSA filler and
Figure BDA00038745651300000820
At least one of the PRS fillers.

步骤(2)中，混匀于混匀设备中进行，且混匀采用的设备转速为5r/min至200r/min，转动时间为0.5h至10h。转速可但不限于为5r/min、10r/min、15r/min、25r/min、35r/min、45r/min、50r/min、65r/min、75r/min、95r/min、110r/min、130r/min、150r/min、170r/min、190r/min、200r/min。转动时间为0.5h、1h、2h、3h、4h、5h、6h、7h、8h、9h、10h。作为示例，转速为50r/min，转动时间为6h。振动可为将预烧混料装入烧结模具之后对模具外壁进行操作，振动可采用行业公知的相关设备。振动采用的频率为5Hz至200Hz，振动时间为3s至600s。频率可但不限于为5Hz、10Hz、15Hz、25Hz、35Hz、50Hz、75Hz、95Hz、110Hz、130Hz、150Hz、175Hz、200Hz。振动时间可但不限于为3s、6s、10s、15s、20s、25s、35s、45s、60s、80s、100s、150s、200s、250s、300s、350s、400s、450s、500s、550s、600s。作为示例，振动频率为50Hz，振动时间为15s。压缩程度可影响烧结后所得滤芯中第一聚合物颗粒之间的孔隙尺寸，故可根据实际情况调节压缩强度。In step (2), the mixing is carried out in a mixing equipment, and the rotation speed of the equipment used for mixing is 5r/min to 200r/min, and the rotation time is 0.5h to 10h. The speed can be but not limited to 5r/min, 10r/min, 15r/min, 25r/min, 35r/min, 45r/min, 50r/min, 65r/min, 75r/min, 95r/min, 110r/min, 130r/min, 150r/min, 170r/min, 190r/min, 200r/min. The rotation time is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h. As an example, the rotation speed is 50r/min, and the rotation time is 6h. Vibration can be performed on the outer wall of the mold after the pre-sintered mixture is loaded into the sintering mold, and related equipment known in the industry can be used for vibration. The vibration frequency is from 5Hz to 200Hz, and the vibration time is from 3s to 600s. The frequency can be but not limited to 5Hz, 10Hz, 15Hz, 25Hz, 35Hz, 50Hz, 75Hz, 95Hz, 110Hz, 130Hz, 150Hz, 175Hz, 200Hz. The vibration time can be but not limited to 3s, 6s, 10s, 15s, 20s, 25s, 35s, 45s, 60s, 80s, 100s, 150s, 200s, 250s, 300s, 350s, 400s, 450s, 500s, 550s, 600s. As an example, the vibration frequency is 50Hz, and the vibration time is 15s. The degree of compression can affect the pore size between the first polymer particles in the obtained filter element after sintering, so the compression strength can be adjusted according to the actual situation.

步骤(3)中，烧结的温度为110℃至250℃，时间为1.5min至50min。温度具体可但不限于为110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃。时间可但不限于为1.5min、3min、5min、7min、10min、15min、20min、25min、35min、40min、45min、47min、50min。作为示例，烧结的温度为180℃，时间为20min。烧结中第一聚合物颗粒之间形成孔隙以用于样液的过滤。In step (3), the sintering temperature is 110°C to 250°C, and the time is 1.5min to 50min. The temperature can be but not limited to 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C ℃. The time can be but not limited to 1.5 min, 3 min, 5 min, 7 min, 10 min, 15 min, 20 min, 25 min, 35 min, 40 min, 45 min, 47 min, 50 min. As an example, the sintering temperature is 180° C. and the time is 20 minutes. During sintering, pores are formed between the first polymer particles for filtering the sample liquid.

