阅读说明：本技术 一种柔性拉曼增强胶带及其制备方法 (Flexible Raman-enhanced adhesive tape and preparation method thereof ) 是由 黄霞 周升 毛贺毅 王蕾 张玲丽 于 2021-07-16 设计创作，主要内容包括：本发明涉及一种柔性拉曼增强胶带的制备方法,其包括如下步骤：1)胺基化：将洁净的PET膜浸入温度80-90℃的胺液中反应2-6h,取出、洗涤、干燥,获得胺基化PET膜,备用；2)吸附银胶：将步骤1)所得胺基化PET膜浸入银胶溶液中,静置24-48h,即得。本发明柔性拉曼增强胶带具有优异的拉曼增强效应,还具有成本低、制作简单、易运输保存、强度高韧性好等优点。(The invention relates to a preparation method of a flexible Raman-enhanced adhesive tape, which comprises the following steps: 1) amination: immersing the clean PET film into amine liquid at the temperature of 80-90 ℃ for reaction for 2-6h, taking out, washing and drying to obtain an aminated PET film for later use; 2) adsorbing silver colloid: immersing the aminated PET film obtained in the step 1) into a silver colloid solution, and standing for 24-48h to obtain the product. The flexible Raman enhancement adhesive tape has an excellent Raman enhancement effect, and also has the advantages of low cost, simplicity in manufacturing, easiness in transportation and storage, high strength, good toughness and the like.)

1. A preparation method of a flexible Raman-enhanced adhesive tape is characterized by comprising the following steps:

1) amination: immersing the clean PET film into amine liquid at the temperature of 80-90 ℃ for reaction for 2-6h, taking out, washing and drying to obtain an aminated PET film for later use;

2) adsorbing silver colloid: immersing the aminated PET film obtained in the step 1) into a silver colloid solution, and standing for 24-48h to obtain the product.

2. The method for preparing a flexible Raman-enhanced adhesive tape according to claim 1, wherein in the step 1), the amine solution is triethylene tetramine or a mixture of ethylene diamine and dimethyl sulfoxide in a molar ratio of 1-2: 1.

3. The method of preparing a flexible raman reinforced tape according to claim 1 or 2, wherein the silver colloid solution in step 2) is prepared by the following steps: adding 1.2-2.0ml of 1% trisodium citrate dihydrate solution into 0.001-0.002mol/L silver nitrate solution, heating and keeping the solution boiling for 30-50min, stopping heating, and naturally cooling to obtain the silver colloid solution.

4. The method of preparing a flexible raman reinforced tape according to claim 3, wherein in step 1), the clean PET film is obtained by the following pre-treatments: washing the PET film with a water solution of a teepol detergent or a detergent at 50-70 ℃ for 20-30min, then washing with deionized water for 10-20min, then washing with ethyl acetate at 50-70 ℃ for 20-30min, and drying in an oven at 50-70 ℃ to constant weight to obtain the PET film.

5. The method for preparing the flexible Raman-enhanced adhesive tape according to claim 1, wherein 25 to 35ml of saturated N-N dimethylformamide solution of epoxy CYC and 10 to 20ml of dibutyltin dilaurate are uniformly mixed, put into the aminated PET film adsorbed with the silver colloid obtained in step 2) and completely immersed, and stirred and heated in a water bath at 40 to 60 ℃ for 1 to 3 hours to obtain the flexible Raman-enhanced adhesive tape;

or, uniformly mixing 25-35ml of saturated N-N dimethylformamide solution of epoxy CYC and 10-20ml of dibutyltin dilaurate, putting the mixture into the aminated PET film obtained in the step 1), ensuring complete immersion, stirring and heating in water bath at 40-60 ℃ for 1-3h, taking out, cleaning, drying, then immersing in silver colloid solution, and standing for 24-48h to obtain the epoxy resin.

6. A flexible Raman-enhanced adhesive tape produced by the production method according to any one of claims 1 to 5.

Technical Field

The invention belongs to the technical field of adhesive tape preparation, and particularly relates to a flexible Raman-enhanced adhesive tape and a preparation method thereof.

Background

The spectrum technology is widely applied to rapid identification and screening of pollutants as a rapid and efficient detection means, wherein Surface Enhanced Raman Spectroscopy (SERS) is one of spectrum detection technologies, has the characteristics of high sensitivity, less moisture interference, capability of providing near-field enhancement, suitability for researching interface effect and the like, and has remarkable advantages in the aspect of trace nondestructive rapid detection. At present, surface enhanced raman spectroscopy is applied to the rapid detection of organic pollutants such as catalysis, spectroelectrochemistry, sensing, drug residues, antibiotics and the like and heavy metal pollutants. In the research of surface enhanced raman spectroscopy, the preparation of low-cost and high-performance enhanced substrates has been a hot point of research.

The surface enhanced Raman substrate is the core of SERS, and silicon wafers and glass sheets are the most commonly used substrate materials for preparing the SERS substrate, but the rigid characteristics of the silicon wafers and the glass sheets limit the application range of the SERS substrate. In recent years, researchers have been searching for a filter paper surface enhanced raman detection substrate made of a flexible substrate material, and the filter paper substrate has attracted attention in recent years in consideration of low preparation cost of filter paper and flexibility of detection modes. Compared with a silicon or metal film substrate, the filter paper material has wide sources and low cost, and can be cut, curled and folded, and the surface of the filter paper material has a porous structure which is beneficial to uniform distribution of Raman active nano particles to form more surface enhanced detection hot spots. The method can obtain structural information which is not easily obtained by conventional Raman spectroscopy, and is widely used for surface research, adsorption interface surface state research, interface orientation and configuration of biological large and small molecules, conformation research, structural analysis and the like, so that the adsorption orientation, adsorption state change, interface information and the like of a compound on an interface can be effectively analyzed. Therefore, the surface enhanced Raman detection technology based on the flexible substrate is applied to trace tests in more special fields, and a new idea is provided for the application of Raman spectroscopy in actual detection.

The researchers have conducted more intensive research on the SERS substrate with the super-surface structure aiming at the problems of single testing wavelength, difficult preparation, weak signal and the like existing in the conventional SERS substrate. In combination with interaction between different materials and special resonance modes, a plurality of novel SERS substrates based on super surfaces are provided.

In 2013, the Dongxing Wang group obtained a super-surface structure using thin film deposition technology, and experiments showed that the super-surface with the SIOM structure showed an order of magnitude larger enhancement factor than that of glass with silver particles. The research group of sequence Ayas of Bilkent university adopts an electron beam evaporation method to obtain the same similar structure, and realizes the unmarked nano-scale resolution imaging of the biological structure through the surface enhanced Raman scattering effect. Zhiming Jin et al deposited silver particles into the nanogap of a silver substrate to achieve a strong SERS effect, and the subject group where Kai Liu is located also utilized a sputtering deposition method to prepare a super-surface with good absorption properties, but the difference lies in that they deposited metal particles on a flexible substrate, thus greatly improving the practical applicability of the device. Nan Zhang et al obtained a stronger field enhancement phenomenon using a Metal-dielectric-Metal, MDM, structure consisting of randomly distributed Metal particles, and all had strong light trapping capacity (>80%) in the visible to near infrared spectrum (435 nm-1100 nm). In addition, the corresponding results can be further enhanced by the introduction of tiny metal nanoparticles. Zhengqi Liu et al achieve broadband optical absorption by introducing dense and random patterns onto opaque metal films, which is based on excitation of a variety of optical and plasmon resonance modes. The existing substrate has the defects of complex technology, expensive required experimental equipment and raw materials; easy to be damaged and not easy to be stored and carried.

