CN111748080B - 苯硼酸取代交联聚二乙炔、其制备方法与一种试纸 - Google Patents
苯硼酸取代交联聚二乙炔、其制备方法与一种试纸 Download PDFInfo
- Publication number
- CN111748080B CN111748080B CN202010698538.XA CN202010698538A CN111748080B CN 111748080 B CN111748080 B CN 111748080B CN 202010698538 A CN202010698538 A CN 202010698538A CN 111748080 B CN111748080 B CN 111748080B
- Authority
- CN
- China
- Prior art keywords
- phenylboronic acid
- test paper
- solvent
- polydiacetylene
- diacetylene
- 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.)
- Active
Links
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical group OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000012360 testing method Methods 0.000 title claims abstract description 74
- 229920000015 polydiacetylene Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000002904 solvent Substances 0.000 claims abstract description 51
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclo-pentanone Natural products O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000007641 inkjet printing Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000002120 nanofilm Substances 0.000 claims description 3
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical group O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000000862 absorption spectrum Methods 0.000 abstract description 12
- 238000004451 qualitative analysis Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
- C08G2261/1432—Side-chains containing nitrogen containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/147—Side-chains with other heteroatoms in the side-chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3328—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkyne-based
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/76—Post-treatment crosslinking
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/7756—Sensor type
- G01N2021/7759—Dipstick; Test strip
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Plasma & Fusion (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明提供了一种试纸，其是由苯硼酸取代交联聚二乙炔制备得到，该试纸可用于检测有机溶剂；本申请提供的试纸在检测不同溶剂时可以直接通过肉眼辨别蓝红颜色转变程度，并依此判定溶剂种类，也可以使用紫外‑可见吸收光谱对溶剂处理后的试纸进行定性分析，计算出比色(CR)值，根据CR值判定溶剂种类。进一步的，本申请提供的试纸还可在已知溶剂组分的情况下根据颜色偏移或CR值判断出组分体积分数。
Description
技术领域
本发明涉及检测技术领域，尤其涉及一种苯硼酸取代交联聚二乙炔、其制备方法与一种试纸。
背景技术
有机溶剂检测在化工及实验室中愈加重要，例如对正己烷、丙酮、甲苯、N，N-二甲基甲酰胺等有机溶剂的鉴别。常用的环境传感方式有许多，比如电化学、光化学、光学和比色技术的传感；其中的比色传感技术具有快速反馈、操作简便、可视化检测、无需使用大型仪器等突出优点，因此成为一种对环境进行高效检测的方法。
聚二乙炔是一类可用于有机溶剂检测的聚合物，它受外界刺激时会发生肉眼可辨的蓝色到红色转变现象，这种独特的性质使得聚二乙炔被广泛地用于比色传感器。但是未经改进的聚二乙炔耐溶剂性差，蓝色聚二乙炔遇到一些溶剂迅速转变成红色聚二乙炔，肉眼无法辨别这些溶剂对聚二乙炔作用结果的区别。因此，利用聚二乙炔的特性且针对其上述缺点对其改进后制备的试纸若能实现有机溶剂的检测，且能够肉眼区别出明显差异对有机溶剂的检测具有重要意义。
发明内容
本发明解决的技术问题在于提供一种苯硼酸取代交联聚二乙炔试纸，该试纸可直接通过肉眼辨别颜色转变程度，实现溶剂种类的判断。
有鉴于此，本申请提供了一种苯硼酸取代交联聚二乙炔，由如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔缩合后辐照交联得到；
优选的，所述苯硼酸取代二乙炔和所述二乙炔的摩尔比为1:(2.9～3.1)。
本申请还提供了一种苯硼酸取代交联聚二乙炔的制备方法，包括：
将如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔在溶剂中混合、加热，反应后再进行辐照，得到苯硼酸取代交联聚二乙炔；
优选的，所述加热的温度为80～100℃，所述溶剂为环戊酮和四氢呋喃。
优选的，所述辐照为200～320nm的紫外光辐照。
本申请还提供了一种试纸，由上述方案所述的苯硼酸取代交联聚二乙炔或上述方案所述的制备方法所制备的苯硼酸取代交联聚二乙炔制备得到，所述试纸用于检测有机溶剂。
本申请还提供了一种试纸的制备方法，包括以下步骤：
将如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔在溶剂中混合，将得到的混合液复合于纸张上，得到混合分子膜；
将所述混合分子膜加热后进行辐照，得到试纸；
优选的，所述复合的方式具体为采用喷墨打印的方式在纸张上打印所述混合溶液。
本申请提供了一种试纸，其是由苯硼酸取代交联聚二乙炔制备得到，该试纸可用于检测有机溶剂，在检测有机溶剂的过程中，溶剂分子与苯硼酸取代交联聚二乙炔的侧基烷基链发生相互作用，侧链受到扰动，带动主链构象发生改变，共轭长度变短，从而引起苯硼酸取代交联聚二乙炔紫外可见吸收谱峰蓝移，肉眼观察到试纸显现出红色。因此，本申请提供的试纸在检测不同溶剂时可以直接通过肉眼辨别其蓝红颜色转变程度，并依此判定溶剂种类，也可以使用紫外-可见吸收光谱对溶剂处理后的试纸进行定性分析，计算出比色(CR)值，根据CR值判定溶剂种类。进一步的，本申请提供的试纸还可在已知溶剂组分的情况下根据颜色偏移或CR值判断出组分体积分数。另一方面，本申请提供的试纸的制备过程简单、成本低廉，检测溶剂过程简便，可以非常快速地给出检测结果。
附图说明
图1为实施例1制备的苯硼酸取代二乙炔分子的核磁谱图；
图2为实施例1制备的苯硼酸取代二乙炔分子的红外光谱图；
图3为实施例2纸张上混合分子层在90℃加热处理以及随后用紫外光辐照所发生的反应；
图4为实施例2中苯硼酸取代二乙炔分子端基苯硼酸基团加热反应前后的红外表征图；
图5为实施例3试纸用不同溶剂处理后发生蓝红颜色转变图；
图6为实施例3试纸用不同溶剂处理后在紫外-可见吸收光谱上测得的吸收光谱图；
图7为实施例3试纸用不同溶剂处理过后的CR值柱状图；
图8为实施例4试纸用正己烷和氯仿配制成的不同比例混合溶剂处理后发生蓝红颜色转变图；
图9为实施例4试纸经混合溶剂处理前后的紫外可见吸收光谱图；
图10为实施例4试纸经混合溶剂处理后CR值随fv变化的点线图；
图11为苯硼酸取代交联聚二乙炔检测溶剂的机理图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
鉴于聚二乙炔耐溶剂差的问题，本申请对聚二乙炔进行了改进，制备了一种苯硼酸取代交联聚二乙炔，且将其用于溶剂的检测，可以快速对常见的溶剂进行检测。具体的，本发明实施例首先公开了一种苯硼酸取代交联聚二乙炔，由如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔聚合后辐射交联得到；
在本申请中，所述苯硼酸取代二乙炔的制备方法具体为：
在催化剂的作用下，将二乙炔单体和草酰氯在溶剂中反应，得到初始产物；
将所述初始产物和3-氨基苯硼酸在碱性环境下反应，得到苯硼酸取代二乙炔。
在上述制备过程中，所述催化剂具体选自N，N-二甲基甲酰胺，所述溶剂选自二氯甲烷，所述碱性环境具体在三乙胺中进行。
本申请还提供了一种苯硼酸取代交联聚二乙炔的制备方法，包括以下步骤：
将如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔在溶剂中混合、加热，反应后再进行辐照，得到苯硼酸取代交联聚二乙炔；
在上述制备苯硼酸取代交联聚二乙炔的过程中，本申请首先将苯硼酸取代二乙炔和二乙炔在溶剂中混合，所述溶剂为本领域技术人员熟知的有机溶剂，更具体地，所述溶剂为环戊酮和四氢呋喃，且体积比为1:1。所述加热的温度为80～100℃，在此阶段，苯硼酸取代二乙炔和二乙炔发生缩合反应，具体如图3所示。所述苯硼酸取代二乙炔和所述二乙炔的摩尔比为1:(2.9～3.1)，在具体实施例中，所述苯硼酸取代二乙炔和所述二乙炔的摩尔比为1:3。
在上述反应之后，则进行辐照，上述缩合反应后的产物发生聚合反应，得到苯硼酸取代交联聚二乙炔；所述辐照具体采用的是200～320nm的紫外光辐照。
在上述制备苯硼酸取代交联聚二乙炔的过程中，必须先进行缩合再进行交联，才能使得到的聚合物应用于有机溶剂的检测，而不能直接将苯硼酸取代二乙炔和二乙炔进行辐照。
本申请还提供了一种试纸，其是由上述苯硼酸取代交联聚二乙炔制备得到，所述试纸具体用于检测有机溶剂。
在本申请中，所述试纸对有机溶剂的检测具体是针对本领域技术人员熟知的有机溶剂，在本申请中，所述有机溶剂可以为正己烷、甲醇、乙醇、丙酮、甲苯、氯仿或N，N-二甲基甲酰胺。
该种由苯硼酸取代交联聚二乙炔制备得到的试纸未检测有机溶剂前是蓝色，当利用试纸检测不同有机溶剂后，试纸因试剂不同而表现出不同程度的蓝色到红色转变，因此根据蓝红颜色转变的程度判定溶剂种类，即达到有机溶剂的检测，具体是将试纸的颜色与标准比色卡对比，即可确定该种溶剂；还可进一步根据试纸测试紫外-可见吸收光谱，计算出CR值，由于不同溶剂有不同的CR值，将计算出的CR值与溶剂的CR值对比，即可精确确定该种溶剂。
本申请提供的试纸还可进一步检测体积分数未知的两组分混合溶剂中其中一种溶剂的体积分数fv，当试纸用这种混合溶剂处理后，试纸发生一定程度蓝红颜色转变，与标准试纸溶致变色比色卡对比便可判定混合溶剂中fv，若要更精确的确定fv可以计算试纸的比色(CR)值，根据CR-fv曲线确定，从而实现混合溶剂的检测，这里要求fv≤50％。在具体实施例中，本申请提供的试纸具体可检测不同体积下的正己烷和氯仿的混合溶剂。
上述试纸是由苯硼酸取代交联聚二乙炔制备得到，试纸的制备方法按照本领域技术人员熟知的方法进行即可，可以直接在上述聚合物制备之后再与纸张复合，也可以在制备过程中与纸张复合，为了具有较好的复合效果，本申请还提供了一种试纸的制备方法，包括以下步骤：
将如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔在溶剂中混合，将得到的混合液复合于纸张上，得到混合分子膜；
将所述混合分子膜加热后进行辐照，得到试纸；
上述制备过程具体进行了试纸的制备过程，上述复合具体采用的是喷墨打印技术，以在纸张上打印混合液，得到混合液分子膜。其他过程与苯硼酸取代交联聚二乙炔的参数相同，此处不进行赘述。
本申请提供的试纸可用于检测有机溶剂，在检测有机溶剂的过程中，溶剂分子与苯硼酸取代交联聚二乙炔的侧基烷基链发生相互作用，侧链受到扰动，带动主链构象发生改变，共轭长度变短，从而引起苯硼酸取代交联聚二乙炔紫外可见吸收谱峰蓝移，肉眼观察到试纸显现出红色(具体机理图如图11所示)。
本申请提供的苯硼酸取代交联聚二乙炔试纸由于对聚二乙炔的改进，使得其可对多种不同的溶剂进行区分，进一步的，对于混合溶剂，已知其组分的情况下可以判断组分的体积分数，检测过程简单方便，可以像pH试纸检测pH一样成为实验室常用溶剂检测试纸。
为了进一步理解本发明，下面结合实施例对本发明提供的苯硼酸取代交联聚二乙炔的制备方法及其应用进行详细说明，本发明的保护范围不受以下实施例的限制。
实施例1
在50mL圆底烧瓶中添加0.368g的二乙炔单体，往烧瓶中添加20mL二氯甲烷充分溶解，缓慢滴加0.15mL的草酰氯到烧瓶中，在室温下搅拌30min，滴加催化剂N，N-二甲基甲酰胺50μL，在室温下搅拌反应4h，将反应后的溶液用旋转蒸发法除去溶剂，得到的固体产物备用；在100mL圆底烧瓶中添加30mL二氯甲烷，先后往烧瓶中添加0.2g的3-氨基苯硼酸和0.68mL三乙胺，搅拌使固体充分溶解，将第一步制备的产物溶于15mL四氢呋喃中，缓慢滴加到烧瓶中，在室温下搅拌反应18h，用旋转蒸发法除去溶剂，得到的粗产物用柱层析纯化，苯硼酸取代二乙炔的产率约80～86％，苯硼酸取代二乙炔分子的核磁谱图见图1，其红外光谱见图2。
实施例2
将10mg(0.02mmol)的实施例1制备的苯硼酸取代二乙炔分子和23mg(0.06mmol)的二乙炔分子溶于0.5mL的环戊酮和四氢呋喃混合溶剂中，环戊酮和四氢呋喃的体积比是1：1；利用喷墨打印技术将混合溶液打印到纸张表面，将纸张在90℃条件下加热1h，使苯硼酸取代二乙炔单体不同端基间的苯硼酸基团发生缩合反应，最后将纸张在200～320nm紫外灯下聚合10min，得到用于溶剂检测的苯硼酸取代交联聚二乙炔试纸，涉及的化学反应见图3，图4是苯硼酸取代聚二乙炔加热前后苯硼酸脱水缩合红外光谱图。
实施例3
将实施例2制备的试纸采用正己烷、甲醇、乙醇、丙酮、甲苯、氯仿和N，N-二甲基甲酰胺分别10s；肉眼观察试纸的蓝红颜色转变程度，对溶剂种类得出定性判断(如图5所示)；
或测定试纸紫外-可见吸收光谱，用试纸在650nm处的吸收值表示苯硼酸取代交联聚二乙炔试纸的蓝色成分量，在540nm处的吸收值表示苯硼酸取代聚二乙炔试纸的红色成分量，试纸蓝色到红色的转变程度用比色(CR)值表示，CR％计算公式如下：
PB＝A650/[A650+A540]×100％ (1)；
CR％＝[PB0-PB1]/PB0×100％ (2)；
其中，A650是吸收光谱在650nm吸收峰强度，A540是540nm吸收峰强度，PB0表示在溶剂处理前试纸中蓝色的百分比，PB1表示在溶剂处理后试纸中蓝色的百分比。如图6、图7所示，图6为试纸经不同试剂处理后在紫外-可见吸收光谱上测得的吸收光谱图，图7为在上述不同溶剂处理后试纸的CR值的柱状图。根据图5、图7通过肉眼完全能够区别开不同试剂。
实施例4
将正己烷和氯仿溶剂配制成不同比例的混合溶剂，氯仿混合溶剂体积分数fv分别是0％、25％、50％、75％、100％，用配制的混合溶剂处理苯硼酸取代交联聚二乙炔试纸，试纸蓝红颜色转变如图8所示。
按照实施例3的方法测定不同比例混合溶剂处理过的试纸测试紫外-可见吸收光谱，如图9所示，并根据吸收光谱计算CR值，以CR值为纵坐标，fv为横坐标作图，如图10所示，由图10可以发现，随着fv增大，CR值越大，即试纸蓝红颜色转变程度越大，说明该试纸对于混合溶剂的混合体积具有一定的区分能力。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (8)
1.一种苯硼酸取代交联聚二乙炔，由如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔缩合后辐照交联得到；
2.根据权利要求1所述的苯硼酸取代交联聚二乙炔，其特征在于，所述苯硼酸取代二乙炔和所述二乙炔的摩尔比为1:(2.9～3.1)。