步骤(4)中，冷却的温度为3℃至35℃，时间为1.5min至50min。冷却温度可但不限于为3℃、5℃、8℃、13℃、15℃、18℃、20℃、23℃、26℃、29℃、31℃、33℃、35℃，时间为1.5min、3min、5min、8min、10min、13min、15min、20min、25min、30min、35min、40min、45min、50min。第二聚合物膜通过将第二聚合物溶解或分散于溶剂中得包覆液，再将包覆液设置于滤芯的表面干燥可得。第二聚合物选自硝酸纤维素、醋酸纤维素、聚醚砜和聚偏氟乙烯中的至少一种。溶剂为四氢呋喃、乙二醇二甲醚、正戊烷、正己烷、环己烷、甲苯、二甲苯、三甲苯、乙酸乙酯、甲酸甲酯、邻苯二甲酸二甲酯、乙腈、N甲基吡咯烷酮、N,N二甲基甲酰胺、二氯甲烷和1,2二氯乙烷中的至少一种。包覆液可涂覆于滤芯的表面再进行干燥，或者将滤芯浸渍于包覆液中再拿出进行干燥从而形成包覆层，干燥可于30℃至120℃下进行。In step (4), the cooling temperature is 3°C to 35°C, and the cooling time is 1.5min to 50min. The cooling temperature can be but not limited to 3°C, 5°C, 8°C, 13°C, 15°C, 18°C, 20°C, 23°C, 26°C, 29°C, 31°C, 33°C, 35°C, and the time is 1.5min , 3min, 5min, 8min, 10min, 13min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min. The second polymer film can be obtained by dissolving or dispersing the second polymer in a solvent to obtain a coating solution, and then placing the coating solution on the surface of the filter element to dry. The second polymer is at least one selected from nitrocellulose, cellulose acetate, polyethersulfone and polyvinylidene fluoride. The solvent is tetrahydrofuran, ethylene glycol dimethyl ether, n-pentane, n-hexane, cyclohexane, toluene, xylene, trimethylbenzene, ethyl acetate, methyl formate, dimethyl phthalate, acetonitrile, N-methyl at least one of ylpyrrolidone, N,N dimethylformamide, dichloromethane and 1,2 dichloroethane. The coating liquid can be coated on the surface of the filter element and then dried, or the filter element can be immersed in the coating liquid and then taken out to be dried to form a coating layer, and the drying can be carried out at 30°C to 120°C.

为更好地说明本发明的目的、技术方案和有益效果，下面将结合具体实施例对本发明作进一步说明。需说明的是，下述实施所述方法是对本发明做的进一步解释说明，不应当作为对本发明的限制。In order to better illustrate the purpose, technical solutions and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific examples. It should be noted that the implementation of the method described below is a further explanation of the present invention, and should not be regarded as a limitation of the present invention.

实施例1Example 1

本实施例多功能滤芯的制备方法，包括步骤：The preparation method of the multifunctional filter element of the present embodiment comprises steps:

(1)按照2:1的重量比混合聚丙烯和

Figure BDA0003874565130000091
WAX填料成预烧混料；(1) Mix polypropylene and
Figure BDA0003874565130000091
WAX filler into pre-fired mixture;

(2)将预烧混料于混匀设备中混匀，且采用的设备转速为50r/min，转动时间为6h，混匀后于50Hz频率下振动15s再压缩得预烧料；(2) Mix the pre-fired mixture in a mixing equipment, and the equipment speed used is 50r/min, and the rotation time is 6h. After mixing, vibrate at a frequency of 50Hz for 15s and then compress to obtain the pre-fired material;

(3)将预烧料于180℃进行烧结20min得滤芯；(3) Sintering the pre-sintered material at 180°C for 20 minutes to obtain a filter element;

(4)滤芯于20℃下冷却15min后于表面涂覆浓度为10％的硝酸纤维素溶液(溶解为乙二醇二甲醚)再干燥成聚合物膜。(4) After the filter element is cooled at 20°C for 15 minutes, the surface is coated with nitrocellulose solution (dissolved as ethylene glycol dimethyl ether) with a concentration of 10%, and then dried to form a polymer film.

实施例2Example 2

本实施例多功能滤芯的制备方法，包括步骤：The preparation method of the multifunctional filter element of the present embodiment comprises steps:

(1)按照3:1的重量比混合聚乙烯和

Figure BDA0003874565130000092
Silica硅胶填料成预烧混料；(1) mix polyethylene and
Figure BDA0003874565130000092
Silica silica gel filler into pre-fired mixture;

(2)将预烧混料于混匀设备中混匀，且采用的设备转速为100r/min，转动时间为10h，混匀后于30Hz频率下振动90s再压缩得预烧料；(2) Mix the pre-fired mixture in a mixing equipment, and the equipment speed used is 100r/min, and the rotation time is 10h. After mixing, vibrate at a frequency of 30Hz for 90s and then compress to obtain the pre-fired material;

(3)将预烧料于200℃进行烧结15min得滤芯；(3) Sintering the pre-sintered material at 200°C for 15 minutes to obtain a filter element;

(4)滤芯于18℃下冷却10min后于表面涂覆浓度为10％的聚偏氟乙烯溶液(溶解为N甲基吡咯烷酮)再干燥成聚合物膜。(4) After the filter element is cooled at 18°C for 10 minutes, the surface is coated with a polyvinylidene fluoride solution (dissolved as N-methylpyrrolidone) with a concentration of 10%, and then dried to form a polymer film.

