Technical Field:

This invention relates to the standard luminescent film production method from waste polymers that need high-intensity fluorescent radiation and ultrafast (1-10 ns lifetime) photoluminescence references in fields such as physics, chemistry, optics, photonics, organic-electronics, which can also be used in smart window systems that can generate electricity (organic luminescence light intensifiers) and have the potential to be used in photonic technologies.

State of the Art:

Chemistry, physics, materials science, analytical studies, optical and laser systems, multidisciplinary fields, photonics science, lighting systems such as many universities, Research and Development and industrial organizations need a certified reference material known as high-efficiency and fast-Decaying (fluorescence) <I>, which emits homogeneous light in the calibration method to measure the <I> of a newly produced material or to accurately measure the performance of a laser system. To give examples of these materials, cresyl violet, fluorescein, quinine sulfate, rhodamine 101, rhodamine 6g, rhodamine b, tryptophan and 1-tyrosine can be given as examples of some of them.

[http://www.iss.com/resources/reference/data_tables/FL_Qu antumYieldStandards.html] . The solvents of these reference materials are usually ethanol, methanol, water, cyclohexane, sulfuric acid solution or sodium hydroxide solutions. Most of these solvents, in general (especially rhodamine derivatives), exhibit toxic properties to the environment and living organisms. Water-soluble dyes are also commonly referred to as polluting dyes (Respicio, N.C., Heitz, J.R., 1981. Comparative toxicity of rhodamine B and rhodamine 6Gto the house fly (Musca domesticaL.). Bull. Environ. Contam. Toxicol. 27, 274- 281. https://doi.org/10.1007/BF01611020). In the equation given below, the part defined as known-reference is the chemicals given as an example above, and the reference standard film produced within the scope of this project will be used as an alternative to these chemicals and will be included in the equation below (' known-Reference').

Today, new organic or inorganic materials with photoluminescence are designed and synthesized for different study areas. And the calculation of of each sample has become mandatory for both reporting and potential application areas. For this reason, the use of various reference materials is increasing day by day.

The problems identified in the current technique are as follows;

• Dilute concentrations of references prepared from standard fluorescent chemicals are difficult to prepare and can introduce a margin of error.

• It requires fresh solution preparation for each measurement and is an extra waste of time.

• May include the use of toxic dyes and solvents.

• Their photo-resistance is not always high.

• In addition, the different percent purity of chemicals purchased from different manufacturers breaks the standard. Even 0.1% impurities can cause quenching of fluorescence or a decrease in quantum yield. For this reason, they may introduce errors in the calculation of quantum efficiency in case of their use.

Standard fluorescent chemicals that are commercialized and accepted as reference are available in some international companies. But these chemicals are studied entirely in the solution phase. Since the studies of high-film-phase fluorescent standard films have increased rapidly in the last 10-15 years, there is no commercialized product for measuring fluorescence quantum yields in the film-phase yet. However, it has high potential. Example; Films or solid-state luminescent products developed with quantum dots are developed and used to increase the photosynthesis of plants in the field of agriculture.

As a result, a new technology is needed that allows recycled polymers that can overcome the above disadvantages to be converted into products by a low-cost method, plastic and Perylene paint converted into products to form a compatible film, plastic and Perylene paint converted into products to exhibit high fluorescence efficiency, plastic and Perylene paint converted into products to exhibit high stability, plastic and Perylene paint converted into products to consist of completely organic components and to be environmentally friendly.

Description of the Invention:

This invention is the standard method of luminescent film production method from waste polymers, which can overcome the above-mentioned disadvantages, and its feature is; the conversion of recycled polymers into products by low cost method, the plastic and Perylene paint converted into products form a compatible film, the plastic and Perylene paint converted into products exhibit high fluorescence efficiency, the plastic and Perylene paint converted into products exhibit high stability, the plastic and Perylene paint converted into products consist of completely organic components and it is a new technology that allows the Perylene paint converted into products to be environmentally friendly.

The reference fluorescent films proposed within the scope of the invention will eliminate the need for continuous disposal or repeated solution preparation. It has also been produced by following an environmentally friendly approach by evaluating waste polymers. About 99% of the prototyped film produced is recycled polymer. It is aimed that this product, which can create added value, will turn the increasing waste plastics into an advantage. Waste polymer has been brought into use as a host material. Thanks to this, there is also no need to purchase imported optical resins (such as polystyrene or polyvinyl alcohol).

In this project, a highly efficient (<b >90%) and photo-resistant fluorescent film was produced, which can be an alternative to fluorescent chemicals used as standard reference for measuring photoluminescence quantum yields ( ). The produced film contains a stable and homogeneous dispersion of a fluorescent dye in a host material. The host material, on the other hand, was obtained by recycling (a cheap and easy processing method) of polymer [trade name not given, containing polymethylmethacrylate] (an optically permeable plastic-polymer) which is an industrial waste. Reference fluorescent films have been produced that many universities, research-development units (R&D), chemistry, paint, display and/or lighting technologies may need for <I> measurements. These films allow easy use without pretreatment and can be used over and over again. Many of the chemicals currently used as references are known to be prepared with alkaline aliphatics, halogenated solvents or aqueous sulfuric acid solution. They also require a solution preparation process before each measurement. The reference film produced specifically for this project will meet the needs of many domestic and foreign users due to its reusability, more environmentally friendly and cost-effectiveness.

High <I> fluorescent films produced with the invention;

• Additional sample preparation processes,

• Time spent for solution preparation,

• They do not need toxic or abrasive solvents.

Moreover,

• It provides reusability thanks to its high thermal and optical stability.

• Environmentally and sustainable with the processing of Waste Polymer,

• The production cost is very low.

