CN116651420A - 一种环聚果糖交联聚合物涂层纤维的制备方法与应用 - Google Patents
一种环聚果糖交联聚合物涂层纤维的制备方法与应用 Download PDFInfo
- Publication number
- CN116651420A CN116651420A CN202310947857.3A CN202310947857A CN116651420A CN 116651420 A CN116651420 A CN 116651420A CN 202310947857 A CN202310947857 A CN 202310947857A CN 116651420 A CN116651420 A CN 116651420A
- Authority
- CN
- China
- Prior art keywords
- fiber
- crosslinked polymer
- fructo
- polymer coated
- coated fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 70
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 15
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000011241 protective layer Substances 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- 125000004122 cyclic group Chemical group 0.000 abstract description 10
- 238000004458 analytical method Methods 0.000 abstract description 7
- 229920000157 polyfructose Polymers 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 9
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000012206 bottled water Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000581 reactive spray deposition Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/328—Polymers on the carrier being further modified
- B01J20/3282—Crosslinked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
- B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及一种环聚果糖交联聚合物涂层纤维的制备方法与应用，提供了一种环聚果糖交联聚合物涂层纤维的制备方法，可将环聚果糖交联聚合物均匀的在氨基化玻璃纤维表面原位合成。本发明制得的环聚果糖交联聚合物涂层纤维，用于管内纤维固相微萃取（IT‑SPME）方法后，在后续分析中检测限低、灵敏度高、重现性好。本发明制备的环聚果糖交联聚合物涂层纤维，可重复使用至少200次，其萃取性能无明显变化，具有优异的稳定性和耐用性。
Description
技术领域
本发明涉及管内纤维固相微萃取技术领域，尤其是涉及一种环聚果糖交联聚合物涂层纤维及其制备方法和应用。
背景技术
目前人类生活的环境中存在各种各样的有机污染物，其中最典型的是多环芳烃（PAHs）。PAHs属于是一类具有强致癌性、致突变和致畸性的持久性有机疏水污染物。已有研究发现PAHs在水环境中广泛存在，对人类健康与环境造成了极大的危害。目前，PAHs已被国际环境保护署确定为危险的致癌物。PAHs在水环境中通常以微量和痕量的浓度存在，为了准确检测环境水样中PAHs，需要选择好、灵敏度高和重现性好的分析方法。
管内纤维固相微萃取（IT-SPME）是一种新型的萃取方法。与传统样品前处理方式（液-液萃取和固相萃取）相比，IT-SPME技术具有快速准确、灵敏度高、重现性好和可以与高效液相色谱实现在线自动化联用的优点。纤维涂层是IT-SPME技术能够实现复杂体系中目标物分离富集的关键，同时现有的纤维涂层通常面临使用次数有限、寿命短的缺点，设计合成新型的和耐用性好的纤维涂层是IT-SPME技术面临的难点与挑战。
