WO2020143265A1 - 氟离子显色传感聚酰亚胺薄膜及其制备方法与应用 - Google Patents
氟离子显色传感聚酰亚胺薄膜及其制备方法与应用 Download PDFInfo
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- polyimide film
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- ZFGZAHCWXRBSLP-UHFFFAOYSA-N Cc1cc(C2(c3ccccc3-c3ccccc23)c2cc(C)cc(C)c2)cc(C)c1 Chemical compound Cc1cc(C2(c3ccccc3-c3ccccc23)c2cc(C)cc(C)c2)cc(C)c1 ZFGZAHCWXRBSLP-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N O=C(c(c1c2)ccc2Oc(cc2C(O3)=O)ccc2C3=O)OC1=O Chemical compound O=C(c(c1c2)ccc2Oc(cc2C(O3)=O)ccc2C3=O)OC1=O QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- G01N21/29—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using visual detection
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- 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
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the invention relates to a type of polyimide film sensor material for measuring fluoride ion, in particular to a type of color sensor, a polyimide film sensor material for visual determination of fluoride ion and its preparation method and application , Belongs to the field of material science and ion detection technology.
- fluoride ion plays an important and basic role in many biological and chemical processes.
- a proper amount of fluoride ion can prevent tooth decay and osteoporosis, but excessive intake of fluoride ion will cause fluoride poisoning, and high concentration of fluoride Ions can seriously harm the environment.
- the presence of fluoride ions seriously affects human life.
- the use of chemical substances sensitive to fluoride ions and the use of instruments using UV-visible spectroscopy, fluorescence spectroscopy, and cyclic voltammetry are common methods.
- the fluoride ion chemical sensing substances that have been found are mostly small molecules. Compounds are formulated into solutions for measurement, which have the disadvantages of inconvenience in use and difficulty in recycling. It is of great practical significance to develop simple and convenient methods for detecting fluoride ions.
- the solid film is used as the sensing material, and the color change that can be observed only by visual observation after combining with the fluoride ion is used to determine the fluoride ion concentration, without requiring a complicated instrument, and the operation is simple and convenient.
- the Chinese invention patent CN201010202940.0 loaded a single layer of ligand alizarin complexing agent molecule sensitive to fluoride ion on the filter paper fiber with 10 layers of titanium dioxide film deposited on the surface to realize the color sensing and measurement of fluoride ion, but this invention With the help of quantitative filter paper as a carrier, the preparation method is complicated and can only be used once.
- Chinese invention patent CN201610949644.4 discloses a kind of fluorene using 2-bromo-9,9-(N-carbazole-hexyl) fluorene as raw material, reacting with trimethylethynyl silicon, and then undergoing electrochemical polymerization to obtain poly 1,4 ⁇ Di(4 ⁇ (9,9 ⁇ bis(N ⁇ carbazole ⁇ hexyl)fluorenyl) ⁇ 1,2,3-triazolyl)benzene film, which can be used as a fluorescent sensor membrane for detecting fluoride ions, High sensitivity, but requires a special fluorescence detector. At present, there is no color-sensing solid-state thin film material that can detect fluoride ion by visual color change.
- the object of the present invention is to provide a color-sensing polyimide film capable of measuring fluoride ion by visual color change;
- Another object of the present invention is to provide a method for preparing a fluoride ion color sensing polyimide film
- Another object of the present invention is to provide the application of fluoride ion color sensing polyimide film in the determination of fluoride ion.
- the hydroxyl group on the molecular structure can form a strong hydrogen bond interaction with the fluoride ion, resulting in the deprotonation of the hydroxyl group in the polyimide chain, and the intramolecular
- the charge transfer effect is enhanced, resulting in strong absorption in the visible light region; after the polyimide film is immersed in a fluoride ion solution and taken out, the color changes from yellow to green, and the color change is obvious.
- the corresponding fluoride ion concentration can be estimated to realize the quantitative determination of fluoride ion without resorting to other analytical chemical instruments.
- the polyimide of the present invention is a type of high-performance polymer material containing an imide ring in the main chain, and has excellent thermal stability, water resistance, solvent resistance, dimensional stability and mechanical strength.
- the polyimide film containing hydroxyfluorene of the invention has a sensitive color reaction to fluoride ions, the concentration of fluoride ions can be determined by visual inspection, and the sensing function can be restored by a regeneration method, which is used multiple times. The film can be directly cut into a sheet shape, the sensor device is convenient to manufacture, and the application value is large.
- a fluoride ion color sensing polyimide film contains a hydroxyfluorene group, and the molecular structure formula is:
- n represents the average number of repeating structural units, and the value ranges from 100 to 201;
- R 1 and R 2 are H or CH 3 ;
- Ar is one of the following structural formulas:
- the preparation method of the fluoride ion color-sensing polyimide film includes the following steps:
- the structural formula of the aromatic diamine monomer is:
- R 1 and R 2 are H or CH 3 ;
- the aromatic dianhydride monomer is 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenyl sulfone Tetracarboxylic acid dianhydride or 4,4'-(4,4'-isopropylidene diphenoxy) bis(phthalic anhydride);
- step (2) Dissolve the fibrous polyimide obtained in step (1) in a strong polar aprotic organic solvent, control the solid content to 10 to 15 wt%, stir and dissolve it, and evenly apply it to a clean glass plate. Vacuum again until there are no bubbles, then raise the temperature to remove the solvent, and after cooling, soak in hot water to strip the film to obtain a fluoride ion color sensing polyimide film.
- the molar ratio of the aromatic diamine monomer to the aromatic dianhydride monomer is controlled to be 1:0.9-1.1.
- the strongly polar aprotic organic solvent is N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide and m-cresol. One or two.
