CN105754276A - Polymer film material with temperature fluorescence response and preparation method of polymer film material - Google Patents

Polymer film material with temperature fluorescence response and preparation method of polymer film material Download PDF

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CN105754276A
CN105754276A CN201610177494.XA CN201610177494A CN105754276A CN 105754276 A CN105754276 A CN 105754276A CN 201610177494 A CN201610177494 A CN 201610177494A CN 105754276 A CN105754276 A CN 105754276A
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梁浩
解芳
封科军
冯颖
朱庆英
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Abstract

本发明涉及光学传感材料技术领域，具体公开了一种具有温度荧光响应的聚合物薄膜材料的制备方法，本发明的制备方法在碳纳米管表面键合具有荧光效应的Eu(TTA)3(H2O)2，并将这种表面修饰铕化合物的碳纳米管分散到聚合物中，制备同时具有稀土离子发光特性和碳纳米管优异性能的新型温度荧光响应薄膜材料；本发明将发光的铕化合物、碳纳米管与聚合物结合，不仅可以获得同时具有稀土离子发光特性和碳纳米管优异性能的新型温度荧光响应薄膜材料，而且该方法操作简单，所制备的材料性能稳定。

The invention relates to the technical field of optical sensing materials, and specifically discloses a method for preparing a polymer film material with temperature and fluorescence response. The preparation method of the invention bonds Eu(TTA) 3 ( H 2 O) 2 , and disperse the carbon nanotubes of this surface-modified europium compound into the polymer to prepare a novel temperature-fluorescence-responsive thin-film material with rare earth ion luminescence characteristics and excellent performance of carbon nanotubes; the present invention will emit light Combining europium compounds, carbon nanotubes and polymers can not only obtain a new type of temperature fluorescence responsive thin film material that has both the luminescent properties of rare earth ions and the excellent performance of carbon nanotubes, but also the method is simple to operate and the performance of the prepared material is stable.

Description

一种具有温度荧光响应的聚合物薄膜材料及其制备方法A kind of polymer film material with temperature fluorescence response and preparation method thereof

技术领域technical field

本发明涉及光学传感材料技术领域，尤其涉及一种具有温度荧光响应的聚合物薄膜材料及其制备方法。The invention relates to the technical field of optical sensing materials, in particular to a polymer film material with temperature fluorescence response and a preparation method thereof.

背景技术Background technique

荧光敏感材料与被测物质或环境相互接触时，由于荧光基团内在的光物理特性被影响，从而使光信号的输出形式发生改变以达到传感目的。荧光传感具有灵敏度高，选择性好，可采集信号丰富等优点，被越来越多地用于离子、气体浓度和温度等的检测。各个领域对荧光传感的广泛要求，使得对于荧光传感材料的研究和开发一直十分活跃，并表现出非常广阔的应用前景。When the fluorescent sensitive material is in contact with the measured substance or the environment, because the inherent photophysical properties of the fluorescent group are affected, the output form of the optical signal is changed to achieve the sensing purpose. Fluorescence sensing has the advantages of high sensitivity, good selectivity, and rich signal collection, and is increasingly used for the detection of ions, gas concentrations, and temperatures. The extensive requirements for fluorescent sensing in various fields have made the research and development of fluorescent sensing materials very active, and have shown very broad application prospects.

根据荧光基团的类型不同，通常将荧光敏感材料分为基于有机分子荧光的敏感材料和基于稀土离子发光的敏感材料两类。目前大多数荧光传感都是基于有机分子荧光敏感材料，但有机荧光分子有一个缺点，即容易发生“光漂白”现象，这一缺陷限制了其应用范围。According to the different types of fluorophores, fluorescent sensitive materials are usually divided into two categories: sensitive materials based on organic molecular fluorescence and sensitive materials based on rare earth ion luminescence. Most of the current fluorescent sensing is based on organic molecular fluorescent sensitive materials, but organic fluorescent molecules have a disadvantage that they are prone to "photobleaching", which limits their application range.