实施例3Example 3

本实施例多功能滤芯的制备方法，包括步骤：The preparation method of the multifunctional filter element of the present embodiment comprises steps:

(1)按照4:1的重量比混合聚丙烯和

Figure BDA0003874565130000101
WAX填料成预烧混料；(1) Mix polypropylene and
Figure BDA0003874565130000101
WAX filler into pre-fired mixture;

(2)将预烧混料于混匀设备中混匀，且采用的设备转速为250r/min，转动时间为6h，混匀后于210Hz频率下振动15s再压缩得预烧料；(2) Mix the pre-fired mixture in a mixing equipment, and the equipment speed used is 250r/min, and the rotation time is 6h. After mixing, vibrate at a frequency of 210Hz for 15s and then compress to obtain the pre-fired material;

(3)将预烧料于150℃进行烧结40min得滤芯；(3) Sintering the pre-sintered material at 150°C for 40 minutes to obtain a filter element;

(4)滤芯于30℃下冷却25min后于表面涂覆浓度为15％的硝酸纤维素溶液(溶解为正己烷)再干燥成聚合物膜。(4) After the filter element is cooled at 30°C for 25 minutes, the surface is coated with a nitrocellulose solution (dissolved in n-hexane) with a concentration of 15%, and then dried to form a polymer film.

对比例1Comparative example 1

本实施例多功能滤芯的制备方法，包括步骤：The preparation method of the multifunctional filter element of the present embodiment comprises steps:

(1)按照2:1的重量比混合聚丙烯和

Figure BDA0003874565130000102
WAX填料成预烧混料；(1) Mix polypropylene and
Figure BDA0003874565130000102
WAX filler into pre-fired mixture;

(2)将预烧混料于180℃进行烧结20min得滤芯。(2) Sinter the pre-calcined mixture at 180° C. for 20 minutes to obtain a filter element.

对比例2Comparative example 2

本实施例多功能滤芯的制备方法，包括步骤：The preparation method of the multifunctional filter element of the present embodiment comprises steps:

(1)按照2:1的重量比混合聚丙烯和

Figure BDA0003874565130000103
WAX填料成预烧混料；(1) Mix polypropylene and
Figure BDA0003874565130000103
WAX filler into pre-fired mixture;

(2)将预烧混料于180℃进行烧结20min得滤芯；(2) Sintering the pre-sintered mixture at 180°C for 20 minutes to obtain a filter element;

(3)滤芯于20℃下冷却15min后于表面涂覆浓度为10％的硝酸纤维素溶液(溶解为乙二醇二甲醚)再干燥成聚合物膜。(3) After the filter element is cooled at 20°C for 15 minutes, the surface is coated with nitrocellulose solution (dissolved as ethylene glycol dimethyl ether) with a concentration of 10%, and then dried to form a polymer film.

对比例3Comparative example 3

本实施例多功能滤芯的制备方法，包括步骤：The preparation method of the multifunctional filter element of the present embodiment comprises steps:

(1)按照2:1的重量比混合聚丙烯和

Figure BDA0003874565130000104
WAX填料成预烧混料；(1) Mix polypropylene and
Figure BDA0003874565130000104
WAX filler into pre-fired mixture;

(2)将预烧混料于混匀设备中混匀，且采用的设备转速为50r/min，转动时间为6h，混匀后于50Hz频率下振动15s再压缩得预烧料；(2) Mix the pre-fired mixture in a mixing equipment, and the equipment speed used is 50r/min, and the rotation time is 6h. After mixing, vibrate at a frequency of 50Hz for 15s and then compress to obtain the pre-fired material;

(3)将预烧料于180℃进行烧结20min得滤芯。(3) Sinter the calcined material at 180° C. for 20 minutes to obtain a filter element.

将实施例1～3和对比例1～3所制得的多功能滤芯进行性能测试，其测试条件如下，测试结果如表1所示。The multifunctional filter elements prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests, and the test conditions were as follows, and the test results are shown in Table 1.