交联聚合物具有合成简单、可调孔隙、比表面积大和活性位点多的特点。环聚果糖是由6个呋喃型葡萄糖通过α-1,2糖苷键连接而形成的碗状低聚糖，具有分子强度高，热稳定性好等优点。此外，环聚果糖本身具有内腔和羟基活性基团，可对目标物进行选择性分离与富集。原位聚合方法具有制备聚合物纯度高，稳定性好，具有能够克服普通萃取涂层寿命短的缺陷。因此，采用原位聚合方法制备的环聚果糖聚合物纤维涂层具有重要应用前景。
发明内容
有鉴于此，本发明的目的在提供一种环聚果糖交联聚合物涂层纤维及其制备方法和应用，得到一种环聚果糖交联聚合物涂层纤维，能够实现复杂体系中PAHs的分离富集，用于管内纤维固相微萃取效果良好。
本发明用于解决上述问题的第一个技术方案是：一种环聚果糖交联聚合物涂层纤维的制备方法，包括如下步骤：
S1.将玻璃纤维去除纤维表面保护层后烘干，浸没在无水甲苯溶剂和3-氨丙基三乙氧基硅烷中，无水无氧、溶液微沸条件下反应至少48h，依次分别用二氯甲烷和甲醇清洗后干燥，得到氨基化纤维；
S2.将环聚果糖、交联剂四氟对苯二腈（TFN)和无水碳酸钾溶解在无水四氢呋喃（THF）与N,N-二甲基甲酰胺（DMF）中，加入S1所得氨基化纤维，在无水无氧条件下，70-100℃反应至少48h后，依次分别使用稀盐酸、水、二氯甲烷和甲醇浸泡，真空干燥即得到所述环聚果糖交联聚合物涂层纤维。其中，使用稀盐酸、水、二氯甲烷和甲醇浸泡可在不损害纤维涂层的条件下除去纤维表面杂质。
进一步地，所述的将玻璃纤维去除纤维表面保护层包括如下操作：在索氏提取装置使用二氯甲烷提取至少8h。
进一步地，步骤S1中所述玻璃纤维与3-氨丙基三乙氧基硅烷的质量比为1：（1.5-2.5）。
进一步地，步骤S1中所述的无水甲苯溶剂的用量为足以溶解3-氨丙基三乙氧基硅烷并浸没所述玻璃纤维。通常地，所述无水甲苯溶剂的用量为所述玻璃纤维质量的20-40倍。
进一步地，步骤S2中所述环聚果糖：四氟对苯二腈：无水碳酸钾质量比为2:（0.8-1.2）:（1.6-2.4）。
进一步地，步骤S2中所述无水四氢呋喃与N,N-二甲基甲酰胺体积比是（8-10）:1。通常地，所述无水四氢呋喃与N,N-二甲基甲酰胺的用量为步骤S1中所述无水甲苯溶剂的用量的20-50%。
进一步地，步骤S2中所述稀盐酸浓度为0.05-0.2mol/L。
进一步地，步骤S2中所述浸泡操作的时间各自独立地为20-60min。
本发明用于解决上述问题的第二个技术方案是：一种环聚果糖交联聚合物涂层纤维，使用上文所述制备方法制得。
本发明用于解决上述问题的第三个技术方案是将所述环聚果糖交联聚合物涂层纤维用于管内纤维固相微萃取，以测定环境水样中多环芳烃含量。
与现有技术相比，本发明的有益效果是：
1.本发明提供了一种环聚果糖交联聚合物涂层纤维的制备方法，可将环聚果糖交联聚合物均匀的在氨基化玻纤表面原位合成。
2.本发明制得的环聚果糖交联聚合物涂层纤维，用于管内纤维固相微萃取（IT-SPME）方法后，在后续分析中检测限低、灵敏度高、重现性好。
3.本发明制备的环聚果糖交联聚合物涂层纤维，可重复使用至少200次，其萃取性能无明显变化，具有优异的稳定性和耐用性。
附图说明
图1为环聚果糖交联聚合物涂层纤维的制备方法流程图；
图2为本发明实施例环聚果糖交联聚合物涂层纤维的SEM（副图A标尺为20μm、副图B标尺为2μm）；
图3为本发明实施例环聚果糖交联聚合物涂层纤维的等温吸脱附曲线图；
图4为本发明实施例环聚果糖交联聚合物涂层纤维应用于管内固相微萃取实际水样中六种多环芳烃的色谱图（副图A水样为瓶装水、副图B水样为自来水、副图C水样为湖水）；
图5为本发明实施例环聚果糖交联聚合物涂层纤维用于管内固相微萃取耐用性分析图（副图A为第1-3次萃取、副图B为第1、第50、第100和第200次萃取）。
具体实施方式
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。
首先提供了一种环聚果糖交联聚合物涂层纤维的制备方法实施例，流程图如图1，包括如下步骤：
S1.将3.2g玻璃纤维去除纤维表面保护层后烘干，浸没在100mL无水甲苯溶剂和6.4g3-氨丙基三乙氧基硅烷中，无水无氧、溶液微沸条件下反应48h，依次分别用二氯甲烷和甲醇清洗后干燥，得到氨基化纤维；其中，所述玻璃纤维与3-氨丙基三乙氧基硅烷的质量比为1：2。
S2.将0.4g环聚果糖、0.2g交联剂四氟对苯二腈和0.4g无水碳酸钾溶解在30ml体积比为9：1的无水四氢呋喃：N,N-二甲基甲酰胺中，加入S1所得全部氨基化纤维，在无水无氧条件下，85℃反应48h后，依次分别使用稀盐酸(0.1mol/L)、水、二氯甲烷和甲醇浸泡30min,在不损害纤维涂层的条件下除去纤维表面杂质，真空干燥得到所述环聚果糖交联聚合物涂层纤维。
其中，所述的去除纤维表面保护层步骤为，在索氏提取装置使用二氯甲烷提取12h。
可以理解的是，上述反应条件是一种具体的实施方式，只要符合本发明公开的范围，其它合理的反应条件亦可实现本发明的目的，此处不一一列举。
上述制备方法所得环聚果糖交联聚合物涂层纤维即为本发明提供的环聚果糖交联聚合物涂层纤维的一种具体实施例。其SEM图如图2，从图2A中可以看出，制得的固相微萃取纤维涂层均匀的聚合在纤维上，从图2B中可以看出环聚果糖交联聚合物涂层紧贴在纤维表面。