与有机荧光发射团相比，稀土荧光敏感材料具有较高的量子产率，较大的Storks位移，较窄的发射谱带，以及更稳定的发光性能，这些特点使其在荧光传感和荧光探针方面具有广阔的应用前景。碳纳米管由于具有优异的物理、化学特性，当其应用在传感方面时，不仅具有纳米材料本身的特性，同时由于其比表面积大、表面活性高、表面可带较多官能团以及良好的生物亲和性等优异性质，对于提高传感器性能和响应信号等具有重大意义。Compared with organic fluorescent emission groups, rare earth fluorescent sensitive materials have higher quantum yield, larger Storks shift, narrower emission band, and more stable luminescent properties, which make them suitable for fluorescence sensing and fluorescence Probes have broad application prospects. Due to the excellent physical and chemical properties of carbon nanotubes, when they are used in sensing, they not only have the characteristics of nanomaterials, but also because of their large specific surface area, high surface activity, more functional groups on the surface and good biological properties. Excellent properties such as affinity are of great significance for improving sensor performance and response signals.

发明内容Contents of the invention

本发明的目的在于提供一种以表面修饰铕化合物的碳纳米管/聚合物温度荧光响应薄膜材料的制备方法。The object of the present invention is to provide a method for preparing a carbon nanotube/polymer temperature fluorescence response thin film material with surface modification of europium compound.

为了解决上述技术的问题，本发明采用的技术方案是：将具有荧光效应的铕-噻吩甲酰三氟丙酮化合物(Eu(TTA)3(H2O)2)与碳纳米管结合，并将这种表面修饰铕化合物的碳纳米管分散到聚合物中，得到具有温度荧光响应的聚合物薄膜材料，本发明的方法具体包括以下述步骤：In order to solve the problems of the above-mentioned technologies, the technical scheme adopted in the present invention is: combine europium-thienoyl trifluoroacetone compound (Eu(TTA) 3 (H 2 O) 2 ) with fluorescent effect with carbon nanotubes, and combine The carbon nanotubes of the surface-modified europium compound are dispersed into the polymer to obtain a polymer film material with temperature fluorescence response. The method of the present invention specifically includes the following steps:

步骤1、将一定量的碳纳米管放入浓H2SO4和HNO3的混合液中，在超声波振荡和机械搅拌作用下，20～40℃处理2～6h，然后用大量去离子水洗涤至中性，在50～60℃下真空干燥6～12h；Step 1. Put a certain amount of carbon nanotubes into the mixture of concentrated H 2 SO 4 and HNO 3 , under the action of ultrasonic oscillation and mechanical stirring, treat at 20-40°C for 2-6 hours, and then wash with a large amount of deionized water To neutral, vacuum dry at 50-60°C for 6-12 hours;

步骤2、将步骤1得到的碳纳米管加入20～60份酰氯化试剂中，在超声振荡下加热到60℃，回流24h，之后减压蒸馏除去多余的酰氯化试剂；Step 2, adding the carbon nanotubes obtained in step 1 to 20-60 parts of acyl chloride reagent, heating to 60° C. under ultrasonic vibration, reflux for 24 hours, and then distilling off excess acyl chloride reagent under reduced pressure;

步骤3、将步骤2得到的碳纳米管加入50～100份10wt％的5,6-二氨基-1,10-邻菲罗啉-二甲基甲酰胺溶液中，70～90℃磁力搅拌反应12～24h，过滤，用无水乙醇洗涤，60～70℃真空干燥3～6h；Step 3. Add the carbon nanotubes obtained in step 2 to 50-100 parts of 10 wt% 5,6-diamino-1,10-phenanthroline-dimethylformamide solution, and react with magnetic stirring at 70-90°C 12-24h, filter, wash with absolute ethanol, and vacuum-dry at 60-70°C for 3-6h;