- the amount of the catalyst is 0.01 to 0.1 times the moles of aromatic diamine monomer.
- drying the precipitate as described in step (1) is to place the precipitate in a vacuum drying at 95 to 105°C for 8 to 12 hours; the vacuum pumping at room temperature-the number of argon circulation cycles is two; The amount of ethanol mentioned is 10 to 15 times the volume of the polyimide solution.
- the glass plate in step (2) is a silica glass plate;
- the temperature-removing solvent is vacuum drying from room temperature to 70°C for 8 to 12 hours; and then vacuum drying from 70°C to 120°C 3 to 6 hours; then increase the temperature from 120°C to 200°C and vacuum dry for 2 to 3 hours.
- the polyimide film is cut into strips, soaked in the solution to be tested, soaked for 20 to 60 minutes, taken out and rinsed with ethanol To observe the color change of the film; only when immersed in a solution containing fluoride ion, the polyimide film changes from yellow to green, and the color produces an obvious change that can be recognized by visual inspection.
- the polyimide film has obvious effect on fluoride ion The color sensor function.
- the concentration of the fluoride ion in the solution to be tested is 10 ⁇ 4 to 0.1 mol/L; the polyimide film is cut into long strips of 0.5 ⁇ 2 cm.
- the polyimide film changes from yellow to green and then immersed in an ethanol solution containing 0.01 to 0.1 mol/L trifluoroacetic acid for regeneration treatment. After 5 to 20 minutes, the color of the film returns from green to The original yellow color still has the same sensitive color-sensing effect on fluoride ions; repeated 10 times, the polyimide film has the same sensitive color-sensing effect on fluoride ions.
- 4,4'-(hexafluoroisopropylene) diphthalic anhydride is:
- the structural formula of 4,4'-oxydiphthalic anhydride (ODPA) is:
- the structural formula of 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA) is:
- the structural formula of 4,4'-(4,4'-isopropylidene diphenoxy)bis(phthalic anhydride) (BPADA) is:
- the present invention has the following effects:
- the polyimide film containing hydroxyfluorene of the present invention is insoluble in water and common low-boiling solvents such as ethanol, methanol or acetone.
- the thermal weight loss temperature of 5% in a nitrogen atmosphere reaches 500°C
- the glass transition temperature reaches 370°C
- the coefficient of thermal expansion Less than 70ppm/°C, tensile modulus greater than 3.0GPa, tensile strength greater than 90MPa, elongation at break up to 8% meet the water resistance, solvent resistance, thermal stability, dimensional stability and mechanics of fluoride ion sensing materials The need for strength.
- the polyimide film containing hydroxyfluorene of the present invention can be directly cut into sheets, and the sensor device is very convenient to manufacture. It is used for the determination of fluoride ions, with a sensitivity of 10-4 mol/L and high selectivity;
- the polyimide film containing hydroxyfluorene of the present invention can restore the sensing function through the regeneration method, and is used for the determination of fluoride ion many times.
- Example 1 is a total reflection infrared spectrum of the polyimide film products obtained in Examples 1 to 4 of the present invention, wherein: a is the polyimide film product obtained in Example 1, and b is the polyimide obtained in Example 2. The film product, c is the polyimide film product obtained in Example 3, and d is the polyimide film product obtained in Example 4.
- FIG. 2 is a nuclear magnetic resonance hydrogen spectrum measured by the polyimide obtained in Examples 1 to 4 of the present invention dissolved in deuterated dimethyl sulfoxide.
- the color of the polyimide film is yellow, insoluble in water, ethanol, methanol and acetone; 5% weightlessness temperature measured by thermogravimetric analyzer (TGA) in nitrogen atmosphere is 525°C; dynamic thermomechanical analyzer ( DMA) measured the glass transition temperature of 410 °C; using a static mechanical analyzer (TMA) test to obtain the thermal expansion coefficient (CET) of the polyimide film is 60.57ppm/ °C; measured according to GB/T 1040.3-2006 standard
- TGA thermogravimetric analyzer
- DMA dynamic thermomechanical analyzer
- TMA static mechanical analyzer
- CET thermal expansion coefficient
- the tensile modulus of the film was 4.3 GPa, the tensile strength was 101.5 MPa, and the elongation at break was 14%.
- the total reflection infrared (IR) spectrum of the film product is shown as a in Figure 1.
- the spectrum has a broad characteristic absorption peak corresponding to hydroxyl groups between 3100 and 3600 cm -1 , and the corresponding imide rings at 1777 cm -1 and 1711 cm -1 , respectively.
- the color of the polyimide film is yellow, insoluble in water, ethanol, methanol and acetone; the 5% weight loss temperature measured by TGA in a nitrogen atmosphere is 527°C, and the glass transition temperature measured by DMA method is 452°C
- the CET of the polyimide film obtained by TMA test is 56.76ppm/°C; according to the GB/T 1040.3-2006 standard, the tensile modulus of the film is 3.6GPa, the tensile strength is 93.9MPa, and the elongation at break The rate is 11%.
- the color of the polyimide film is yellow, insoluble in water, ethanol, methanol and acetone; the 5% weight loss temperature measured by TGA in a nitrogen atmosphere is 516 °C, and the glass transition temperature measured by DMA method is 456 °C
- the CET of the polyimide film obtained by TMA test is 62.09ppm/°C; the tensile modulus of the film is 3.5GPa, the tensile strength is 95.5MPa, and the elongation at break is measured according to the GB/T 1040.3-2006 standard The rate is 8%.
- the color of the polyimide film is light yellow, insoluble in water, ethanol, methanol and acetone; the 5% weight loss temperature measured by TGA in a nitrogen atmosphere is 501 °C, and the glass transition temperature measured by DMA method is 370 °C;
- the polyimide films obtained in Examples 1 to 4 are insoluble in water and common low-boiling solvents such as ethanol, methanol or acetone.