图3是本发明实施例环聚果糖交联聚合物涂层纤维的等温吸脱附曲线图，从图中可以看出该材料的比表面积高达1227 m2·g-1，孔径为7.18nm，这表明本发明提供的聚果糖交联聚合物涂层纤维可给目标分析物提供大量附着位点，有利于增强分析物的萃取。
本发明还提供一种所述环聚果糖交联聚合物涂层纤维在管内纤维固相微萃取中的应用，具体实施例如下：
本发明的一种环聚果糖交联聚合物涂层纤维应用于管内纤维固相微萃取与高效液相色谱（HPLC）联用。将环聚果糖交联聚合物涂层纤维填充至30cm的不锈钢管中获得萃取管。通过将萃取管和样品泵分别连接到HPLC的六通阀上，建立了在线提取和分析***。当阀门处于“负载”状态时，将样品溶液泵入萃取管中进行提取。提取后，阀门自动切换到“注入”状态，流动相洗脱萃取管，将分析物洗脱到柱和DVD上进行分离和检测。对六种PAHs(萘、苊、菲、蒽、荧蒽、芘）的线性范围、检出限、检测限、线性相关系数（r)、富集倍率(EFs)、回收率、管间重现性及精密度的测定的最佳条件：萃取体积70mL，采样率为2.5mL /min，无乙腈，解吸时间2.0min。
图4为本发明实施例环聚果糖交联聚合物涂层纤维应用于管内固相微萃取实际水样中六种多环芳烃的色谱图（A是瓶装水、B是自来水、C是湖水）。
利用管内纤维固相微萃取与高效液相色谱联用测得六种PAHs(萘、苊、菲、蒽、荧蒽、芘）线性范围、检出限、检测限、管间重现性、精密度、线性相关系数（r)和富集倍率(EFs)见下表1。
表1
图5为本发明实施例环聚果糖交联聚合物涂层纤维用于管内固相微萃取耐用性分析图，可以看出，不同批次的所有分析物的峰面积差异不显著，如图5A所示,所有分析物的RSDs（n=3）均在1.4%-2.7%范围内。根据这些结果，可以看出本发明提供的在线分析方法具有可重复性，试管重现性好。提取管具有良好的耐久性，保证了实验结果的准确性。如图5B所示，通过比较单管上第1、第50、第100次和第200次试验的峰面积，获得了持久性，这些峰面积之间的差异较小（RSDs≤10.8%）。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。
Claims (9)
1.一种环聚果糖交联聚合物涂层纤维的制备方法，其特征在于，包括如下步骤：
S1.将玻璃纤维去除纤维表面保护层后烘干，浸没在无水甲苯溶剂和3-氨丙基三乙氧基硅烷中，无水无氧、溶液微沸条件下反应至少48h，依次分别用二氯甲烷和甲醇清洗后干燥，得到氨基化纤维；
S2.将环聚果糖、交联剂四氟对苯二腈和无水碳酸钾溶解在无水四氢呋喃与N,N-二甲基甲酰胺中，加入S1所得氨基化纤维，在无水无氧条件下，70-100℃反应至少48h后，依次分别使用稀盐酸、水、二氯甲烷和甲醇浸泡，真空干燥即得到所述环聚果糖交联聚合物涂层纤维。
2.根据权利要求1所述的制备方法，其特征在于，所述的将玻璃纤维去除纤维表面保护层包括如下操作：在索氏提取装置使用二氯甲烷提取至少8h。
3.根据权利要求1所述的制备方法，其特征在于，步骤S1中所述玻璃纤维与3-氨丙基三乙氧基硅烷的质量比为1：（1.5-2.5）。
4.根据权利要求1所述的制备方法，其特征在于，步骤S2中所述环聚果糖：四氟对苯二腈：无水碳酸钾质量比为2:（0.8-1.2）:（1.6-2.4）。
5.根据权利要求1所述的制备方法，其特征在于，步骤S2中所述无水四氢呋喃与N,N-二甲基甲酰胺体积比是（8-10）:1。
6.根据权利要求1所述的制备方法，其特征在于，步骤S2中所述稀盐酸浓度为0.05-0.2mol/L。
7.根据权利要求1所述的制备方法，其特征在于，步骤S2中所述浸泡操作的时间各自独立地为20-60min。
8.一种环聚果糖交联聚合物涂层纤维，其特征在于，使用权利要求1-7任一项所述制备方法制得。
9.一种如权利要求8所述环聚果糖交联聚合物涂层纤维的应用，其特征在于，用于管内纤维固相微萃取，以测定环境水样中多环芳烃含量。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310947857.3A CN116651420A (zh) | 2023-07-31 | 2023-07-31 | 一种环聚果糖交联聚合物涂层纤维的制备方法与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310947857.3A CN116651420A (zh) | 2023-07-31 | 2023-07-31 | 一种环聚果糖交联聚合物涂层纤维的制备方法与应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116651420A true CN116651420A (zh) | 2023-08-29 |
Family