Since the randomly distributed particle film has a certain uncontrollable property in processing, it is not favorable for commercial mass production of the substrate. Meanwhile, considering that the Raman signal enhancement mechanism is based on the principle of local surface plasmon resonance, mainly chemical enhancement and electromagnetic enhancement, the selective preparation of the flexible substrate material realizes the combination of multiple enhancement strong mechanisms, and the SERS substrate with high repeatability and enhancement factors is designed aiming at different research fields, so that the method is the main research direction of the current surface enhanced Raman spectrum analysis.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a flexible Raman-enhanced adhesive tape which has an excellent Raman enhancement effect and has the characteristics of low cost, simplicity in manufacturing, easiness in transportation and storage, high strength, good toughness and the like.

The invention also provides a preparation method of the flexible Raman-enhanced adhesive tape.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a flexible Raman-enhanced adhesive tape comprises the following steps:

1) amination: immersing a clean PET film (polyethylene terephthalate) into amine liquid at the temperature of 80-90 ℃ for reaction for 2-6h, taking out, washing and drying to obtain an aminated PET film for later use;

2) adsorbing silver colloid: immersing the aminated PET film obtained in the step 1) into a silver colloid solution, and standing for 24-48h to obtain the product.

Specifically, in the step 1), the amine solution is triethylene tetramine or is formed by mixing ethylene diamine and dimethyl sulfoxide (DMSO) in a molar ratio of 1-2: 1.

Further, the silver colloid solution in the step 2) is prepared by the following steps: adding 1.2-2.0ml of 1% trisodium citrate dihydrate solution serving as a reducing agent into 0.001-0.002mol/L silver nitrate solution, heating and keeping the solution boiling for 30-50min, stopping heating, and naturally cooling to obtain the silver colloid solution.

Further, in step 1), the clean PET film is obtained by the following pretreatment: washing the PET film with a water solution of a teepol detergent or a detergent with the mass concentration of 0.1% at 50-70 ℃ for 20-30min, then washing with deionized water for 10-20min, then washing with ethyl acetate at 50-70 ℃ for 20-30min, and drying in an oven at 50-70 ℃ to constant weight to obtain the PET film.

In order to obtain a better Raman enhancement effect, preferably, 25-35ml of saturated N-N dimethylformamide (CMF) solution of epoxy CYC and 10-20ml of dibutyltin dilaurate (used for catalytic reaction and surface finish enhancement) are uniformly mixed, put into the aminated PET film adsorbing the silver colloid obtained in the step 2) and completely immersed, and slowly stirred and heated for 1-3 hours in water bath at the temperature of 40-60 ℃ to obtain the Raman enhancement film;

or, uniformly mixing 25-35ml of saturated N-N dimethylformamide solution of epoxy CYC and 10-20ml of dibutyltin dilaurate, putting the mixture into the aminated PET film obtained in the step 1), ensuring complete immersion, stirring and heating in water bath at 40-60 ℃ for 1-3h, taking out, cleaning with methanol, drying (drying at 60 ℃ for 30 min), then immersing in silver colloid solution, and standing for 24-48h to obtain the product.

The epoxy CYC is generated by the reaction of CYC and epichlorohydrin, and the specific steps are as follows: 1mol of CYC, 1mol of epichlorohydrin and 0.2mol of K₂CO₃Putting into a reaction vessel, stirring and mixing, heating to 110 ℃, and continuously reacting for 3 h. And filtering after the reaction is finished, carrying out reduced pressure distillation on the filtrate, adding 50ml of toluene, and continuing reduced pressure distillation to remove residual epichlorohydrin, wherein the distillation substrate light yellow resin-like substance is the product epoxy CYC.

CYC is an abbreviation for cyclic peptide herein, and can be synthesized specifically by reference to the literature (Huang, Xia, Zheng, et al. Synthesis, characterization, and characterization of a novel L-tyrosine-derived polycarbonates for porous biological applications [ J ]. Journal of Applied Polymer Science, 2008.)).

The invention also provides the flexible Raman-enhanced adhesive tape prepared by the preparation method.

The Raman spectrum, as a commonly used material characterization technology, can effectively reflect the structural characteristic information of molecules to be detected, and has the characteristics of non-destructiveness and no need of specially-made samples. However, the signal intensity of a pure raman spectrum is extremely weak, and the sensitivity is not high, which limits the application of the raman spectrum in the aspect of practical analysis and detection. The advent of surface enhanced raman scattering technology has greatly enhanced the molecular signature of raman spectra, making it a detection technology with great potential in the fields of analytical science, surface science, explosives detection and biological detection, and is constantly evolving. The intensity of the enhancement amplitude of the SERS active substrate determines the intensity of a target molecule Raman spectrum signal, and the prior SERS active substrate is mainly divided into a traditional rigid substrate and a novel flexible substrate. Compared with a rigid substrate, the flexible SERS substrate can be subjected to mechanical deformation such as cutting and bending, so that the flexible SERS substrate can be better attached to the surface of an irregular and complex material, is fully combined with target molecules, keeps a certain number of substrate 'hot spots', and maintains excellent Raman enhancement performance. The novel flexible Raman enhancement adhesive tape provided by the invention adopts polyethylene terephthalate (PET) as a main component, has an excellent Raman enhancement effect by a surface amination modification means and silver particle adsorption, and also has the advantages of low cost, simplicity in manufacturing, easiness in transportation and storage. High strength and good toughness.

Compared with the prior art, the invention has the following beneficial effects:

1) the invention can better adapt to the complicated sample surface condition by physical means such as cutting, bending deformation and the like, the target molecules are tightly combined, and the enhancement effect is stable;

2) the existing Raman reinforced adhesive tape is mostly an electrostatic spinning substrate layer, so that hot spot arrangement has certain orientation, and homogeneous detection on the surface of a complex apparatus cannot be carried out; because epoxy CYC has certain adhesiveness, after the surface of the PET film is modified, the surface of the PET film is endowed with certain adhesiveness, so that the PET film can adsorb more target molecules, such as the target molecules can be adsorbed on the surface of a bronze ware, and the evaluation and analysis of the surface corrosion of the bronze ware are facilitated. The adhesive tape can be possibly used for carrying out measurement analysis detection on residual chloride ions on the surface of mineralized bronze, and can change the reaction condition of a substrate layer according to different bronze objects to realize flexible customization of detection;

3) the preparation method adopts silver sol, and realizes the synergistic enhancement effect by the surface modified epoxy CYC and the adsorbed nano silver particles, thereby having the synergistic enhancement effect on trace adsorbates. The adhesive tape has a good Raman enhancement effect.

Description of the drawings:

FIG. 1 is a clean PET film obtained after the pretreatment of step 1) of example 1;

FIG. 2 is an aminated PET film of step 2) of example 1;

FIG. 3 is the silver colloid solution in step 3) of example 1;

FIG. 4 is a photograph of product A1 CYC modified aminated PET obtained from the preparation of example 1;

FIG. 5 is a photograph of product A2 CYC modified aminated PET obtained from the preparation of example 2;

FIG. 6 is a photograph of product A3 CYC modified aminated PET obtained from example 3;

FIG. 7 is a photograph of product A4 CYC modified aminated PET obtained from the preparation of example 4;

fig. 8 is a raman spectrum of the products prepared in examples 1 to 4 using carbon nanotubes as probe molecules.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1

A preparation method of a flexible Raman-enhanced adhesive tape comprises the following steps:

1) pretreatment of a PET film: washing the PET film with a water solution of a tepol detergent with the mass concentration of 0.1% at 60 ℃ for 30min, then washing with deionized water for 10min, then washing with ethyl acetate at 60 ℃ for 30min, and drying in a 60 ℃ oven to constant weight to obtain a clean PET film (see figure 1);