步骤4、将步骤3得到的碳纳米管和1～5份Eu(TTA)3(H2O)2，加入到乙醇溶液中，加热回流反应24～48h后，用无水乙醇洗涤，60～70℃真空干燥3～6h；Step 4. Add the carbon nanotubes obtained in step 3 and 1 to 5 parts of Eu(TTA) 3 (H 2 O) 2 into the ethanol solution, heat to reflux for 24 to 48 hours, and then wash with absolute ethanol for 60 to 40 hours. Vacuum dry at 70°C for 3 to 6 hours;

步骤5、将步骤4得到的碳纳米管超声分散10～30min于聚合物溶液中，使用旋涂机在基片上旋涂，转速1000～2000转/分，在红外灯下干燥20～30min，得到具有温度荧光响应的聚合物薄膜材料。Step 5, ultrasonically dispersing the carbon nanotubes obtained in step 4 in the polymer solution for 10 to 30 minutes, spin coating on the substrate with a spin coater at a speed of 1000 to 2000 rpm, and drying under an infrared lamp for 20 to 30 minutes to obtain Polymer thin film materials with temperature fluorescent response.

优选的，步骤1中所述浓H2SO4和HNO3的体积比为3：1。Preferably, the volume ratio of concentrated H 2 SO 4 and HNO 3 in step 1 is 3:1.

优选的，步骤1中所述的碳纳米管为单壁碳纳米管，外径为1～2nm，长度为5～20μm。Preferably, the carbon nanotubes described in step 1 are single-walled carbon nanotubes with an outer diameter of 1-2 nm and a length of 5-20 μm.

优选的，步骤2中所述的酰氯化试剂为氯化亚砜，草酰氯中的至少一种。Preferably, the acid chloride reagent described in step 2 is at least one of thionyl chloride and oxalyl chloride.

优选的，步骤5中所述的聚合物溶液为聚甲基丙烯酸甲酯-环己酮、聚甲基丙烯酸甲酯-丙酮、聚苯乙烯-四氢呋喃、聚苯乙烯-二甲基甲酰胺、聚苯乙烯-氯仿、聚碳酸酯-氯仿、聚碳酸酯-二氯甲烷中的至少一种。Preferably, the polymer solution described in step 5 is polymethyl methacrylate-cyclohexanone, polymethyl methacrylate-acetone, polystyrene-tetrahydrofuran, polystyrene-dimethylformamide, poly At least one of styrene-chloroform, polycarbonate-chloroform, and polycarbonate-methylene chloride.

本发明还提供了一种如上述的制备方法制得的具有温度荧光响应的聚合物薄膜材料。The present invention also provides a polymer film material with temperature fluorescence response prepared by the above-mentioned preparation method.

本发明的制备方法在碳纳米管表面键合具有荧光效应的Eu(TTA)3(H2O)2，并将这种表面修饰铕化合物的碳纳米管分散到聚合物中，制备同时具有稀土离子发光特性和碳纳米管优异性能的新型温度荧光响应薄膜材料。The preparation method of the present invention bonds Eu(TTA) 3 (H 2 O) 2 with fluorescent effect on the surface of carbon nanotubes, and disperses the carbon nanotubes of this surface-modified europium compound into polymers to prepare rare earth A new type of temperature fluorescence responsive thin film material with ion luminescence characteristics and excellent performance of carbon nanotubes.

本发明将发光的铕化合物、碳纳米管与聚合物结合，不仅可以获得同时具有稀土离子发光特性和碳纳米管优异性能的新型温度荧光响应薄膜材料，而且该方法操作简单，所制备的材料性能稳定。The present invention combines luminescent europium compounds, carbon nanotubes and polymers, not only can obtain a new type of temperature fluorescence responsive thin film material that has both rare earth ion luminescent characteristics and excellent performance of carbon nanotubes, but also the method is simple to operate, and the prepared material properties Stablize.

附图说明Description of drawings

图1为表面修饰铕化合物的碳纳米管的合成路线图。Fig. 1 is a synthetic route diagram of carbon nanotubes surface-modified with europium compounds.