ID=87717510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310947857.3A Pending CN116651420A (zh) | 2023-07-31 | 2023-07-31 | 一种环聚果糖交联聚合物涂层纤维的制备方法与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116651420A (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174043A (zh) * | 2018-08-07 | 2019-01-11 | 济南大学 | 一种聚乙烯亚胺改性酚醛气凝胶涂层萃取纤维的制备方法 |
| WO2020123888A1 (en) * | 2018-12-14 | 2020-06-18 | The Procter & Gamble Company | Water disintegrable, foam producing article |
| CN112427021A (zh) * | 2020-11-25 | 2021-03-02 | 西安交通大学 | 一种磁性纳米颗粒-环糊精复合吸附剂、制备方法及应用 |
| CN112646058A (zh) * | 2019-10-11 | 2021-04-13 | 南京大学 | 一种两亲性多孔环糊精聚合物 |
-
2023
- 2023-07-31 CN CN202310947857.3A patent/CN116651420A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174043A (zh) * | 2018-08-07 | 2019-01-11 | 济南大学 | 一种聚乙烯亚胺改性酚醛气凝胶涂层萃取纤维的制备方法 |
| WO2020123888A1 (en) * | 2018-12-14 | 2020-06-18 | The Procter & Gamble Company | Water disintegrable, foam producing article |
| CN112646058A (zh) * | 2019-10-11 | 2021-04-13 | 南京大学 | 一种两亲性多孔环糊精聚合物 |
| CN112427021A (zh) * | 2020-11-25 | 2021-03-02 | 西安交通大学 | 一种磁性纳米颗粒-环糊精复合吸附剂、制备方法及应用 |
Non-Patent Citations (2)
| Title |
|---|
| ZHANG, YP，ET AL.: "Smart Titanium Wire Used for the Evaluation of Hydrophobic/Hydrophilic Interaction by In-Tube Solid Phase Microextraction", 《MOLECULES》, pages 1 - 14 * |
| 李晨亮等: "含磁性微球固相微萃取头的制备及对水中多环芳烃含量的测定", 《山东化工》, vol. 47, pages 60 - 61 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103543233B (zh) | 一种涂料中短链或中链氯化石蜡含量的测定方法 | |
| Ma et al. | Determination of endocrine-disrupting compounds in water by carbon nanotubes solid-phase microextraction fiber coupled online with high performance liquid chromatography | |
| CN109696499B (zh) | 一种基于高分辨率质谱的水中亚硝胺高灵敏测定方法 | |
| Kataoka et al. | Development of automated in‐tube SPME/LC/MS method for drug analysis | |
| Feng et al. | Poly (ionic liquids)‐coated stainless‐steel wires packed into a polyether ether ketone tube for in‐tube solid‐phase microextraction | |
| Cui et al. | An etched stainless steel wire/ionic liquid-solid phase microextraction technique for the determination of alkylphenols in river water | |