孔径和孔隙率测试：利用孔径分析仪、测孔仪(参考GB/T 21650.1-2008第一部分：压汞法)分别测试多功能滤芯的平均孔径和孔隙率。Pore size and porosity test: Use a pore size analyzer and a porosimeter (refer to GB/T 21650.1-2008 Part I: Mercury porosimetry) to test the average pore size and porosity of the multifunctional filter element.

回收率：指滤芯经过过滤后的回收量与滤芯投入样本量的百分比。Recovery rate: refers to the percentage of the recovered amount of the filter element after filtration and the input sample volume of the filter element.

表1实施例中各多功能滤芯的性能The performance of each multifunctional filter element in the embodiment of table 1

Figure BDA0003874565130000111
Figure BDA0003874565130000111

由表1的结果可知，实施例1～3的多功能滤芯在制备时经过振动压缩和聚合物包覆之后，其吸附综合性能更佳。From the results in Table 1, it can be seen that the comprehensive adsorption performance of the multifunctional filter elements of Examples 1-3 is better after vibration compression and polymer coating during preparation.

最后应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，但是也并不仅限于实施例中所列，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, they are not limited to those listed in the examples. Those of ordinary skill in the art should understand that the technical solution of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1.用于样液分离的多功能滤芯的制备方法，其特征在于，包括步骤：1. the preparation method of the multifunctional filter core that is used for sample liquid separation is characterized in that, comprises steps: (1)按照配方比混合第一聚合物和吸附性填料成预烧混料；(1) Mixing the first polymer and the adsorptive filler according to the formula ratio to form a pre-calcined mixture; (2)将所述预烧混料混匀后振动压缩得预烧料；(2) vibrating and compressing the calcined mixture to obtain calcined material after mixing; (3)将所述预烧料进行烧结得滤芯；(3) sintering the pre-fired material to obtain a filter element; (4)所述滤芯冷却后于表面包覆第二聚合物膜。(4) The surface of the filter core is coated with a second polymer film after cooling. 2.根据权利要求1所述的用于样液分离的多功能滤芯的制备方法，其特征在于，所述吸附性填料占所述第一聚合物和所述吸附性填料总重量的比例大于等于0.05％小于等于60％。2. The method for preparing a multifunctional filter element for sample liquid separation according to claim 1, wherein the ratio of the adsorptive filler to the total weight of the first polymer and the adsorptive filler is greater than or equal to 0.05% or less than 60%. 3.根据权利要求1所述的用于样液分离的多功能滤芯的制备方法，其特征在于，所述吸附性填料为硅胶、活性铝、碳类吸附剂、分子筛、聚合物吸附剂或生物吸附剂。3. the preparation method of the multifunctional filter core that is used for sample liquid separation according to claim 1, is characterized in that, described adsorptive filler is silica gel, activated aluminum, carbon-based adsorbent, molecular sieve, polymer adsorbent or biological Adsorbent. 4.根据权利要求1所述的用于样液分离的多功能滤芯的制备方法，其特征在于，所述吸附性填料为
Figure FDA0003874565120000011
HLB填料、
Figure FDA0003874565120000012
WAX填料、
Figure FDA0003874565120000013
WCX填料、
Figure FDA0003874565120000014
MAX填料、
Figure FDA0003874565120000015
MCX填料、
Figure FDA0003874565120000016
C18填料、
Figure FDA0003874565120000017
C8填料、SPE C4硅胶填料、
Figure FDA0003874565120000018
Silica硅胶填料、
Figure FDA0003874565120000019
Diol填料、
Figure FDA00038745651200000110
CN填料、
Figure FDA00038745651200000111
Carb-GCB填料、
Figure FDA00038745651200000112
Florisil填料、
Figure FDA00038745651200000113
ALA填料、
Figure FDA00038745651200000114
ALN填料、
Figure FDA00038745651200000115
ALB填料、
Figure FDA00038745651200000116
SCX填料、
Figure FDA00038745651200000117
SAX填料、
Figure FDA00038745651200000118
NH2填料、
Figure FDA00038745651200000119
PSA填料和
Figure FDA00038745651200000120
PRS填料中的至少一种。4. the preparation method of the multifunctional filter core that is used for sample liquid separation according to claim 1, is characterized in that, described adsorptive filler is
Figure FDA0003874565120000011
HLB filler,
Figure FDA0003874565120000012
WAX filler,