图2为实施例1制备的聚合物薄膜在不同温度下的荧光光谱曲线。FIG. 2 is the fluorescence spectrum curves of the polymer film prepared in Example 1 at different temperatures.

具体实施方式detailed description

实施例1：Example 1:

一种具有温度荧光响应的聚合物薄膜材料的制备方法，具体包括以下步骤：A method for preparing a polymer thin film material with temperature fluorescence response, specifically comprising the following steps:

1、将1g碳纳米管放入浓H2SO4和HNO3的混合液(体积比为3:1)中，在超声波振荡和机械搅拌作用下，30℃处理3h，然后用大量去离子水洗涤至中性，50℃真空干燥6h；1. Put 1g of carbon nanotubes into a mixture of concentrated H 2 SO 4 and HNO 3 (volume ratio 3:1), treat it at 30°C for 3 hours under the action of ultrasonic oscillation and mechanical stirring, and then use a large amount of deionized water Wash until neutral, and dry in vacuum at 50°C for 6 hours;

2、将1得到的碳纳米管加入25g氯化亚砜中，在超声振荡下加热到60℃，回流24h，之后减压蒸馏除去多余的酰氯化试剂；2. Add the carbon nanotubes obtained in 1 into 25 g of thionyl chloride, heat to 60° C. under ultrasonic oscillation, reflux for 24 hours, and then distill off excess acyl chloride reagent under reduced pressure;

3、将2得到的碳纳米管加入60g10wt％的5,6-二氨基-1,10-邻菲罗啉-二甲基甲酰胺溶液中，80℃磁力搅拌反应12h，过滤，用无水乙醇洗涤，65℃真空干燥5h；3. Add the carbon nanotubes obtained in 2 into 60g of 10wt% 5,6-diamino-1,10-phenanthroline-dimethylformamide solution, stir with magnetic force at 80°C for 12h, filter, and wash with absolute ethanol Wash and dry in vacuum at 65°C for 5h;

4、将3得到的碳纳米管和1.5gEu(TTA)3(H2O)2，加入到乙醇溶液中，加热回流反应24h，用无水乙醇洗涤，60℃真空干燥4h；4. Add the carbon nanotubes obtained in 3 and 1.5g Eu(TTA) 3 (H 2 O) 2 into the ethanol solution, heat to reflux for 24 hours, wash with absolute ethanol, and dry under vacuum at 60°C for 4 hours;

5、将4得到的碳纳米管超声分散15min于聚甲基丙烯酸甲酯-环己酮溶液中，使用旋涂机在基片上旋涂，转速1000转/分，在红外灯下干燥20min，得到具有温度荧光响应的薄膜材料。5. Ultrasonic disperse the carbon nanotubes obtained in 4 in polymethyl methacrylate-cyclohexanone solution for 15 minutes, spin-coat on the substrate with a spin coater at a speed of 1000 rpm, and dry for 20 minutes under an infrared lamp to obtain Thin film materials with temperature fluorescent response.

实施例2：Example 2:

一种具有温度荧光响应的聚合物薄膜材料的制备方法，具体包括以下步骤：A method for preparing a polymer thin film material with temperature fluorescence response, specifically comprising the following steps:

1、将2g碳纳米管放入浓H2SO4和HNO3的混合液(体积比为3:1)中，在超声波振荡和机械搅拌作用下，40℃处理6h，然后用大量去离子水洗涤至中性，55℃真空干燥10h；1. Put 2g of carbon nanotubes into a mixture of concentrated H 2 SO 4 and HNO 3 (volume ratio 3:1), treat it at 40°C for 6 hours under the action of ultrasonic oscillation and mechanical stirring, and then use a large amount of deionized water Wash until neutral, then vacuum dry at 55°C for 10 hours;