- the temperature of 5% thermal weight loss in a nitrogen atmosphere reaches 500°C and the glass transition temperature reaches 370 °C, thermal expansion coefficient is less than 70ppm/°C, tensile modulus is greater than 3.0GPa, tensile strength is greater than 90MPa, elongation at break reaches 8%, to meet the water resistance, solvent resistance, thermal stability and size of fluoride ion sensing materials The need for stability and mechanical strength.
- Example 5 Sensitivity test of polyimide film to fluoride ion color sensor
- the polyimide film obtained in Example 4 was cut into long strips of 0.5 ⁇ 2 cm, and dissolved in ethanol using tetrabutylammonium fluoride to prepare fluoride ion concentrations of 10 -6 , 10 -5 , and 10 ⁇ 4 , 10-3 , 10-2 and 0.1mol/L solution; take the cut polyimide film strips and soak them in each solution for 40 minutes, rinse with ethanol after taking out, observe the color change of the film; As the fluoride ion concentration increases, the color of the polyimide film gradually changes from light green to dark green; even when immersed in a fluoride ion solution with a concentration as low as 10 -4 mol/L, the color of the solution can be observed to change significantly to Light green, the resulting polyimide film has a more sensitive color-sensing effect on fluoride ions.
- the polyimide films obtained in Example 1, Example 2 and Example 3 are all the same as in Example 4, and the sensitivity to the measurement of fluoride ion
- Example 6 Selective experiment of polyimide film for color sensing of fluoride ion
- the polyimide film obtained in Example 2 was cut into long strips of 0.5 ⁇ 2 cm and immersed in 0.1 mol/L Cl - , Br - , I - , AcO - , H 2 PO 4 - , HSO 4 - , BF 4 - , NO 3 - or ClO 4 - ethanol solution, soak for 60 minutes and take out, rinse with ethanol, it can be found that even if the concentration of these anions is as high as 0.1mol/L, it will not cause polyimide
- the color change of the film and it is mentioned in Example 5 that even when the fluoride ion concentration is as low as 10 -4 mol/L, it still causes the color of the polyimide film to change to light green, indicating that the polyimide film is The recognition of fluoride ion has high selectivity; the polyimide film obtained in Example 2 is changed to the polyimide film obtained in Example 1, Example 3 and Example 4 and the color transmission of fluoride ion is the same Sense effect has high
- Example 7 Regeneration of polyimide film on the fluoride ion color sensor
- Example of a long sheet of polyimide film is cut into three 0.5 ⁇ 2cm obtained, which was immersed in the formulation of tetrabutylammonium fluoride was dissolved in ethanol 0.1mol / L of fluoride ions - solution, After 60 minutes, remove and dry, the film becomes green; soak it in 0.05mol/L trifluoroacetic acid ethanol solution for regeneration treatment, remove and dry after 10 minutes, the color of the film returns from green to the original yellow, still has Color-sensing effect on fluoride ions; and used more than 10 times, after each regeneration process, for the determination of fluoride ions, it can still maintain the same color-sensitivity;
- Example 1, Example 2 and Example 4 The polyimide film obtained is the same as in Example 3, and can be used for the determination of fluoride ion many times after regeneration treatment.
- the polyimide film of the present invention can be directly cut into a sheet, and the sensor device is very convenient to manufacture. It is used for the color sensing of fluoride ions, and the measurement sensitivity reaches 10-4 mol/L, and The selectivity is high, and the sensing function can be restored through the regeneration method, which is used for the determination of fluoride ion many times.
- the prior art fluoride ion detection color sensor is based on a small molecule compound (Chinese invention patent CN201010202940.0), which cannot be directly formed into a film, and needs to be loaded on filter paper fibers with 10 layers of titanium dioxide film deposited on the surface, the preparation method is very complicated, and Can only be used once.
- the polyimide film of the present invention has obvious convenience advantages, cost advantages, and greater application value for sensing and measuring fluoride ions.