Figure FDA0003874565120000013
WCX packing,
Figure FDA0003874565120000014
MAX packing,
Figure FDA0003874565120000015
MCX packing,
Figure FDA0003874565120000016
C18 packing,
Figure FDA0003874565120000017
C8 packing, SPE C4 silica gel packing,
Figure FDA0003874565120000018
Silica silica gel packing,
Figure FDA0003874565120000019
Diol filler,
Figure FDA00038745651200000110
CN filler,
Figure FDA00038745651200000111
Carb-GCB filler,
Figure FDA00038745651200000112
Florisil filler,
Figure FDA00038745651200000113
ALA filler,
Figure FDA00038745651200000114
ALN packing,
Figure FDA00038745651200000115
ALB packing,
Figure FDA00038745651200000116
SCX packing,
Figure FDA00038745651200000117
SAX filler,
Figure FDA00038745651200000118
NH 2 filler,
Figure FDA00038745651200000119
PSA filler and
Figure FDA00038745651200000120
At least one of the PRS fillers. 5.根据权利要求1所述的用于样液分离的多功能滤芯的制备方法，其特征在于，所述第一聚合物选自聚对苯二甲酸乙二醇酯、聚丙烯和聚乙烯中的至少一种。5. the preparation method of the multifunctional filter core that is used for sample liquid separation according to claim 1 is characterized in that, described first polymer is selected from polyethylene terephthalate, polypropylene and polyethylene at least one of . 6.根据权利要求1所述的用于样液分离的多功能滤芯的制备方法，其特征在于，所述第二聚合物膜通过将第二聚合物溶解或分散于溶剂中得包覆液，再将所述包覆液设置于所述滤芯的表面干燥可得。6. the preparation method of the multifunctional filter element that is used for sample liquid separation according to claim 1, is characterized in that, described second polymer membrane obtains coating liquid by dissolving or dispersing second polymer in solvent, Then the coating solution is placed on the surface of the filter element to dry. 7.根据权利要求6所述的用于样液分离的多功能滤芯的制备方法，其特征在于，所述第二聚合物选自硝酸纤维素、醋酸纤维素、聚醚砜和聚偏氟乙烯中的至少一种。7. the preparation method of the multifunctional filter core that is used for sample liquid separation according to claim 6 is characterized in that, described second polymer is selected from nitrocellulose, cellulose acetate, polyethersulfone and polyvinylidene fluoride at least one of the 8.根据权利要求1所述的用于样液分离的多功能滤芯的制备方法，其特征在于，包括下述特征(1)至(4)中的至少一个：8. The preparation method of a multifunctional filter element for sample liquid separation according to claim 1, characterized in that, comprising at least one of the following features (1) to (4): (1)所述混匀采用的设备转速为5r/min至200r/min，转动时间为0.5h至10h；(1) The rotating speed of the equipment used for the mixing is 5r/min to 200r/min, and the rotation time is 0.5h to 10h; (2)所述振动采用的频率为5Hz至200Hz，振动时间为3s至600s；(2) The frequency used for the vibration is 5Hz to 200Hz, and the vibration time is 3s to 600s; (3)所述烧结的温度为110℃至250℃，时间为1.5min至50min；(3) The temperature of the sintering is 110°C to 250°C, and the time is 1.5min to 50min; (4)所述冷却的温度为3℃至35℃，时间为1.5min至50min。(4) The cooling temperature is 3°C to 35°C, and the cooling time is 1.5min to 50min. 9.根据权利要求1至8任意一项所述的用于样液分离的多功能滤芯的制备方法所制备的多功能滤芯，其特征在于，包括由所述第一聚合物和所述吸附性填料混合烧结而成的芯核和包裹所述芯核的包覆层。9. The multifunctional filter element prepared by the method for preparing a multifunctional filter element for sample liquid separation according to any one of claims 1 to 8, characterized in that, comprising the first polymer and the adsorptive The filler is mixed with a sintered core and a cladding layer surrounding the core. 10.根据权利要求1至8任意一项所述的用于样液分离的多功能滤芯的制备方法所制备的多功能滤芯或权利要求9所述的多功能滤芯于生物或医药类样液分离中的应用。10. The multifunctional filter element prepared according to the preparation method of the multifunctional filter element for sample liquid separation according to any one of claims 1 to 8 or the multifunctional filter element according to claim 9 is used for biological or medical sample liquid separation in the application.
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