2、将1得到的碳纳米管加入40g草酰氯中，在超声振荡下加热到60℃，回流24h，之后减压蒸馏除去多余的酰氯化试剂；2. Add the carbon nanotubes obtained in 1 into 40 g of oxalyl chloride, heat to 60° C. under ultrasonic vibration, and reflux for 24 hours, and then distill under reduced pressure to remove excess acyl chloride reagent;

3、将2得到的碳纳米管加入120g10wt％的5,6-二氨基-1,10-邻菲罗啉-二甲基甲酰胺溶液中，70℃磁力搅拌反应20h，过滤，用无水乙醇洗涤，65℃真空干燥6h；3. Add the carbon nanotubes obtained in 2 into 120g of 10wt% 5,6-diamino-1,10-phenanthroline-dimethylformamide solution, stir with magnetic force at 70°C for 20 hours, filter, and wash with absolute ethanol Wash and dry in vacuum at 65°C for 6h;

4、将3得到的碳纳米管和5gEu(TTA)3(H2O)2，加入到乙醇溶液中，加热回流反应36h，用无水乙醇洗涤，70℃真空干燥3h；4. Add the carbon nanotubes obtained in 3 and 5g Eu(TTA) 3 (H 2 O) 2 into the ethanol solution, heat to reflux for 36 hours, wash with absolute ethanol, and dry in vacuum at 70°C for 3 hours;

5、将4得到的碳纳米管超声分散20min于聚苯乙烯-氯仿溶液中，使用旋涂机在基片上旋涂，转速1500转/分，在红外灯下干燥20min，得到具有温度荧光响应的薄膜材料。5. Ultrasonically disperse the carbon nanotubes obtained in 4 in a polystyrene-chloroform solution for 20 minutes, spin-coat on the substrate with a spin coater at a speed of 1500 rpm, and dry for 20 minutes under an infrared lamp to obtain a temperature-fluorescent response. film material.

实施例3：Example 3:

一种具有温度荧光响应的聚合物薄膜材料的制备方法，具体包括以下步骤：A method for preparing a polymer thin film material with temperature fluorescence response, specifically comprising the following steps:

1、将1.5g碳纳米管放入浓H2SO4和HNO3的混合液(体积比为3:1)中，在超声波振荡和机械搅拌作用下，35℃处理4h，然后用大量去离子水洗涤至中性，60℃真空干燥8h；1. Put 1.5g of carbon nanotubes into a mixture of concentrated H 2 SO 4 and HNO 3 (volume ratio 3:1), treat it at 35°C for 4 hours under the action of ultrasonic oscillation and mechanical stirring, and then use a large amount of deionized Wash with water until neutral, and dry in vacuum at 60°C for 8 hours;

2、将1得到的碳纳米管加入75g氯化亚砜中，在超声振荡下加热到60℃，回流24h，之后减压蒸馏除去多余的酰氯化试剂；2. Add the carbon nanotubes obtained in 1 into 75 g of thionyl chloride, heat to 60° C. under ultrasonic oscillation, reflux for 24 hours, and then distill off excess acyl chloride reagent under reduced pressure;

3、将2得到的碳纳米管加入100g10wt％的5,6-二氨基-1,10-邻菲罗啉-二甲基甲酰胺溶液中，90℃磁力搅拌反应16h，过滤，用无水乙醇洗涤，70℃真空干燥3h；3. Add the carbon nanotubes obtained in 2 into 100g of 10wt% 5,6-diamino-1,10-phenanthroline-dimethylformamide solution, stir with magnetic force at 90°C for 16 hours, filter, and wash with absolute ethanol Wash and dry in vacuum at 70°C for 3h;

4、将3得到的碳纳米管和2.5gEu(TTA)3(H2O)2，加入到乙醇溶液中，加热回流反应48h，用无水乙醇洗涤，65℃真空干燥5h；4. Add the carbon nanotubes obtained in 3 and 2.5g Eu(TTA) 3 (H 2 O) 2 into the ethanol solution, heat to reflux for 48 hours, wash with absolute ethanol, and dry under vacuum at 65°C for 5 hours;

5、将4得到的碳纳米管超声分散30min于聚碳酸酯-二氯甲烷溶液中，使用旋涂机在基片上旋涂，转速2000转/分，在红外灯下干燥30min，得到具有温度荧光响应的薄膜材料。5. Ultrasonic disperse the carbon nanotubes obtained in 4 in the polycarbonate-dichloromethane solution for 30 minutes, spin-coat on the substrate with a spin coater at a speed of 2000 rpm, and dry for 30 minutes under an infrared lamp to obtain a fluorescent film with temperature. Responsive film material.

