EP3662035A1 - Material for optically doping a polymer substrate - Google Patents
Material for optically doping a polymer substrateInfo
- Publication number
- EP3662035A1 EP3662035A1 EP18762365.7A EP18762365A EP3662035A1 EP 3662035 A1 EP3662035 A1 EP 3662035A1 EP 18762365 A EP18762365 A EP 18762365A EP 3662035 A1 EP3662035 A1 EP 3662035A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- poly
- photoluminescent materials
- concentration
- methyl methacrylate
- weight
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Definitions
- the present invention relates to the field of optically active materials for modifying the spectrum of light passing therethrough.
- These materials usually consist of a polymer matrix in which are incorporated different types of organic luminescent compounds, two types of organic luminescent compounds have respectively an absorption spectrum and an emission spectrum, and the emission spectrum of the one of two types of luminescent organic compounds overlaps the absorption spectrum of the other luminescent organic compound.
- the two spectra corresponding to two curves of intensity of a radiation as a function of the wavelength, have a surface of recovery.
- This phenomenon is known under the name of "luminous cascades" invented by Mr. Philippe Gravisse and finds different applications, especially in the agricultural field or the production of photovoltaic energy.
- the modulation of the spectrum of incident solar light can be, by application of this phenomenon, adapted to optimally match the spectral specificities of the illuminated element (a plant or a photovoltaic cell for example).
- Pigments, or photoluminescent organic compounds generally have insufficient efficiency for use in photovoltaic systems that must have a life of 20 years or more.
- the most commonly used polymer is polyethylene PE, and it is known that the organic pigments are not stable in the PE, not more than a few weeks or months due in particular oxidation phenomena.
- the modulation material comprises a polymer matrix and at least two types of luminescent organic compounds. At least two types of luminescent organic compounds have an absorption spectrum and an emission spectrum respectively, the emission spectrum of one of the at least two types of luminescent organic compounds overlapping the absorption spectrum of the other at least two types of luminescent organic compounds.
- the modulation material further comprises nanoparticles incorporated within said polymer matrix, and said nanoparticles contain said at least two types of luminescent organic compounds.
- This solution of the prior art uses nanoparticles connecting at least two types of organic luminescent compounds whose respective emission and absorption spectra overlap with at least partial overlap.
- the molecules of luminescent organic compounds of the two types would be, according to this patent application, statistically located close to each other, and therefore the phenomenon of resonance energy transfer would be favored by a alleged energy transfer, known as the Fordist type, is commonly known as FRET, acronym for "Fôrster résonance energy transfert", corresponding to a non-radiative energy transfer between two luminescent organic compounds.
- This document proposes a polymer matrix of silicone, poly (ethylene-vinyl acetate) (EVA), polyolefins, poly (methyl methacrylate) (PMMA), polyurethane, polyamide, poly (ethylene tetrafluoroethylene) (ETFE), polytetrafluoroethylene (PTFE) ).
- the nanoparticles proposed are silica nanoparticles, and the luminescent organic compounds are either incorporated inside porous silica or grafted onto the surface of the nanoparticles.
- this document also proposes the use of metal nanoparticles, for example gold or silver, or else nanoparticles made of an organic polymer, for example poly (methyl methacrylate) (PMMA), polyethylene (PE) or else polystyrene (PS).
- PMMA poly (methyl methacrylate)
- PE polyethylene
- PS polystyrene
- the present invention aims to provide an effective and not only theoretical solution to the problem of the accounting of organic photoluminescent dopants with the transparent material in which they are incorporated, and the improvement of the resistance to aging as well as the resistance to light.
- the invention firstly relates to a material for the optical doping of a polymer substrate, characterized in that it consists of particles of poly (methyl methacrylate) and at least two organic photoluminescent materials with a concentration of the solubility limit of the photoluminescent materials in the MMA between 0.1% and 2% by weight.
- said substrate is a polymer excluding PMMA.
- said substrate is a polyolefin or a polyolefin copolymer.
- said substrate is a poly (ethylene-vinyl acetate).
- said material is powdery.
- said material is a colloidal dispersion.
- the material consists of a mixture of poly (methyl methacrylate) and two organic powdery photoluminescent materials.
- it consists of a mixture of at least N kinds of crosslinked poly (methyl methacrylate) each integrating at least M organic photoluminescent materials, M and N being integers, with M + N ⁇ 2.