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Abstract
一种氟离子显色传感聚酰亚胺薄膜及其制备方法与应用;氟离子显色传感聚酰亚胺薄膜的制备方法是将芳香二胺单体与芳香二酐单体在强极性非质子有机溶剂中混合,加入催化剂,在室温下抽真空‐通氩气循环多次,然后在氩气保护下反应,得到聚酰亚胺溶液;再制备纤维状聚酰亚胺;将纤维状聚酰亚胺溶解在强极性非质子有机溶剂中,充分搅拌溶解后均匀涂抹在干净的玻璃板上,除去溶剂,冷却后浸泡在热水中剥膜,得到氟离子显色传感聚酰亚胺薄膜。该含有羟基芴的聚酰亚胺薄膜可以直接裁剪成片状使用,传感器件制作十分方便,用于氟离子的测定,灵敏度达到10‐4mol/L,且选择性高。
Description
本发明涉及一类测定氟离子的聚酰亚胺薄膜传感材料,特别是涉及一类显色传感,目视即可测定氟离子的聚酰亚胺薄膜传感材料及其制备方法与应用,属于材料科学领域与离子检测技术领域。
氟离子作为最小的阴离子,在许多生物和化学过程起到重要而基础的作用,适量的氟离子能够预防蛀牙和骨质疏松症,但过量的摄入氟离子将引起氟中毒,高浓度的氟离子会严重危害环境,氟离子的存在严重影响人类的生活,很多场合都需要快速、高效地识别和检测氟离子浓度。利用对氟离子敏感的化学物质,借助仪器,采用紫外‐可见光谱法、荧光光谱法和循环伏安法等进行测定是较普遍的方法,目前已发现的氟离子化学传感物质多为小分子化合物,配制成溶液测定,存在使用不方便、难以实现循环使用等缺点,开发简单、方便的检测氟离子方法具有十分重要的现实意义。
以固态薄膜为传感材料,利用其与氟离子结合后发生只需目视即可观察到的颜色变化,以此测定氟离子浓度,不需要复杂的仪器,操作简单、方便。中国发明专利CN201010202940.0将对氟离子敏感的配体茜素络合剂分子单层负载到表面沉积10层二氧化钛膜的滤纸纤维上,实现对氟离子的显色传感和测定,但该发明借助定量滤纸作载体,制备方法复杂,只能一次使用。
中国发明专利CN201610949644.4公开了一种以2‐溴‐9,9‐(N‐咔唑‐己基)芴为原料,与三甲基乙炔基硅反应,再经过电化学聚合得到聚1,4‐二(4‐(9,9‐双(N‐咔唑‐己基)芴基)‐1,2,3‐三唑基)苯薄膜,该薄膜可用作检测氟离子的荧光传感膜,灵敏度高,但需要专门的荧光检测仪。目前尚未有通过目视颜色变化即可测定氟离子的显色传感固态薄膜材料。
发明内容
本发明的目的在于提供一种通过目视颜色变化即可测定氟离子的显色传感聚酰亚胺薄膜;
本发明的另一个目的是提供氟离子显色传感聚酰亚胺薄膜的制备方法;
本发明还有一个目的是提供氟离子显色传感聚酰亚胺薄膜在氟离子测定中的应用。
本发明通过将羟基芴结构引入到聚酰亚胺中,其分子结构上的羟基可以与氟离子形成较强的氢键相互作用,致使聚酰亚胺链中的羟基发生去质子化,分子内的电荷转移效应增 强,导致在可见光区域有强吸收;该聚酰亚胺薄膜放入氟离子溶液中浸泡后,取出,颜色从黄色变成绿色,颜色变化明显,通过目视绿色的深浅,就可以估算对应的氟离子浓度,实现氟离子的定量测定,不需要借助其他分析化学仪器。
通常氟离子都是溶解在水或乙醇、甲醇或丙酮等常用低沸点溶剂中配制成溶液进行测定,这就需要传感材料有好的耐水性、耐溶剂性、热稳定性、尺寸稳定性和一定的力学强度。本发明聚酰亚胺是一类主链含有亚酰胺环的高性能聚合物材料,具有优异的热稳定性、耐水性、耐溶剂性、尺寸稳定性和力学强度等。本发明含有羟基芴的聚酰亚胺薄膜对氟离子具有灵敏的显色反应,通过目视即可测定氟离子的浓度,且可以通过再生的方法恢复传感作用,多次使用。该薄膜可以直接裁剪成片状,传感器件制作方便,应用价值大。
本发明目的通过如下技术方案实现:
一种氟离子显色传感聚酰亚胺薄膜,聚酰亚胺分子结构中含有羟基芴基团,分子结构通式为:
其中n表示重复结构单元的平均个数,取值为100~201;R
1和R
2为H或者CH
3;Ar为以下结构通式中的一种:
所述的氟离子显色传感聚酰亚胺薄膜的制备方法,包括以下步骤:
(1)将芳香二胺单体与芳香二酐单体在强极性非质子有机溶剂中混合,加入催化剂,在室温下抽真空‐通氩气循环多次,然后在氩气保护下,先在25~85℃反应2~12小时,然后升温到150~220℃继续反应12~48小时,得到聚酰亚胺溶液;将该聚酰亚胺溶液滴加到乙醇中,产生纤维状沉淀,滴加完成后,静置过滤,除去有机溶剂,将沉淀干燥,得到纤维状聚酰亚胺;所述催化剂为异喹啉、乙酸酐、三乙胺和吡啶中的一种或者两种;
所述芳香二胺单体的结构式为:
其中R
1和R
2为H或者CH
3;
所述芳香二酐单体为4,4'‐(六氟异丙烯)二酞酸酐、4,4'‐氧双邻苯二甲酸酐、3,3',4,4'‐二苯基砜四羧酸二酸酐或4,4'‐(4,4'‐异亚丙基二苯氧基)双(酞酸酐);
(2)将步骤(1)所得的纤维状聚酰亚胺溶解在强极性非质子有机溶剂中,控制固含量为10~15wt%,充分搅拌溶解后均匀涂抹在干净的玻璃板上,多次抽真空,直至无气泡,再升温除去溶剂,冷却后浸泡在热水中剥膜,得到氟离子显色传感聚酰亚胺薄膜。
为进一步实现本发明目的,优选地,所述芳香二胺单体与芳香二酐单体的摩尔比控制为1:0.9~1.1。
优选地,所述强极性非质子有机溶剂为N,N‐二甲基甲酰胺、N‐甲基吡咯烷酮、二甲基亚砜、N,N‐二甲基乙酰胺和间甲酚中的一种或者两种。
优选地,所述的催化剂的用量为芳香二胺单体摩尔数的0.01~0.1倍。
优选地,步骤(1)所述的将沉淀干燥是将沉淀置于95~105℃下真空干燥8~12小时;所述的在室温下抽真空‐通氩气循环的次数为两次;所述的乙醇用量为聚酰亚胺溶液体积的10~15倍。
优选地,步骤(2)所述的玻璃板为二氧化硅玻璃板;所述的升温除去溶剂是从室温升至70℃真空干燥8~12小时;再从70℃升至120℃真空干燥3~6小时;再从120℃升至200℃真空干燥2~3小时。
所述的氟离子显色传感聚酰亚胺薄膜测定氟离子的应用:将所述聚酰亚胺薄膜裁成条状,浸泡在待测溶液中,浸泡20~60分钟,取出用乙醇冲洗,观察薄膜颜色变化;只有浸泡在含有氟离子的溶液中时,聚酰亚胺薄膜由黄色变为绿色,颜色产生通过目视可以识别的明显变化,该聚酰亚胺薄膜对氟离子具有明显的显色传感作用。
优选地,所述的待测溶液中氟离子的浓度为10
‐4~0.1mol/L;将所述聚酰亚胺薄膜裁成0.5×2cm的长条片状。
优选地,所述的聚酰亚胺薄膜由黄色变为绿色后浸泡在含有0.01~0.1mol/L的三氟乙酸的乙醇溶液中进行再生处理,5~20分钟后,薄膜颜色由绿色恢复到原来的黄色,仍然对氟离子具有同样灵敏的显色传感作用;反复10次,该聚酰亚胺薄膜对氟离子具有同样灵敏的显色传感作用。
本发明中,4,4'‐(六氟异丙烯)二酞酸酐的为:
4,4'‐氧双邻苯二甲酸酐(ODPA)的结构式为:
3,3',4,4'‐二苯基砜四羧酸二酸酐(DSDA)的结构式为:
4,4'‐(4,4'‐异亚丙基二苯氧基)双(酞酸酐)(BPADA)的结构式为:
本发明与现有技术相比,具有以下的效果:
1、本发明含有羟基芴的聚酰亚胺薄膜不溶于水和乙醇、甲醇或丙酮等常用低沸点溶剂,氮气氛围中5%热失重温度达到500℃,玻璃化转变温度达到370℃,热膨胀系数小于70ppm/℃,拉伸模量大于3.0GPa,拉伸强度大于90MPa,断裂伸长率达到8%,满足氟离子传感材料对耐水性、耐溶剂性、热稳定性、尺寸稳定性和力学强度的需要。
2、本发明含有羟基芴的聚酰亚胺薄膜可以直接裁剪成片状使用,传感器件制作十分方便,用于氟离子的测定,灵敏度达到10
‐4mol/L,且选择性高;
3、本发明含有羟基芴的聚酰亚胺薄膜可通过再生的方法恢复传感作用,多次用于氟离子的测定。
图1为本发明实施例1~4所得到聚酰亚胺薄膜产物的全反射红外光谱图,其中:a为实施例1所得聚酰亚胺薄膜产物,b为实施例2所得聚酰亚胺薄膜产物,c为实施例3所得聚酰亚胺薄膜产物,d为实施例4所得聚酰亚胺薄膜产物。
图2为本发明实施例1~4所得到聚酰亚胺溶于氘代二甲基亚砜测得的核磁共振氢谱图。
为更好地理解本发明,以下结合附图和实施例对本发明作进一步的说明,但本发明的实施方式不限于此。
实施例1
将1.241g 4,4'‐氧双邻苯二甲酸酐(ODPA)与1.522g 2,7‐二羟基‐9,9‐二(4‐氨苯基)芴(AHF)加入到100mL单口烧瓶中,加入25毫升间甲酚为溶剂,8滴异喹啉作为催化剂,磁力搅拌混合均匀,在室温下抽真空‐通氩气循环两次,然后在氩气保护下,分别在85℃和200℃各反应12小时;结束反应,冷却到室温,得到粘稠的聚酰亚胺溶液;将其滴加到400mL乙醇中,产生纤维状沉淀,滴加完成后,静置过滤;将沉淀在100℃下真空干燥10小时得到纤维状聚酰亚胺;取部分干燥的纤维状聚酰亚胺溶解在N,N‐二甲基乙酰胺中,控制固含量为10%,充分搅拌溶解后,均匀涂抹在干净的二氧化硅玻璃板上,多次抽真空,直至无气泡,在真空干燥箱中70℃下干燥12小时,120℃下干燥3小时,200℃下干燥3小时,冷却后浸泡在热水中剥膜,得到氟离子显色传感ODPA‐AHF型聚酰亚胺薄膜;
该聚酰亚胺薄膜的颜色为黄色,不溶于水、乙醇、甲醇和丙酮;采用热重分析仪(TGA)测得在氮气氛围中5%失重温度为525℃;采用动态热机械分析仪(DMA)测得其玻璃化转变温度为410℃;采用静态机械分析仪(TMA)测试得到该聚酰亚胺薄膜的热膨胀系数(CET)为60.57ppm/℃;根据GB/T 1040.3‐2006标准测得该薄膜的拉伸模量为4.3GPa,拉伸强度为101.5MPa,断裂伸长率为14%。薄膜产物的全反射红外(IR)光谱如附图1中a,谱图上3100~3600cm
‐1间出现宽的对应羟基的特征吸收峰,1777cm
‐1和1711cm
‐1处分别对应酰亚 胺环中C=O的不对称和对称伸缩振动的特征峰,1368cm
‐1处对应酰亚胺环的C‐N键伸缩振动吸收峰,其它峰归属如下:3063、3043cm
‐1(芳香环不饱和C‐H伸缩振动),1607、1509cm
‐1(芳香环骨架振动),1337cm
‐1(C‐N伸缩振动),1273、1234、1084cm
‐1(C‐O伸缩振动);其核磁共振氢谱(600MHz,DMSO‐d6)如附图2中a,各化学位移(ppm)归属为δ9.46(s,2H),8.04(d,J=7.8Hz,2H),7.65‐7.54(m,6H),7.39(d,J=8.5Hz,4H),7.27(d,J=8.5Hz,4H),6.82(s,2H),6.77(d,J=8.0Hz,2H);将其溶解于N,N‐二甲基甲酰胺中,采用GPC法测得其数均分子量为7.15×104,PDI=1.64,重复结构单元平均个数为109;由上推知所得聚酰亚胺的分子结构式为:
实施例2
将1.241g 4,4'‐氧双邻苯二甲酸酐(ODPA)与1.572g 2,7‐二羟基‐9,9‐二(3,5‐二甲基‐4‐氨苯基)芴(DMAHF)加入到100mL单口烧瓶中,加入30毫升N,N‐二甲基甲酰胺为溶剂,6ml乙酸酐和4ml吡啶作为催化剂,磁力搅拌混合均匀,在室温下抽真空‐通氩气循环两次,然后在氩气保护下,分别在25℃反应6小时,然后升温到150℃继续反应18小时;结束反应,冷却到室温,得到粘稠的聚酰亚胺溶液;将其滴加到400mL乙醇中,产生纤维状沉淀,滴加完成后,静置过滤;将沉淀在105℃下真空干燥8小时得到纤维状聚酰亚胺;取部分干燥的纤维状聚酰亚胺溶解在N,N‐二甲基甲酰胺中,控制固含量为10%,充分搅拌溶解后,均匀涂抹在干净的二氧化硅玻璃板上,多次抽真空,直至无气泡,在真空干燥箱中70℃下干燥6小时,120℃下干燥5小时,200℃下干燥4小时,冷却后浸泡在热水中剥膜,得到氟离子显色传感ODPA‐DMAHF型聚酰亚胺薄膜。
该聚酰亚胺薄膜的颜色为黄色,不溶于水、乙醇、甲醇和丙酮;采用TGA测得在氮气氛围中5%失重温度为527℃,采用DMA法测得其玻璃化转变温度为452℃;采用TMA测试得到该聚酰亚胺薄膜的CET为56.76ppm/℃;根据GB/T 1040.3‐2006标准测量得到该薄膜的拉伸模量为3.6GPa,拉伸强度为93.9MPa,断裂伸长率为11%。薄膜产物的全反射IR光谱如附图1中b,数据结果为:IR(cm
‐1):ν=3100~3600(O‐H伸缩振动),3067、3031(芳香环不饱和C‐H伸缩振动),2955、2922、2864(饱和C‐H伸缩振动),1776、1713(C=O伸缩振动),1605、1472(芳香环骨架振动),1363(C‐N伸缩振动),1272、1232、1102(C‐O伸缩振动);产物的核磁共振氢谱(
1H NMR,600MHz,DMSO‐d
6)如附图2中b,各化学位移(ppm)归属为:δ9.46(s,2H),8.07(d,J=8.3Hz,2H),7.70(s,2H),7.65(d,J=8.1Hz,2H),7.56 (d,J=8.2Hz,2H),6.97(s,4H),6.84(s,2H),6.77(d,J=7.8Hz,2H),2.01(s,12H),将其溶解于N,N‐二甲基甲酰胺中,采用GPC法测得数均分子量为1.43×10
5,PDI=2.46,重复结构单元平均个数为201;由上推知所得聚酰亚胺的分子结构式为:
实施例3
将1.746g 4,4'‐(六氟异丙烯)二酞酸酐(6FDA)与1.921g 2,7‐二羟基‐9,9‐二(4‐氨苯基)芴(DMAHF)加入到100mL单口烧瓶中,加入30毫升间甲酚为溶剂,10滴异喹啉作为催化剂,磁力搅拌混合均匀,在室温下抽真空‐通氩气循环两次,然后在氩气保护下,分别在80℃反应6小时,然后升温到220℃反应6小时;结束反应,冷却到室温,得到粘稠的聚酰亚胺溶液;将其滴加到500mL乙醇中,产生纤维状沉淀,滴加完成后,静置过滤;将沉淀在95℃下真空干燥12小时得到纤维状聚酰亚胺;取部分干燥的纤维状聚酰亚胺溶解在N,N‐二甲基乙酰胺中,控制固含量为10%,充分搅拌溶解后,均匀涂抹在干净的二氧化硅玻璃板上,多次抽真空,直至无气泡,在真空干燥箱中70℃下干燥8小时,120℃下干燥6小时,200℃下干燥2小时,冷却后浸泡在热水中剥膜,得到氟离子显色传感6FDA‐DMAHF型聚酰亚胺薄膜。
该聚酰亚胺薄膜的颜色为黄色,不溶于水、乙醇、甲醇和丙酮;采用TGA测得在氮气氛围中5%失重温度为516℃,采用DMA法测得其玻璃化转变温度为456℃;采用TMA测试得到该聚酰亚胺薄膜的CET为62.09ppm/℃;根据GB/T 1040.3‐2006标准测得该薄膜的拉伸模量为3.5GPa,拉伸强度为95.5MPa,断裂伸长率为8%。薄膜产物的全反射IR光谱如附图1中c,数据结果为:IR(cm
‐1):ν=3100~3600(O‐H伸缩振动),3072、3030(芳香环不饱和C‐H伸缩振动),2958、2924、2865(饱和C‐H伸缩振动),1783、1714(C=O伸缩振动),1609、1479(芳香环骨架振动),1366(C‐N伸缩振动),1293、1251、1191、1142、1103(C‐O伸缩振动);产物的
1H NMR(600MHz,DMSO‐d
6)如附图2中c,各化学位移(ppm)归属为:δ9.46(s,2H),8.15(d,J=7.2Hz,2H),7.90(s,4H),7.56(d,J=8.0Hz,2H),6.97(s,4H),6.84(s,2H),6.77(d,J=7.5Hz,2H),2.02(s,12H);将其溶解于N,N‐二甲基甲酰胺中,采用GPC法测得数均分子量为9.74×10
4,PDI=1.76,重复结构单元平均个数为115;由上推知所得聚酰亚胺的分子结构式为:
实施例4
将2.082g 4,4'‐(4,4'‐异亚丙基二苯氧基)双(酞酸酐)(BPADA)与1.834g 2,7‐二羟基‐9,9‐二(4‐氨苯基)芴(DMAHF)加入到100mL单口烧瓶中,加入30毫升间甲酚为溶剂,10滴异喹啉作为催化剂,磁力搅拌混合均匀,在室温下抽真空‐通氩气循环两次,然后在氩气保护下,分别在80℃反应8小时,然后升温到200℃反应12小时;结束反应,冷却到室温,得到粘稠的聚酰亚胺溶液;将其滴加到400mL乙醇中,产生纤维状沉淀,滴加完成后,静置过滤;将沉淀在100℃下真空干燥10小时得到纤维状聚酰亚胺;取部分干燥的纤维状聚酰亚胺溶解在N,N‐二甲基甲酰胺中,控制固含量为10%,充分搅拌溶解后,均匀涂抹在干净的二氧化硅玻璃板上,多次抽真空,直至无气泡,在真空干燥箱中70℃下干燥12小时,120℃下干燥4小时,200℃下干燥3小时,冷却后浸泡在热水中剥膜,得到氟离子显色传感BPADA‐DMAHF型聚酰亚胺薄膜。
该聚酰亚胺薄膜的颜色为淡黄色,不溶于水、乙醇、甲醇和丙酮;采用TGA测得在氮气氛围中5%失重温度为501℃,采用DMA法测得其玻璃化转变温度为370℃;采用TMA测试得到该聚酰亚胺薄膜的CET为69.06ppm/℃;根据GB/T 1040.3‐2006标准测得该薄膜的拉伸模量为3.3GPa,拉伸强度为92.8MPa,断裂伸长率为13%;薄膜产物的全反射IR光谱如附图1中d,数据结果为:IR(cm
‐1):ν=3100~3600(O‐H伸缩振动),3061、3023(芳香环不饱和C‐H伸缩振动),2968、2924、2852(饱和C‐H伸缩振动),1777、1709(C=O伸缩振动),1608、1460(芳香环骨架振动),1365(C‐N伸缩振动),1291、1214、1102(C‐O伸缩振动);产物的
1H NMR(600MHz,DMSO‐d
6)如附图2中d,各化学位移(ppm)归属为:δ=9.45(s,2H),7.97(d,J=8.2Hz,2H),7.56(d,J=8.1Hz,2H),7.38(dd,J=20.7,8.9Hz,8H),7.14(d,J=8.0Hz,4H),6.95(s,4H),6.84(s,2H),6.76(d,J=7.7Hz,2H),1.97(s,12H),1.69(s,6H);将其溶解于N,N‐二甲基甲酰胺中,采用GPC法测得数均分子量为9.2×10
4,PDI=1.52,重复结构单元平均个数为100,由上推知所得聚酰亚胺的分子结构式为:
由上可知,实施例1~4所得到的聚酰亚胺薄膜不溶于水和乙醇、甲醇或丙酮等常用低 沸点溶剂,氮气氛围中5%热失重温度达到500℃,玻璃化转变温度达到370℃,热膨胀系数小于70ppm/℃,拉伸模量大于3.0GPa,拉伸强度大于90MPa,断裂伸长率达到8%,满足氟离子传感材料对耐水性、耐溶剂性、热稳定性、尺寸稳定性和力学强度的需要。
实施例5:聚酰亚胺薄膜对氟离子显色传感的灵敏性实验
将实施例4所得到聚酰亚胺薄膜裁成0.5×2cm的长条片状,采用四丁基氟化铵溶解在乙醇中配制成氟离子浓度分别为10
‐6、10
‐5、10
‐4、10
‐3、10
‐2和0.1mol/L的溶液;取所裁聚酰亚胺薄膜条分别浸泡在各溶液中40分钟,取出后用乙醇冲洗,观察薄膜颜色变化;结果发现随着氟离子浓度的增加,聚酰亚胺薄膜的颜色由淡绿色逐渐变为深绿色;即使当浸泡在浓度低至10
‐4mol/L的氟离子溶液时,也可以观察到溶液颜色明显转变为淡绿色,所得到的聚酰亚胺薄膜对氟离子具有较灵敏的显色传感作用。实施例1、实施例2和实施例3所得的聚酰亚胺薄膜均如同实施例4一样,对氟离子的测定灵敏度达到10
‐4mol/L。
实施例6:聚酰亚胺薄膜对氟离子显色传感的选择性实验
将实施例2所得到聚酰亚胺薄膜裁成0.5×2cm的长条片状,分别浸泡在0.1mol/L的Cl
‐、Br
‐、I
‐、AcO
‐、H
2PO
4
‐、HSO
4
‐、BF
4
‐、NO
3
‐或ClO
4
‐的乙醇溶液中,浸泡60分钟后取出,用乙醇冲洗,可以发现,即使这些阴离子的浓度高达0.1mol/L,仍然不会引起聚酰亚胺薄膜颜色的变化,而实施例5中提到即使当氟离子浓度低至10
‐4mol/L时,仍然引起该聚酰亚胺薄膜的颜色变为淡绿色,说明该聚酰亚胺薄膜对氟离子的识别具有高的选择性;将实施例2所得到聚酰亚胺薄膜改为实施例1、实施例3和实施例4所得的聚酰亚胺薄膜均一样对氟离子的显色传感作用具有高的选择性。