本发明所述的5,6-二氨基-1,10-邻菲罗啉为商品化试剂，Eu(TTA)3(H2O)2为商品化试剂，也可以按照《美国化学会会志》(J.Am.Chem.Soc.1964年86卷5117页)中所述的方法制备。The 5,6-diamino-1,10-phenanthroline described in the present invention is a commercial reagent, and Eu(TTA) 3 (H 2 O) 2 is a commercial reagent. "(J.Am.Chem.Soc.1964 volume 86 page 5117) described method preparation.

本发明的制备方法在碳纳米管表面键合具有荧光效应的Eu(TTA)3(H2O)2，并将这种表面修饰铕化合物的碳纳米管分散到聚合物中，制备同时具有稀土离子发光特性和碳纳米管优异性能的新型温度荧光响应薄膜材料。The preparation method of the present invention bonds Eu(TTA) 3 (H 2 O) 2 with fluorescent effect on the surface of carbon nanotubes, and disperses the carbon nanotubes of this surface-modified europium compound into polymers to prepare rare earth A new type of temperature fluorescence responsive thin film material with ion luminescence characteristics and excellent performance of carbon nanotubes.

以上对本发明实施例所提供的技术方案进行了详细介绍，本文中应用了具体个例对本发明实施例的原理以及实施方式进行了阐述，以上实施例的说明只适用于帮助理解本发明实施例的原理；同时，对于本领域的一般技术人员，依据本发明实施例，在具体实施方式以及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。The technical solutions provided by the embodiments of the present invention have been introduced in detail above, and the principles and implementation modes of the embodiments of the present invention have been explained by using specific examples in this paper. The descriptions of the above embodiments are only applicable to help understand the embodiments of the present invention At the same time, for those of ordinary skill in the art, according to the embodiment of the present invention, there will be changes in the specific implementation and application scope. In summary, the content of this specification should not be construed as limiting the present invention.

Claims (6)

1.一种具有温度荧光响应的聚合物薄膜材料的制备方法，其特征在于，包括以下述步骤：1. a kind of preparation method with the polymer film material of temperature fluorescence response, is characterized in that, comprises the following steps: 步骤1、将一定量的碳纳米管放入浓H2SO4和HNO3的混合液中，在超声波振荡和机械搅拌作用下，20～40℃处理2～6h，然后用大量去离子水洗涤至中性，在50～60℃下真空干燥6～12h；Step 1. Put a certain amount of carbon nanotubes into the mixture of concentrated H 2 SO 4 and HNO 3 , under the action of ultrasonic oscillation and mechanical stirring, treat at 20-40°C for 2-6 hours, and then wash with a large amount of deionized water To neutral, vacuum dry at 50-60°C for 6-12 hours; 步骤2、将步骤1得到的碳纳米管加入20～60份酰氯化试剂中，在超声振荡下加热到60℃，回流24h，之后减压蒸馏除去多余的酰氯化试剂；Step 2, adding the carbon nanotubes obtained in step 1 to 20-60 parts of acyl chloride reagent, heating to 60° C. under ultrasonic vibration, reflux for 24 hours, and then distilling off excess acyl chloride reagent under reduced pressure; 步骤3、将步骤2得到的碳纳米管加入50～100份10wt％的5,6-二氨基-1,10-邻菲罗啉-二甲基甲酰胺溶液中，70～90℃磁力搅拌反应12～24h，过滤，用无水乙醇洗涤，60～70℃真空干燥3～6h；Step 3. Add the carbon nanotubes obtained in step 2 to 50-100 parts of 10 wt% 5,6-diamino-1,10-phenanthroline-dimethylformamide solution, and react with magnetic stirring at 70-90°C 12-24h, filter, wash with absolute ethanol, and vacuum-dry at 60-70°C for 3-6h; 步骤4、将步骤3得到的碳纳米管和1～5份Eu(TTA)3(H2O)2，加入到乙醇溶液中，加热回流反应24～48h后，用无水乙醇洗涤，60～70℃真空干燥3～6h；Step 4. Add the carbon nanotubes obtained in step 3 and 1 to 5 parts of Eu(TTA) 3 (H 2 O) 2 into the ethanol solution, heat to reflux for 24 to 48 hours, and then wash with absolute ethanol for 60 to 40 hours. Vacuum dry at 70°C for 3 to 6 hours; 步骤5、将步骤4得到的碳纳米管超声分散10～30min于聚合物溶液中，使用旋涂机在基片上旋涂，转速1000～2000转/分，在红外灯下干燥20～30min，得到具有温度荧光响应的聚合物薄膜材料。Step 5, ultrasonically dispersing the carbon nanotubes obtained in step 4 in the polymer solution for 10 to 30 minutes, spin coating on the substrate with a spin coater at a speed of 1000 to 2000 rpm, and drying under an infrared lamp for 20 to 30 minutes to obtain Polymer thin film materials with temperature fluorescent response. 2.根据权利要求1所述的一种具有温度荧光响应的聚合物薄膜材料的制备方法，其特征在于：步骤1中所述浓H2SO4和HNO3的体积比为3：1。2 . The method for preparing a polymer film material with temperature and fluorescence response according to claim 1 , wherein the volume ratio of concentrated H 2 SO 4 and HNO 3 in step 1 is 3:1. 3.根据权利要求1所述的一种具有温度荧光响应的聚合物薄膜材料的制备方法，其特征在于：步骤1中所述的碳纳米管为单壁碳纳米管，外径为1～2nm，长度为5～20μm。3. A method for preparing a polymer film material with temperature and fluorescence response according to claim 1, characterized in that: the carbon nanotubes described in step 1 are single-walled carbon nanotubes with an outer diameter of 1 to 2 nm , and the length is 5-20 μm. 4.根据权利要求1所述的一种具有温度荧光响应的聚合物薄膜材料的制备方法，其特征在于：步骤2中所述的酰氯化试剂为氯化亚砜，草酰氯中的至少一种。4. a kind of preparation method with the polymer film material of temperature fluorescence response according to claim 1, is characterized in that: the acyl chloride reagent described in step 2 is sulfur oxychloride, at least one in oxalyl chloride . 5.根据权利要求1所述的一种具有温度荧光响应的聚合物薄膜材料的制备方法，其特征在于：步骤5中所述的聚合物溶液为聚甲基丙烯酸甲酯-环己酮、聚甲基丙烯酸甲酯-丙酮、聚苯乙烯-四氢呋喃、聚苯乙烯-二甲基甲酰胺、聚苯乙烯-氯仿、聚碳酸酯-氯仿、聚碳酸酯-二氯甲烷中的至少一种。5. a kind of preparation method with the polymer film material of temperature fluorescence response according to claim 1, it is characterized in that: the polymer solution described in step 5 is polymethyl methacrylate-cyclohexanone, polymethyl methacrylate At least one of methyl methacrylate-acetone, polystyrene-tetrahydrofuran, polystyrene-dimethylformamide, polystyrene-chloroform, polycarbonate-chloroform, polycarbonate-methylene chloride. 6.一种如权利要求1～5任意一项所述的制备方法制得的具有温度荧光响应的聚合物薄膜材料。6. A polymer film material with temperature fluorescence response prepared by the preparation method according to any one of claims 1-5.
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