• In addition, it has photo resistance that can maintain its standard for a long time. Description of the Figures:

The invention will be described with reference to the accompanying figures, so that the features of the invention will be more clearly understood and appreciated, but the purpose of this is not to limit the invention to these certain regulations. On the contrary, it is intended to cover all alternatives, changes and equivalences that can be included in the area of the invention defined by the accompanying claims. The details shown should be understood that they are shown only for the purpose of describing the preferred embodiments of the present invention and are presented in order to provide the most convenient and easily understandable description of both the shaping of methods and the rules and conceptual features of the invention. In these drawings.

Figure 1 A schematic view of the production steps.

Figure 2 A view of the film in daylight and under UV light.

Figure 3 A view of a waste plastic after laser cutting.

Figure 4 A view of the synthesis scheme of PTHE.

Figure 5 Absorption, PL and Photostability test view of the PTHE film.

The figures to help understand the present invention are numbered as indicated in the attached image and are given below along with their names.

Description of References:

10. Processing of waste polymer

20. Synthesis of fluorescent dye

30. Controlled combination of polymer and fluorescent dye and high ensuring an efficient stable green light emission

40. Film production step and optical characterization Description of The Invention:

The production method of the invention is as follows; Processing the waste polymer (10) by mixing the recycled waste plastic in organic solvent in a magnetic stirrer for 12 hours, Perylene-3,4,9,10-tetracarboxylic trahexylester derivative (or PTHE for short), Synthesis of fluorescent dye (20), into the polymer whose homogeneous solution is prepared, The mass concentration of the dye in the polymer from the PTHE stock solution is adjusted by adding 0.1 - 1%, the photoluminescence fading due to the aggregation in the film phase of the low mass perylene dyes is minimized in this way, making Controlled combination of polymer and fluorescent dye and high ensuring an efficient stable green light emission (30), the perylene-polymer solution prepared on a clean 2x2 cm glass, consists of the film production step and optical characterization (40) after 10 re-coatings at a range of 2000 to 3000 rpm/min.

In the Controlled combination of polymer and fluorescent dye and high ensuring an efficient stable green light emission (30), as a result of the optimization obtained, films were produced from 0.5% perylene dye added solution.

In the film production step and optical characterization (40), the findings obtained; <b of the film is 92%. In addition, the photo stability of the film is high as a result of 1.5 hours of photo excitation and the intensity of photoluminescence (PL) taken every second (photostability test).

Detailed Description of The Invention:

Invention; It aims to be an optically permeable host of a recycled plastic and to be a 'super fluorescence reference film' with the fluorescent dye doped into it. The visual of the prototype of the film under sunlight and UV light is shown in Figure-2.

Squared letters “IM” appear in yellow. The filled part under UV light appears to be phosphorescent green. (Figure-2) The steps of the invention are as follows;

1. Processing of waste polymer (recycling step),

2. Synthesis of fluorescent dye,

3. Controlled combination of polymer and fluorescent dye,

4. Film production step and optical characterization.

Details of the steps;

1- Processing of waste polymer:

Recycled waste plastic was laser cut and the waste product was converted as described in Figure-3.

Some product was taken from the plastic and mixed in the organic solvent for 12 hours on a magnetic stirrer.

2- Synthesis of fluorescent dye:

In this study, Perylene-3,4,9,10-tetracarboxylictrahexylester derivative (or PTHE for short) was chosen as a fluorescent dye due to its high thermal, optical and electronic properties as well as its high light absorption ability and high fluorescence quantum efficiency. The synthetic process is briefly described in Figure-4.

Its synthesis and characterization; PTHE was synthesized from the commercial starting material of perylene-3,4,9,10-tetracarboxylicdianhydride (PTCDA) [The synthesis of PTHE has been reported in the relevant literature. However, it is not the final product and there are no reports on its photophysical properties and behavior in the polymer.

L0XV9B-63754-1] Into a lOOmL 2-neck reaction flask 1 g PTCDA, 1.52 mL DBU, 2 mL hexanol and 20 mL of DMF was added, followed by stirring 30' at 80°C in an argon atmosphere. Then, 1 -iodohexane was added and the reaction was completed by stirring at 80°C under reflux for 6 hours. The reaction solution was poured into 200 mL of distilled water and the precipitated solid was filtered in vacuo and washed with distilled water. After drying in an oven, it was purified by column chromatography (SiO2, chloroform). The synthesis efficiency is about 90%. Characterized by 1H-NMR and FTIR.

3 -Controlled combination of polymer and fluorescent dye:

The homogeneous solution was adjusted by adding the dye from the PTHE stock solution to the prepared polymer so that the mass concentration of the dye in the polymer was 0.1 - 1%. Photoluminescence fading due to aggregation in the film phase of low-mass peryl ene dyes was also minimized in this way

As a result of the obtained optimization, films were produced from 0.5% perylene dye added solution.

4-Film production step and optical characterization:

There are many different methods of thin film coatings (such as spin coated or spin coating, dripping, spraying, stripping and dipping). Among them, it is known that the 'spin coated' method creates a more homogeneous film morphology than the others. The perylene-polymer solution prepared on a clean 2x2 cm glass was coated over and over again at a range of 2000 to 3000 rpm/min. The film produced after 10 recoats is shown above (presented in the image under day and UV light). Recycled plastic has the potential to be an optically permeable host and a reference for fluorescence measurements by containing a homogeneous dispersion of a perylene dye. In the findings obtained; <b of the film is 92% (measured with an absolute integrated sphere). In addition, as a result of 1.5 hours of photo excitation and photoluminescence (PL) intensity (photostability test) taken every second, the photo stability of the film was proven to be high. (Figure-5)