3.一种苯硼酸取代交联聚二乙炔的制备方法，包括：
将如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔在溶剂中混合、加热，反应后再进行辐照，得到苯硼酸取代交联聚二乙炔；
4.根据权利要求3所述的制备方法，其特征在于，所述加热的温度为80～100℃，所述溶剂为环戊酮和四氢呋喃。
5.根据权利要求3所述的制备方法，其特征在于，所述辐照为200～320nm的紫外光辐照。
6.一种试纸，由权利要求1～2任一项所述的苯硼酸取代交联聚二乙炔或权利要求3～5任一项所述的制备方法所制备的苯硼酸取代交联聚二乙炔制备得到，所述试纸用于检测有机溶剂。
7.一种试纸的制备方法，包括以下步骤：
将如式(Ⅰ)所示的苯硼酸取代二乙炔和二乙炔在溶剂中混合，将得到的混合液复合于纸张上，得到混合分子膜；
将所述混合分子膜加热后进行辐照，得到试纸；
8.根据权利要求7所述的制备方法，其特征在于，所述复合的方式具体为采用喷墨打印的方式在纸张上打印所述混合溶液。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010698538.XA CN111748080B (zh) | 2020-07-20 | 2020-07-20 | 苯硼酸取代交联聚二乙炔、其制备方法与一种试纸 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010698538.XA CN111748080B (zh) | 2020-07-20 | 2020-07-20 | 苯硼酸取代交联聚二乙炔、其制备方法与一种试纸 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111748080A CN111748080A (zh) | 2020-10-09 |
| CN111748080B true CN111748080B (zh) | 2021-04-23 |
Family
ID=72711523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010698538.XA Active CN111748080B (zh) | 2020-07-20 | 2020-07-20 | 苯硼酸取代交联聚二乙炔、其制备方法与一种试纸 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111748080B (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359034A (zh) * | 2018-02-07 | 2018-08-03 | 中国科学技术大学 | 一种具有螺旋结构的聚二乙炔及其制备方法和应用 |
| CN109476946A (zh) * | 2016-04-13 | 2019-03-15 | 西甘产业股份有限公司 | 光学渐逝变色组合物及其制备和使用的方法 |
-
2020
- 2020-07-20 CN CN202010698538.XA patent/CN111748080B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476946A (zh) * | 2016-04-13 | 2019-03-15 | 西甘产业股份有限公司 | 光学渐逝变色组合物及其制备和使用的方法 |
| CN108359034A (zh) * | 2018-02-07 | 2018-08-03 | 中国科学技术大学 | 一种具有螺旋结构的聚二乙炔及其制备方法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| Diacetylenic monolayers containing a boronic acid moiety form a chemically and thermally stable poly(diacetylene) film on water;Masazo Niwa et al.;《Journal of Materials Chemistry》;20001103;第10卷;第2647-2651页 * |
| Polydiacetylenes Bearing Boronic Acid Groups as Colorimetric and Fluorescence Sensors for Cationic Surfactants;Songyi Lee et al.;《ACS Applied Materials & Interfaces (2013)》;20130208;第5卷(第11期);第4521-4526页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111748080A (zh) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | An eco-friendly imprinted polymer based on graphene quantum dots for fluorescent detection of p-nitroaniline | |
| Bosch et al. | Fluorescent probes for sensing processes in polymers | |
| Ma et al. | A fluorescent sensor for low pH values based on a covalently immobilized rhodamine–napthalimide conjugate | |