| CN108872415A (zh) | 一种尿液中单羟基多环芳烃的分析检测方法 | |
| CN113075309B (zh) | 膜保护固相微萃取装置及其在检测牛奶中***的应用 | |
| LU102485B1 (en) | Method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water | |
| Sun et al. | Nanostructured‐silver‐coated polyetheretherketone tube for online in‐tube solid‐phase microextraction coupled with high‐performance liquid chromatography | |
| Feng et al. | Triazine-based covalent porous organic polymer for the online in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons prior to high-performance liquid chromatography-diode array detection | |
| CN102798689A (zh) | 分离富集并检测水环境中痕量氟喹诺酮类抗生素的方法 | |
| Shi et al. | Tris (pentafluoroethyl) trifluorophosphate-basd ionic liquids as advantageous solid-phase micro-extraction coatings for the extraction of organophosphate esters in environmental waters | |
| CN113376305A (zh) | 一种水体中咔唑及多卤咔唑的固相膜萃取气相色谱质谱检测方法 | |
| CN115308319A (zh) | 一种全氟及多氟烷基化合物非靶向筛查的定量方法 | |
| Wang et al. | Inorganic–organic hybrid coating material for the online in‐tube solid‐phase microextraction of monohydroxy polycyclic aromatic hydrocarbons in urine | |
| CN112755592B (zh) | 一种共价有机骨架纳米微球功能化固相微萃取整体柱 | |
| CN116651420A (zh) | 一种环聚果糖交联聚合物涂层纤维的制备方法与应用 | |
| Wu et al. | Synthesis and evaluation of dummy molecularly imprinted microspheres for the specific solid‐phase extraction of six anthraquinones from slimming tea | |
| Huang et al. | Electrochemical preparation of composite polyaniline coating and its application in the determination of bisphenol A, 4‐n‐nonylphenol, 4‐tert‐octylphenol using direct solid phase microextraction coupled with high performance liquid chromatography | |
| CN108414637B (zh) | 一种利用固相微萃取-气相色谱-质谱联用技术检测水中挥发性消毒副产物的方法 | |
| Amiri et al. | Polypyrrole/carbon nanotube coated stainless steel mesh as a novel sorbent | |
| Murugan et al. | A review on method development and validation by using HPLC | |
| Lou et al. | Preparation and application of a coated‐fiber needle extraction device | |
| CN108802243B (zh) | 同时检测水中灭草松、2，4-d、2，4-二氯酚、2，4，6-三氯酚、五氯酚的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |