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WO1996036647A1 - Amelioration concernant des materiaux fluorescents - Google Patents

Amelioration concernant des materiaux fluorescents Download PDF

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Publication number
WO1996036647A1
WO1996036647A1 PCT/AU1996/000303 AU9600303W WO9636647A1 WO 1996036647 A1 WO1996036647 A1 WO 1996036647A1 AU 9600303 W AU9600303 W AU 9600303W WO 9636647 A1 WO9636647 A1 WO 9636647A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorescent
dye
polymer composition
solution
fluorescent dye
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.)
Ceased
Application number
PCT/AU1996/000303
Other languages
English (en)
Inventor
Paul Desmond Swift
James Bruce Franklin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Technology Sydney
Skydome Industries Ltd
Original Assignee
University of Technology Sydney
Skydome Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Technology Sydney, Skydome Industries Ltd filed Critical University of Technology Sydney
Priority to EP96913386A priority Critical patent/EP0898583B1/fr
Priority to DE69627205T priority patent/DE69627205T2/de
Priority to AT96913386T priority patent/ATE236197T1/de
Priority to AU56402/96A priority patent/AU717665B2/en
Priority to JP53440296A priority patent/JP3713580B2/ja
Publication of WO1996036647A1 publication Critical patent/WO1996036647A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to improvements in fluorescent materials and, in particular, to a luminescent sunlight collector or solar concentrator that includes a fluorescent dyed polymer composition having improved half-length properties that creates enhanced light emission from a long length of dyed polymer composition in the luminescent sunlight collector.
  • a luminescent sunlight collector or solar concentrator that includes a fluorescent dyed polymer composition having improved half-length properties that creates enhanced light emission from a long length of dyed polymer composition in the luminescent sunlight collector.
  • the red fluorescent dye known by the trade name Lumogen F Red 300 and having the formula perylene-1 , 6,7,12-tetraphenoxy-3, 4, 9,10- tetracarboxylic acid -bis (2',6'-diisopropylanilide), has been incorporated into a poly(methyl methacrylate) (PMMA) polymer to provide sunlight collector sheets for use in solar based illumination of buildings and as fluorescent concentrators for solar cells.
  • PMMA poly(methyl methacrylate)
  • Fluorescent dyes of this type have, however, suffered from the shortcoming that there are light emission losses through various mechanisms, such as from absorption and from scattering in dyed polymer.
  • Losses through absorption include dye based self-absorption due to overlap between the dye's emission and absorption spectra (i.e. insufficient Stokes Shift in the dye molecules), non-radiative absorption by the dye, and absorption by the polymer. Scattering losses are primarily due to inhomogeneities in the polymer from which the collector is fabricated. Sources of scattering include complexes of dye molecules, colloidal particles, crystal boundaries, regional variations in refractive index, bubbles, voids, foreign inclusions (such as dust particles) and surface defects.
  • any type of absorption or scattering will decrease the dyed polymer's half-length.
  • the half-length of a material is the distance over which light generated by fluorescent emission falls by a factor of two.
  • the value of this parameter is a key factor in the suitability of a dyed material for making a luminescent sunlight collector. This is because any material in a luminescent sunlight collector located more than one half-length from the point at which fluorescent light is taken out of the system (usually through the sheet's edges) makes only a small contribution to the collector's output.
  • the material's half-length limits the maximum useful size of a luminescent sunlight collector and hence the maximum luminous output.
  • a process for preparing a fluorescent dyed polymer composition useful in a luminescent sunlight collector comprising dissolving by means of ultrasonic agitation a fluorescent dye in a solution of mono(methyl methacrylate) or partially polymerised methyl methacrylate, so that in the presence of a sufficient quantity of an organic peroxide initiator added either before, during or after the dissolution of the fluorescent dye in the solution, and at a sufficient temperature, polymerisation is initiated so as to produce the fluorescent dyed polymer composition without the formation of voids or bubbles.
  • the fluorescent dye is a perylene dye or a napthalimide dye of a type that is useful for luminescent sunlight collectors or solar concentrators.
  • these dyes are the red fluorescent dye, known by the trade name Lumogen F Red 300 and having the formula perylene-1 ,6,7, 12-tetraphenoxy-3, 4,9, 10-tetracarboxylic acid - bis (2',6'-diisopropylanilide), the green fluorescent dye (sometimes called a "yellow” dye), known by the trade name Lumogen F Yellow 083, and having the formula isobutyl 4,10-dicyanoperylene-3,9-dicarboxylate, the violet/blue fluorescent dye, known by the trade name Lumogen F Violet 570, and having the formula 4,5-dimethyloxy-N-(2-ethyl hexyl) napthalimide, and the orange fluorescent dye, known by the trade name Lumogen F 240, and having the formula perylene-3, 4,9, 1 1 -tetracarboxylic acid bis-(2'6'-diisopropylanilide).
  • the red fluorescent dye known by the trade name Lumogen F Red 300 and
  • the dye is dissolved in a solution of mono(methyl methacrylate) or partially polymerised methyl methacrylate at a temperature between about 30°C and about 100°C by means of ultrasonic agitation for between about 1 and 5 minutes combined with stirring.
  • a fluorescent dye in the aforementioned process may refer to a mixture of fluorescent dyes considered suitable by persons skilled in the art.