实施例7:聚酰亚胺薄膜对氟离子显色传感作用的再生
将实施例3所得到聚酰亚胺薄膜裁成0.5×2cm的长条片状,将其浸泡在由四丁基氟化铵溶解在乙醇中配制的0.1mol/L的氟离子
‐溶液中,60分钟后取出晾干,薄膜变为绿色;将其浸泡在0.05mol/L三氟乙酸的乙醇溶液中进行再生处理,10分钟后取出晾干,薄膜颜色由绿色恢复到原来的黄色,仍然具有对氟离子的显色传感作用;且使用10次以上,每次经过再生处理后,用于氟离子的测定,仍可保持同样的显色灵敏性;实施例1、实施例2和实施例4所得的聚酰亚胺薄膜均如同实施例3一样,可以通过再生处理后多次用于氟离子的测定。
由实施例5~7可知,本发明聚酰亚胺薄膜可以直接裁剪成片状使用,传感器件制作十分方便,用于氟离子的显色传感,测定灵敏度达到10
‐4mol/L,且选择性高,还可通过再生的方法恢复传感作用,多次用于氟离子的测定。现有技术氟离子检测显色传感器是基于小分子化合物的(中国发明专利CN201010202940.0),其不能直接成膜,需负载到表面沉积10层二氧化钛膜的滤纸纤维上,制备方法十分复杂,且只能使用一次。与现有技术相比, 本发明的聚酰亚胺薄膜用于氟离子的传感测定具有明显的便利优势,成本优势,应用价值更大。
需要说明的是,本发明不受上述实施例的限制,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明保护范围内;本发明要求保护范围由权利要求书界定。
Claims (10)
- 根据权利要求1所述的氟离子显色传感聚酰亚胺薄膜的制备方法,其特征在于,包括以下步骤:(1)将芳香二胺单体与芳香二酐单体在强极性非质子有机溶剂中混合,加入催化剂,在室温下抽真空‐通氩气循环多次,然后在氩气保护下,先在25~85℃反应2~12小时,然后升温到150~220℃继续反应12~48小时,得到聚酰亚胺溶液;将该聚酰亚胺溶液滴加到乙醇中,产生纤维状沉淀,滴加完成后,静置过滤,除去有机溶剂,将沉淀干燥,得到纤维状聚酰亚胺;所述催化剂为异喹啉、乙酸酐、三乙胺和吡啶中的一种或者两种;所述芳香二胺单体的结构式为:其中R 1和R 2为H或者CH 3;所述芳香二酐单体为4,4'‐(六氟异丙烯)二酞酸酐、4,4'‐氧双邻苯二甲酸酐、3,3',4,4'‐二苯基砜四羧酸二酸酐或4,4'‐(4,4'‐异亚丙基二苯氧基)双(酞酸酐);(2)将步骤(1)所得的纤维状聚酰亚胺溶解在强极性非质子有机溶剂中,控制固含量为10~15wt%,充分搅拌溶解后均匀涂抹在干净的玻璃板上,多次抽真空,直至无气泡,再升温除去溶剂,冷却后浸泡在热水中剥膜,得到氟离子显色传感聚酰亚胺薄膜。
- 根据权利要求2所述的氟离子显色传感聚酰亚胺薄膜的制备方法,其特征在于:所述芳 香二胺单体与芳香二酐单体的摩尔比控制为1:0.9~1.1。
- 根据权利要求2所述的氟离子显色传感聚酰亚胺薄膜的制备方法,其特征在于:所述强极性非质子有机溶剂为N,N‐二甲基甲酰胺、N‐甲基吡咯烷酮、二甲基亚砜、N,N‐二甲基乙酰胺和间甲酚中的一种或者两种。
- 根据权利要求2所述的氟离子显色传感聚酰亚胺薄膜的制备方法,其特征在于:所述的催化剂的用量为芳香二胺单体摩尔数的0.01~0.1倍。
- 根据权利要求2所述的氟离子显色传感聚酰亚胺薄膜的制备方法,其特征在于:步骤(1)所述的将沉淀干燥是将沉淀置于95~105℃下真空干燥8~12小时;所述的在室温下抽真空‐通氩气循环的次数为两次;所述的乙醇用量为聚酰亚胺溶液体积的10~15倍。
- 根据权利要求2所述的氟离子显色传感聚酰亚胺薄膜的制备方法,其特征在于:步骤(2)所述的玻璃板为二氧化硅玻璃板;所述的升温除去溶剂是从室温升至70℃真空干燥8~12小时;再从70℃升至120℃真空干燥3~6小时;再从120℃升至200℃真空干燥2~3小时。
- 权利要求1所述的氟离子显色传感聚酰亚胺薄膜测定氟离子的应用,其特征在于:将所述聚酰亚胺薄膜裁成条状,浸泡在待测溶液中,浸泡20~60分钟,取出用乙醇冲洗,观察薄膜颜色变化;只有浸泡在含有氟离子的溶液中时,聚酰亚胺薄膜由黄色变为绿色,颜色产生通过目视可以识别的明显变化,该聚酰亚胺薄膜对氟离子具有明显的显色传感作用。
- 根据权利要求8所述的氟离子显色传感聚酰亚胺薄膜测定氟离子的应用,其特征在于:所述的待测溶液中氟离子的浓度为10 ‐4~0.1mol/L;将所述聚酰亚胺薄膜裁成0.5×2cm的长条片状。
- 根据权利要求8所述的氟离子显色传感聚酰亚胺薄膜测定氟离子的应用,其特征在于:所述的聚酰亚胺薄膜由黄色变为绿色后浸泡在含有0.01~0.1mol/L的三氟乙酸的乙醇溶液中进行再生处理,5~20分钟后,薄膜颜色由绿色恢复到原来的黄色,仍然对氟离子具有同样灵敏的显色传感作用;反复10次,该聚酰亚胺薄膜对氟离子具有同样灵敏的显色传感作用。
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