2) amination: soaking the clean PET film in amine solution at 85 deg.C for 2h, taking out, washing with methanol for 90min, and drying at 60 deg.C for 30min to obtain aminated PET film (see FIG. 2); the amine liquid is formed by mixing ethylenediamine and dimethyl sulfoxide in a molar ratio of 1: 1;

3) adsorbing silver colloid: immersing the aminated PET film obtained in the step 2) into a silver colloid solution (the silver colloid solution is prepared by the following steps: diluting 0.01 mol/L10 ml silver nitrate standard solution with deionized water to 100ml, slowly dripping 1.6ml trisodium citrate dihydrate solution with mass fraction of 1%, heating and keeping the solution boiling for 40min, stopping heating, naturally cooling to obtain silver colloid solution, see figure 3), standing for 24h,

4) and (3) uniformly stirring 30ml of saturated N-N dimethylformamide solution of epoxy CYC and 15ml of dibutyltin dilaurate, putting the aminated PET film adsorbed with the silver colloid obtained in the step 3), completely immersing the aminated PET film, and slowly stirring and heating for 2 hours in a water bath at 50 ℃ to obtain the CYC modified aminated PET. The product obtained was designated A1 (see FIG. 4).

Example 2

The difference from the embodiment 1 is that: the amine liquid is triethylene tetramine. The product obtained was designated A2 (see FIG. 5).

Example 3

The difference from the example 1 is that 0.02mol/L silver nitrate standard solution is used in the step 3). The product obtained was designated A3 (see FIG. 6).

Example 4

The difference from the embodiment 1 is that: the amine liquid is triethylene tetramine; and step 3) and step 4) are exchanged in sequence. The product obtained was designated A4 (see FIG. 7).

Example 5

The difference from the example 1 is that the reaction time in the amine solution in the step 2) is 4 h.

Example 6

The difference from the example 1 is that the reaction time in the amine solution in the step 2) is 6 h.

Application test

In order to verify the difference of the actual raman enhancement effect of the samples under different preparation conditions, the prepared samples, namely A1, A2, A3 and A4, and the blank group (aminated PET, namely only step 1) and step 2)) are paved with a layer of carbon nanotubes on the surface of the sample, and data acquisition is carried out by using a raman spectrometer with the set laser wavelength of 532 nm.

The carbon nano tube has four obvious characteristic peaks in a Raman spectrum and is an advantageous material for Raman analysis. The raman spectrum observed with carbon nanotubes as probe molecules is shown in fig. 8. As can be seen in fig. 8: four characteristic peaks were observed. At 1580 cm^-1Nearby and 1350 cm^-1The nearby peaks are generally called G peak and D peak, wherein the G peak is the representation of the order degree in the carbon nanotube, and the D peak is the reflection of the disorder degree and the defect in the carbon nanotube, 2670 cm^-1Nearby 2D peak, 2910 cm^-1The vicinity is a D + G peak. The raman enhancing effect was examined by using the D peak as a representative, and the results are shown in table 1.

TABLE 1D-Peak Strength and fold relation of the products obtained in the different examples

In table 1, taking the D peak with the highest peak intensity as an example, the peak intensities of the samples are arranged in order of a2, A3, a4 and a1 from large to small. The peak intensity of a2 was 5.45 times, the peak intensity of A3 was 3.76 times, the peak intensity of a4 was 3.62 times, and the peak intensity of a1 was 3.59 times, all based on the D peak intensity of the aminated PET blank 297. The fold relation ratio can provide a basis for the difference of SERS performances.

The comprehensive analysis shows that: the A2 group has the best Raman enhancement performance, and the other groups have similar Raman enhancement performance, and have better Raman enhancement effect compared with the blank group. The flexible Raman enhancement adhesive tape has an excellent Raman enhancement effect, and also has the advantages of low cost, simplicity in manufacturing, easiness in transportation and storage, high strength, good toughness and the like.