  • Partially polymerised methyl methacrylate solutions may comprise solutions of varying mixtures of mono(methyl methacrylate), di(methylmethacrylate) and possibly small amounts of higher molecular weight methyl methacrylates that a person skilled in the art would appreciate as providing a sufficient starting solution for casting poly- (methyl methacrylate).
  • solutions of partially polymerised methyl methacrylate may be prepared by terminating polymerisation of mono(methyl methacrylate) prior to completion.
  • Advantageous features of utilizing a starting solution of partially polymerised methyl methacrylate in the process of the present invention are that shrinkage of the resulting solidified polymer is reduced and heat production during the polymerisation step of the process of the present invention is reduced.
  • the organic peroxide initiator is an alkyl peroxy ester.
  • a particularly preferred alkyl peroxy ester is t-Butyl Per-(2-Ethyl)
  • Hexanoate also known as TBPEH.
  • an especially advantageous characteristic of the organic peroxide initiator selected for use in the process of the present invention is that it has low cross-linking tendency, so that polymerisation results in a preponderance of linear chain dyed polymer molecules over cross linked chains of dyed polymer molecules.
  • Polymerisation should not result in the formation of voids or bubbles in the resultant fluorescent dyed polymer composition as these may cause unwanted light scattering effects and other diminutions of the half length of the fluorescently emitted light.
  • the organic peroxide initiator may be added to the solution either before, during or after the dissolution of the fluorescent dye in the solution, without adversely affecting the reaction kinetics of the process or the fluorescent dyed polymer composition so produced.
  • the process may further include the step of adding diethylenegiycolbis(allylcarbonate) (DEGBAC).
  • DEGBAC diethylenegiycolbis(allylcarbonate)
  • a fluorescent dyed polymer composition prepared by any of the above mentioned processes.
  • a luminescent sunlight collector comprising a fluorescent dyed polymer composition prepared by any of the abovementioned processes.
  • TPEH t-Butyl Per-(2-Ethyl) Hexanoate
  • the solution was cast in a verticle Teflon (trade mark) tube and then heat treated by immersion in a hot water bath to enable polymerisation to proceed to completion, thereby forming a fluorescent dyed polymer composition that can be used as a luminescent sunlight collector.
  • a fluorescent dyed polymer composition was prepared in accordance with the process conditions described in Example 1 but using the green dye
  • Lumogen F Yellow 083 at a concentration of 0.007% W/W instead of the aforementioned Lumogen F Red 300 dye. (This dye gives green fluorescent emission at the aforementioned concentration.) The half-length of the fluorescent emission of the green Lumogen F Yellow 083 dye incorporated in the luminescent sunlight collector produced as in this
  • Example was found to be about 98cm. This compares favourably with the half-length of 56cm for Lumogen F Yellow 083 dye incorporated in a
  • PMMA based polymer made with standard techniques.
  • Lumogen F Red 300 dye (powder form) was dissolved in mono(methylmethacrylate) (MMA) at 50°C by ultrasonic agitation for about 5 minutes. No solvents were used for dissolution purposes.
  • the Lumogen F Red 300 dye had a final concentration in the solution of about 0.005% W/W.
  • the solution was cast in a verticle Teflon (trade mark) tube and then heat treated by immersion in a hot water bath to cause polymerisation to completion.
  • the half-length of the fluorescent emission of the Lumogen F was cast in a verticle Teflon (trade mark) tube and then heat treated by immersion in a hot water bath to cause polymerisation to completion.
  • Red 300 dye incorporated in a luminescent sunlight collector produced as in this Example was found to be 1 09 cm.
  • a fluorescent composition was prepared in accordance with the process conditions described in Example 3 except that it had final concentrations of about 4% W/W DEGBAC and about 96% W/W MMA.
  • the half-length of fluorescent emission of the Lumogen F Red 300 dye incorporated in such a collector was found to be 93cm.
  • a fluorescent dyed polymer composition was prepared in accordance with the process conditions described in Example 1 but using the green dye Lumogen F Yellow 083 at a concentration of 0.007% W/W instead of the Lumogen F Red 300 dye, and adding DEGBAC in liquid form to the solution by stirring for about 1 minute so that the solution comprised about 96% W/W MMA and 4% W/W DEGBAC.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La préparation d'une composition de polymère colorée avec une substance fluorescente et servant de capteur solaire luminescent consiste à dissoudre, par agitation ultrasonique, un colorant fluorescent dans une solution de méthacrylate de méthyle monomère ou de méthacrylate de méthyle partiellement polymérisé. Une quantité suffisante d'initiateur à base de peroxyde organique est ajoutée avant, pendant ou après la dissolution du colorant fluorescent dans la solution de sorte que, à une température suffisante, la polymérisation soit amorcée pour donner une composition polymère colorée avec une substance fluorescente, sans formation de vides ou de bulles. Lorsqu'elle est coulée de manière appropriée, la composition de polymère colorée avec une substance fluorescente peut servir de capteur solaire luminescent.
PCT/AU1996/000303 1995-05-17 1996-05-17 Amelioration concernant des materiaux fluorescents Ceased WO1996036647A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP96913386A EP0898583B1 (fr) 1996-05-17 1996-05-17 Amelioration concernant des materiaux fluorescents
DE69627205T DE69627205T2 (de) 1996-05-17 1996-05-17 Verbesserungen bei fluoreszierenden materialien
AT96913386T ATE236197T1 (de) 1996-05-17 1996-05-17 Verbesserungen bei fluoreszierenden materialien
AU56402/96A AU717665B2 (en) 1996-05-17 1996-05-17 Improvements in fluorescent materials
JP53440296A JP3713580B2 (ja) 1996-05-17 1996-05-17 蛍光材料の改善