- it consists of a mixture of at least N kinds of non-crosslinked poly (methyl methacrylate) each integrating at least M organic photoluminescent materials, M and N being integers, with M + N ⁇ 2.
- the particles have an average cross section of between 30 and 500 nanometers.
- the particles have a mean section ⁇ 150 nanometers.
- the particles have a section> 150 nanometers. This solution makes it possible to produce a material in colloidal form that is mainly diffusing.
- the invention also relates to an optically active paint comprising a dopant incorporated in a polyacrylic matrix, characterized in that said dopant consists of poly (methyl methacrylate) and at least two organic photoluminescent materials with a concentration of between 0.1 % and 2% by weight.
- the concentration of said dopant is advantageously between 2 and 8% by weight, the proportion polymer / polyethylene being between 10 and 20%.
- the invention also relates to an optically active extrudable film comprising a dopant incorporated in a polymer matrix, characterized in that said dopant consists of polymer powder and at least two organic photoluminescent materials with a concentration of between 0.1% and 2%. by weight, the concentration of said dopant being ⁇ 5% by weight, the proportion vinyl acetate / ethylene being between 4 and 20%.
- an optically active greenhouse cover characterized in that it consists of an extruded polyethylene-vinyl acetate film incorporating a material consisting of poly (methyl methacrylate) and at least two photoluminescent materials. organic compounds with a concentration of between 0.1% and 2% by weight.
- said film has several layers of which at least one intermediate layer consists of poly (ethylene-vinyl acetate) incorporating a material consisting of poly (methyl methacrylate) and at least two organic photoluminescent materials with a concentration between 0.1% and 2% by weight, the concentration of said dopant being ⁇ 5% by weight, the proportion vinyl acetate / ethylene being between 4 and 20%.
- the invention also relates to a photovoltaic panel comprising an optically active coating characterized in that it consists of a poly (ethylene-vinyl acetate) film incorporating a material consisting of powder of poly (methyl methacrylate) and of at least two organic photoluminescent materials with a concentration of between 0.1% and 2% by weight, said film being disposed between the photovoltaic cell and a transparent coating.
- an optically active coating characterized in that it consists of a poly (ethylene-vinyl acetate) film incorporating a material consisting of powder of poly (methyl methacrylate) and of at least two organic photoluminescent materials with a concentration of between 0.1% and 2% by weight, said film being disposed between the photovoltaic cell and a transparent coating.
- the invention also relates to a method for preparing a material for optical doping of poly (ethylene-vinyl acetate) substrate, characterized in that it consists of a polymer base and at least two organic photoluminescent materials. with a concentration of between 0.1% and 2% by weight.
- said base is poly (methyl methacrylate).
- FIG. 1 represents a first example of size distribution curve of optically active doped latex
- FIG. 2 represents a second example of size distribution curve of the optically active doped latex.
- the size of the nanoparticles is between 30 - 200 nm or 300-500 nm.
- the nanoparticles can be doped with a single optically active molecule: they are called monovalent, or several optically active molecules forming a cascade, and they are then said to be polyvalent.
- the size of the 40-50nm doped particles promotes the luminous transmissibility of the film.
- the resonance of the optically active molecules between them can exalt the effect of light Cascade (conditions of distances between the optically active molecules and active population).
- the first step is to introduce into a reactor:
- the solution thus prepared is degassed by bubbling argon or other inert gas for 20 minutes.
- This first degassed solution is then heated at 70 ° C. with mechanical stirring for 2 hours.
- a second solution is prepared in a flask consisting of:
- the solution thus prepared is degassed by bubbling argon or other inert gas for 10 minutes.
- this second solution is transferred to the first solution under an inert atmosphere.
- the mixture which forms an optically active doped latex having a size distribution shown in FIG. 1 is allowed to cool.
- This doped latex is stable and can then be incorporated as a colloidal dispersion in a polymer matrix, in particular of polyacrylic type, to form an optically active paint.
- the technical effect of this preparation is to significantly improve the stability over time of luminescent materials in a polymer base.
- a process for preparing a material comprising
- An optically active material is then obtained in the form of a colloidal dispersion, having a diffusing character whose size distribution curve of the optically active doped latex is shown in FIG.
- Figure 3 shows the comparison of the lifetime of a dye in two different types of matrices.