| CN103588960A (zh) | 一类非标记离子型共轭聚电解质及其合成方法、在生物检测的应用 | |
| Nie et al. | Visual and reversible detection of cyanide ions in protic solvents by a novel colorimetric receptor | |
| Rychlý et al. | Chemiluminescence from paper I. Kinetic analysis of thermal oxidation of cellulose | |
| Peinado et al. | Following in situ photoinitiated polymerization of multifunctional acrylic monomers by fluorescence and photocalorimetry simultaneously | |
| Winnik et al. | Phase separation of poly (N-isopropylacrylamide) in water: a spectroscopic study of a polymer tagged with a fluorescent dye and a spin label | |
| Vallejos et al. | Polymeric chemosensor for the detection and quantification of chloride in human sweat. Application to the diagnosis of cystic fibrosis | |
| CA2905521A1 (en) | Surface oxidation for sequestering biomolecules and related methods | |
| Chen et al. | An AIE dye based smartphone and LDA integrated portable, intelligent and rapid detection system as trace water indicator and cyanide detector | |
| Chiriac et al. | Electrochemically active polyimides containing hydroxyl-functionalized triphenylmethane as molecular sensors for fluoride anion detection | |
| CN111748080B (zh) | 苯硼酸取代交联聚二乙炔、其制备方法与一种试纸 | |
| KR100692623B1 (ko) | 화학센서 및 반응 중간체용 방향족 아민계 고분자 화합물및 이를 포함하는 수지 조성물 | |
| Muñoz-Bartual et al. | Development of paper-immobilized molecularly imprinted polymers by laser pointer activation for methamphetamine extraction with analysis by ion mobility spectrometry | |
| Sha et al. | Synthesis of polymer with defined fluorescent end groups via reversible addition fragmentation transfer polymerization for characterizing the conformations of polymer chains in solutions | |
| Williams et al. | Nano-molecularly imprinted polymers for serum creatinine sensing using the heat transfer method | |
| Wiktorowicz et al. | Multi-stimuli responsive poly (azodibenzo-18-crown-6-ether) s | |
| CN112574739B (zh) | 一种基于改性荧光素衍生物的水凝胶传感器及其制备方法 | |
| CN104151867A (zh) | 温度与pH双响应型环糊精探针及其制备方法 | |
| Xiao et al. | BODIPY-based fluorescent polymeric probes for selective detection of Fe3+ ions in aqueous solution | |
| CN111138313B (zh) | 一种具有聚集诱导发光特性的席夫碱化合物及其用于制备比率荧光探针的方法 | |
| Zhao et al. | A study of polymer blends by nonradiative energy transfer fluorescence spectroscopy | |
| CN108279223B (zh) | 一种基于阳离子聚合物检测芥子碱硫氰酸盐的荧光检测方法 | |
| Peng et al. | Robust and reversible vapoluminescent organometallic copper polymers |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |