WO2004087782A1 - Copolymere de benzene et de benzene substitue - Google Patents

Copolymere de benzene et de benzene substitue Download PDF

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Publication number
WO2004087782A1
WO2004087782A1 PCT/IN2003/000099 IN0300099W WO2004087782A1 WO 2004087782 A1 WO2004087782 A1 WO 2004087782A1 IN 0300099 W IN0300099 W IN 0300099W WO 2004087782 A1 WO2004087782 A1 WO 2004087782A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
benzene
organic solvent
anthracene
aromatic hydrocarbon
Prior art date
Application number
PCT/IN2003/000099
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English (en)
Inventor
Sundeep Kumar Dhawan
Kamalasasan Narayanan Modeeparampu
Sukhwant Singh Bawa
Original Assignee
Council Of Scientific And Industrial Research
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 Council Of Scientific And Industrial Research filed Critical Council Of Scientific And Industrial Research
Priority to AU2003226630A priority Critical patent/AU2003226630A1/en
Priority to PCT/IN2003/000099 priority patent/WO2004087782A1/fr
Publication of WO2004087782A1 publication Critical patent/WO2004087782A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Definitions

  • the present invention relates to a copolymer of benzene and substituted benzenes useful for electroluminescent devices. More particularly tile invention relates to a copolymer of benzene and anthracene as shown in the formula below and a process for the preparation of the said copolymer. Background of the invention
  • organic layers consisting of two layers namely N,N' -Bis(3-methyl phenyl) N,N' diphenylbenzidine (TPD) and aluminum quinolate (Alq3) are used as hole transport layer and emitter layer respectively which are sandwiched between the anode (ITa) and cathode (Aluminum).
  • TPD N,N' -Bis(3-methyl phenyl) N,N' diphenylbenzidine
  • Alq3 aluminum quinolate
  • Both small molecules bases as well as polymer based organic LEOs work on nearly same principles and have nearly the same structure.
  • US Patent, 6,353,082 relates to preparation of fluorine copolymers comprising disubstituted fluorine moieties and two other moieties containing delocalized pi - electrons which leads to making of a polymer light emitting diodes. These copolymers have excellent solubility in common organic solvents. However, the preparation involves first the synthesis of 9,9'-disubstituted 2,7-dibromofluorene at -78°C under nitrogen. The process involves multistage synthesis and the resultant copolymer gives a red LED device.
  • US Patent No. 6,117,529 provides an electroluminescent device made using double stranded poly-p-phenylene (LPPP) with alkylated side chains attached to the matrix.
  • LPPP poly-p-phenylene
  • the process involves multi steps for the preparation of polymer and moreover involves the incorporation of Coumarin 102 dye in the polymethylmethacrylate matrix.
  • US Patent 6,404,126 describes an electro luminescent device containing a light emitting layer containing a conjugated polymer poly phenylenevinylene (PPV) having substituent attached on the phenylene ring, an inorganic insulative electron injecting and transporting layer consisting of lithium oxide, rubidium oxide, potassium oxide etc.
  • PPV conjugated polymer poly phenylenevinylene
  • the patent relates to the development of device using PPV, commercially available and a costly precursor polymer.
  • US Patent No. 5965281 involves the use of substituted polyphenylene vinylene derivative, MEH-PPV (Poly[2methoxy-5(2'-ethylhexyloxyl)-l,4phenylenevinylene) as the polymer for the fabrication of device by incorporating lithium nonylphenoxy ether sulphate as the surfactant additive. This has resulted in the fabrication of LED device with better efficiency, but involves the use of costly monomers and precursor polymers.
  • MEH-PPV Poly[2methoxy-5(2'-ethylhexyloxyl)-l,4phenylenevinylene
  • US Patent No. 5241044 relates to a process for the preparation of soluble poly (p) - phenylenes) by reacting dihydroxy aromatic compounds such as orthoquinone and bisphenols with halogen substituted aliphatic sulphonic acids, halogen sulphonic acids or their anhydrides.
  • the process involves the preparation of the polymer by using zero valence Ni catalyst. By this process poly-phenylenes have been synthesized but its electroluminescence has not been studied.
  • Objects of the invention are examples of the invention.
  • Another object of the present invention is to provide a copolymer useful for light emitting diodes.
  • Another object of the present invention is to provide a copolymer stable up to 380° C.
  • a further object of the present invention is to provide a copolymer capable of being thermally evaporated for thin film formation.
  • Still further object of the invention is to provide a copolymer which is stable in moist environment.
  • Yet further object of the present invention is to provide a copolymer with a shelf life of at least 1 year.
  • Another object of the invention is to provide a copolymer being soluble in common organic solvents like. chloroform, methylene dichloride, benzene, toluene, dimethylformamide, N-methyl pyrrolidinone. Summary of the invention
  • the present invention provides a copolymer of benzene and substituted benzene useful for electrolumininescent devices, said copolymer comprising benzene and an aromatic hydrocarbon in a molar ratio in the range of 1.0 to 0.1, the copolymer being stable up to a temperature of 380° C, is soluble in an organic solvent, is environmentally stable for at least 1 year, and is capable of being thermally evaporated for thin film formation.
  • the aromatic hydrocarbon is selected from a group consisting of anthracene, tetracene and pentacene.
  • the copolymer is used for fabrication of electroluminescent devices.
  • the copolymer dissolved in an organic solvent is capable of being spin coated on electrode surfaces for film formation.
  • the copolymer dissolved in an organic solvent is sprayable on insulating surfaces for use in antistatic applications.
  • the organic solvent is selected from the group consisting of chloroform, methylene chloride, benzene, toluene, dimethylformamide and N-methyl pyrrolidinone.
  • the present invention also relates to a process for the preparation of a copolymer of benzene and an aromatic hydrocarbon, comprising polymerising benzene and the aromatic hydrocarbon in the presence of AIC 3 and CuCI 2 catalyst, filtering the reaction mixture after the completion of the polymerization to obtain the copolymer, washing the copolymer thoroughly and drying the copolymer, the resulting copolymer being stable up to a temperature of 380° C, is soluble in an organic solvent, is environmentally stable for at least 1 year, and is capable of being thermally evaporated for thin film formation.
  • the aromatic hydrocarbon is selected from a group consisting of anthracene, tetracene and pentacene.
  • the copolymer is used for fabrication of electroluminescent devices.
  • the copolymer dissolved in an organic solvent is capable of being spin coated on electrode surfaces for film formation.
  • the copolymer dissolved in an organic solvent is sprayable on insulating surfaces for use in antistatic applications.
  • the organic solvent is selected from the group consisting of chloroform, methylene chloride, benzene, toluene, dimethylformamide and N-methyl pyrrolidinone.
  • the polymerisation is carried out at a temperature in the range of 30-40°C under continuous stirring for a time period in the range of 4-6 hours
  • the temperature of polymerisation is 35°C.
  • the copolymer obtained after filtration is washed with 50 % hot HCI and then with hot distilled water
  • the drying of the washed copolymer is done at a temperature in the range of 50-60°C and under vacuum
  • Formula 1 below represents structure of poly-p-phenylene (a) and the copolymer of benzene and anthracene (b).
  • Figure 1 represents UV-visible solution spectra of copolymer of benzene and anthracene in chloroform, present in the mole ratios 1.0:0.01. The absorption bands observed are 521 nm, 380nm, 319nm and 252nm.
  • Figure 1 represents UV-visible solution spectra of copolymer of benzene and anthracene in chloroform, present in the mole ratios 1.0: 0.05. The absorption bands observed are 518nm, 380nm and 320nm and 250 nm.
  • Figure 1 (curve c) represents UV-visible solution spectra of copolymer of benzene and anthracene in chloroform, present in the mole ratios 1.0:0.1. The absorption bands observed are 480nm, 380nm, 394nm and 280nm.
  • Figure 1 (curve d) represents UV-visible solution spectra of copolymer of benzene and pentacene in N-metyl pyrrolidinone, present in the mole ratios 1.0:0.01.
  • the absorption bands observed are at 741 nm, 453 nm, 332 nm and 288nm.
  • Figure 2 represents FTJR spectra of the copolymer of benzene and anthracene present in the mole ratios of 1.0:0.01.
  • the characteristic peaks observed in the FTLR spectra of the copolymer are 2924,2861,1469,1019,906,808 and 562 cm-1.
  • Figure 3 represents thermogravimetric analysis curve of the copolymer of benzene and anthracene (1.0:0.01). .
  • Figure 3 shows the thermogravimetric analysis curve of the copolymer of benzene and anthracene present in the mole ratios (1.0:0.1).
  • Figure 4 represents the electroluminescence spectrum of the copolymer of benzene and anthracene present in the mole ratios of 1.0:0.01 of the system ITO/copolymer/AI). Detailed description of the invention
  • a copolymer of benzene and substituted benzene, particularly anthracene is disclosed.
  • the copolymer is soluble in common organic solvents like chloroform, methylene dichloride, 'benzene, toluene, dimethylformamide, N-methyl pyrrolidinone etc unlike the parent polymer poly-p-phenylene which is highly insoluble in organic solvents.
  • the copolymer is thermally stable up to 380°C and environmentally stable for at least 1 year.
  • the copolymer is capable of being thermally evaporated useful for elecroluminescent devices.
  • the copolymer shows electroluminescene and is useful in fabrication of an organic light emitting diode device.
  • the present invention provides a copolymer of benzene and substituted benzene useful for electrolumininescent devices which comprises: benzene and aromatic hydrocarbons in molar ratio in a range of 1.0 to 0.1, characterized in that the copolymer is stable up to g temperature of 380° C, is soluble in common organic solvents, environmentally stable for at least 1 year, is capable of being thermally evaporated for thin film formation.
  • the aromatic hydrocarbon is selected from a group consisting of anthracene, tetracene and pentacene.
  • the copolymer is used for fabrication of electroluminescent devices or is capable of spin coating on electrode surfaces for film formation.
  • the copolymer dissolved in organic solvents can also be sprayed on insulating surfaces for use in antistatic applications.
  • the organic solvent may be selected from a group consisting of chloroform, methylene chloride, benzene, toluene, dimethylformamide and N-methyl pyrrolidinone.
  • the copolymer of benzene and benzene substituted polymer preferably anthracene is prepared in the presence of AIC 3 and CuCI 2 catalyst preferably at a temperature of 35°C temperature in the range of 30-40°C continuously stirring the reaction mixture for 4-6 hours, filtering the reaction mixture after the completion of the polymerization, washing thoroughly with 50 % hot HCI and finally with hot distilled water and drying the copolymer at 50-60°C under vacuum.
  • the resulting copolymer is soluble in common organic solvents like chloroform, methylene dichloride, benzene, ethanol, dimethyl formamide (DMF), N-methyl pyrrolidinone (NMP), tetrahydrofuran (THF) and the like.
  • the UV-visible solution spectra of the copolymer of benzene and anthracene present in the mole ratios 1.0:0.01 gives absorption bands at 521 nm, 380 nm, 319 nm and 252 nm. Increasing the concentration of anthracene in the reaction system leads to shift in the absorption bands and decrease in the intensity of the electroluminescent device.
  • the copolymer of benzene with pentacene gives absorption bands at 741 nm, 453 nm, 332 nm and 288nm.
  • the absorption bands in the UV-visible absorption spectra observed for the copolymer are associated with the different transitions of the conjugated aromatic system of the copolymer.
  • the copolymer shows thermal stability up to 140°C and from 140°C to 380°C and from 380°C to 550°C, the copolymer shows weight loss of the order of 18 % (total weight loss 24 %) and 21 % (total weight loss 45 %). This shows that increasing the concentration of anthracene in the reaction system decreases the thermal stability of the copolymer.
  • the copolymer shows electro luminescence and photoluminescence and the device fabricated using above conjugated copolymer shows red electro luminescence.
  • Novelty of the invention is that the copolymer of benzene and benzene substituted polymer is soluble in common organic solvents and is thermally stable up to 380° C.
  • Example 1 Preparation of copolymer of benzene and anthracene:
  • the copolymer is environmentally and thermally stable without any loss in the stability of the copolymer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un copolymère de benzène et de benzène substitué, notamment de l'anthracène. Ledit copolymère est soluble dans des solvants organiques communs tels que le chloroforme, le chlorure de méthylène, le benzène, le toluène, le diméthylformamide, la N-méthyl pyrrolidinone etc., contrairement au polymère parent de poly-p-phénylène qui est hautement insoluble dans des solvants organiques. Ledit copolymère est thermiquement stable jusqu'à 380 °C et écologiquement stable pendant au moins 1 an. Ledit copolymère pouvant être thermiquement évaporé est utile pour des dispositifs électroluminescents. Ledit copolymère est électroluminescent et peut être utilisé dans la fabrication d'un dispositif de diode électroluminescente organique.
PCT/IN2003/000099 2003-03-31 2003-03-31 Copolymere de benzene et de benzene substitue WO2004087782A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003226630A AU2003226630A1 (en) 2003-03-31 2003-03-31 Copolymer of benzine and substituted benzene
PCT/IN2003/000099 WO2004087782A1 (fr) 2003-03-31 2003-03-31 Copolymere de benzene et de benzene substitue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IN2003/000099 WO2004087782A1 (fr) 2003-03-31 2003-03-31 Copolymere de benzene et de benzene substitue

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WO2004087782A1 true WO2004087782A1 (fr) 2004-10-14

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1000679A (en) * 1963-04-11 1965-08-11 Basf Ag Organic polymers for use as electrical semi-conductors
GB1182077A (en) * 1967-09-05 1970-02-25 Hughes Aircraft Co Resinous Composition and Method of Making Same
US3582498A (en) * 1967-09-05 1971-06-01 Hughes Aircraft Co Method of producing solvent soluble fusible polyphenylene polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1000679A (en) * 1963-04-11 1965-08-11 Basf Ag Organic polymers for use as electrical semi-conductors
GB1182077A (en) * 1967-09-05 1970-02-25 Hughes Aircraft Co Resinous Composition and Method of Making Same
US3582498A (en) * 1967-09-05 1971-06-01 Hughes Aircraft Co Method of producing solvent soluble fusible polyphenylene polymers

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CHEMABS CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BERLIN, A.A. ET AL.: "Thermal stability of oligomeric arylenes", XP002269022 *
DATABASE CHEMABS CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BERLIN, A.A. ET AL.: "Thermomechanical study of oligomeric arylenes", XP002269023 *
VYSOKOMOLEKULYARNYE SOEDINENIYA, vol. 12, 1970, pages 2351 - 2361 *
VYSOKOMOLEKULYARNYE SOEDINENIYA, vol. 12, 1970, pages 793 - 795 *

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