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPN2986A AUPN298695A0 (en) 1995-05-17 1995-05-17 Improvements in fluorescent materials
CA002254740A CA2254740A1 (fr) 1995-05-17 1996-05-17 Amelioration concernant des materiaux fluorescents

Publications (1)

Publication Number Publication Date
WO1996036647A1 true WO1996036647A1 (fr) 1996-11-21

Family

ID=25644955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1996/000303 Ceased WO1996036647A1 (fr) 1995-05-17 1996-05-17 Amelioration concernant des materiaux fluorescents

Country Status (3)

Country Link
AU (1) AUPN298695A0 (fr)
CA (1) CA2254740A1 (fr)
WO (1) WO1996036647A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6312132B1 (en) 2000-09-12 2001-11-06 3M Innovative Properties Company Fluorescent red article and retroreflective article made therefrom
US6572977B1 (en) 2000-09-12 2003-06-03 3M Innovative Properties Company Fluorescent red composition and articles made therefrom
KR20140043741A (ko) * 2011-05-10 2014-04-10 바스프 에스이 신규 색 변환기
WO2017162334A1 (fr) * 2016-03-22 2017-09-28 Technische Universität München Polymérisation de monomères de type michael
US10894845B2 (en) 2016-03-22 2021-01-19 Technische Universität München Polymerization of Michael-type and heterocyclic monomers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0004655A2 (fr) * 1978-04-07 1979-10-17 Hoechst Aktiengesellschaft Utilisation de colorants fluorescents pour l'intensification de la lumière
DE3103936A1 (de) * 1981-02-05 1982-08-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München "einfaerben von transparenten polymermaterialien durch diffusion und ihre anwendung in lichtkonzentrierenden und lichtleitenden systemen"
FR2511840A1 (fr) * 1981-09-02 1983-03-04 Gravisse Philippe Element de couverture pour serres agricoles
DE4142150A1 (de) * 1989-05-26 1993-06-24 Kernforschungsz Karlsruhe Verfahren zur herstellung einer roentgenverstaerkerfolie

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0004655A2 (fr) * 1978-04-07 1979-10-17 Hoechst Aktiengesellschaft Utilisation de colorants fluorescents pour l'intensification de la lumière
DE3103936A1 (de) * 1981-02-05 1982-08-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München "einfaerben von transparenten polymermaterialien durch diffusion und ihre anwendung in lichtkonzentrierenden und lichtleitenden systemen"
FR2511840A1 (fr) * 1981-09-02 1983-03-04 Gravisse Philippe Element de couverture pour serres agricoles
DE4142150A1 (de) * 1989-05-26 1993-06-24 Kernforschungsz Karlsruhe Verfahren zur herstellung einer roentgenverstaerkerfolie

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, C-516, page 83; & JP,A,63 054 465 (ASAHI CHEM IND CO LTD), 8 March 1988. *
PATENT ABSTRACTS OF JAPAN, C-547, page 72; & JP,A,63 175 083 (MITSUI TOATSU CHEM INC), 19 July 1988. *
PATENT ABSTRACTS OF JAPAN, C-963, page 51; & JP,A,04 093 388 (MITSUI TOATSU CHEM INC), 26 March 1992. *
PATENT ABSTRACTS OF JAPAN, E-135, page 77; & JP,A,54 083 365 (HITACHI SEISAKUSHO KK), 7 March 1979. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6312132B1 (en) 2000-09-12 2001-11-06 3M Innovative Properties Company Fluorescent red article and retroreflective article made therefrom
US6572977B1 (en) 2000-09-12 2003-06-03 3M Innovative Properties Company Fluorescent red composition and articles made therefrom
KR20140043741A (ko) * 2011-05-10 2014-04-10 바스프 에스이 신규 색 변환기
KR102047789B1 (ko) * 2011-05-10 2019-11-22 바스프 에스이 신규 색 변환기
WO2017162334A1 (fr) * 2016-03-22 2017-09-28 Technische Universität München Polymérisation de monomères de type michael
CN109071696A (zh) * 2016-03-22 2018-12-21 慕尼黑工业大学 迈克尔型单体的聚合
US10894845B2 (en) 2016-03-22 2021-01-19 Technische Universität München Polymerization of Michael-type and heterocyclic monomers

Also Published As

Publication number Publication date
CA2254740A1 (fr) 1996-11-21
AUPN298695A0 (en) 1995-06-08

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