- the first type disperse the dye directly into an apolar matrix
- the second type allows to encapsulate the dye first in a polar matrix and then to disperse in an apolar matrix.
- the experiment is performed in a weather-o-meter, which emits light to test the aging process of the dye.
- a luminescent red fluorescent dye is used. Even if the experiment is done with a dye, the result of the lifetime is applicable for several dyes integrated together in the matrix.
- the figure shows the time spent in the device on the horizontal axis and the integration of the normalized absorption between 500 and 600 nm in the vertical axis.
- the triangle curve serves as a reference curve, representing the experimental result of the lifetime of the dye directly dispersed in an apolar film, for example, a matrix EVA 14% VA (copolymer of polyethylene and vinyl acetate, evathane d 'Arkema).
- EVA 14% VA copolymer of polyethylene and vinyl acetate, evathane d 'Arkema
- the dot curve represents the lifetime of the same dye but encapsulated in PMMA particles of about 500 nm size. These particles are then dispersed in the same matrix 14% VA EVA. After spending 200 hours in the weather apparatus, some absorption is lost. But after 400 hours, absorption stabilizes on a plateau. After 1000 hours of intense Xe-Ac light, there is still 66% of the initial absorption.
- the initial concentration of the dye in the PMMA particles must be greater than that initially required for the application.
- the additional dye molecules within the PMMA particles replace the holes left by the portion of the dye molecules migrated to the EVA matrix.
- Dye concentration in PMMA is maximized and set near the solubility limit of the dye in MMA (MMA being the PMMA precursor). In the case of the Lumozzo red fluorescent dye, it is 5g / kg.
- the PMMA particles are doped with a dye of 5% by weight. When these particles are dispersed in the EVA matrix, the EVA matrix contains 0.25% by weight of dye. For the other dyes, it is different according to the solubility of each one.
- the maximum solubility limit is smaller at 2 g / kg.
- the solubility depends on the dye and the solvent. Therefore, the weight concentration limit between 0.1 and 2% in claim 1 is not only a random number, but a specific dye-specific concentration to be taken into account.
- the dye concentration range is derived from the experimental results described above and is therefore a new discovery and is not obvious to those skilled in the art.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1757399A FR3069863B1 (en) | 2017-08-02 | 2017-08-02 | MATERIAL FOR OPTICAL DOPING OF POLYMER SUBSTRATE |
PCT/FR2018/052008 WO2019025742A1 (en) | 2017-08-02 | 2018-08-02 | Material for optically doping a polymer substrate |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3662035A1 true EP3662035A1 (en) | 2020-06-10 |
Family
ID=60765741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18762365.7A Pending EP3662035A1 (en) | 2017-08-02 | 2018-08-02 | Material for optically doping a polymer substrate |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3662035A1 (en) |
CN (1) | CN111417698A (en) |
FR (1) | FR3069863B1 (en) |
WO (1) | WO2019025742A1 (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8724054B2 (en) * | 2009-05-27 | 2014-05-13 | Gary Wayne Jones | High efficiency and long life optical spectrum conversion device and process |
FR2971514B1 (en) * | 2011-02-10 | 2014-12-26 | Photofuel Sas | MATERIAL FOR MODULATING SOLAR LIGHT |
FR2993409B1 (en) * | 2012-07-16 | 2015-04-10 | Physique Du Rayonnement Et De La Lumiere Lab De | OPTICALLY ACTIVE COATING FOR IMPROVING PHOTOSOLAR CONVERSION EFFICIENCY |
FR3016369B1 (en) * | 2014-01-13 | 2016-02-12 | Physique Du Rayonnement Et De La Lumiere Lab De | PROCESS FOR MAKING THE ELECTROMAGNETIC CHARACTERISTICS OF OPTICALLY ACTIVE COMPOSITE MATERIALS PERENNIAL |
-
2017
- 2017-08-02 FR FR1757399A patent/FR3069863B1/en active Active
-
2018
- 2018-08-02 WO PCT/FR2018/052008 patent/WO2019025742A1/en unknown
- 2018-08-02 EP EP18762365.7A patent/EP3662035A1/en active Pending
- 2018-08-02 CN CN201880058864.5A patent/CN111417698A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2019025742A1 (en) | 2019-02-07 |
FR3069863A1 (en) | 2019-02-08 |
CN111417698A (en) | 2020-07-14 |
FR3069863B1 (en) | 2020-07-31 |
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