New Method for Preparation of Poly(phenylene-vinylene) Film

Iwatsuki, Shouji; Kubo, Masataka; Kumeuchi, Toshiyuki

doi:10.1246/cl.1991.1071

Cited by 51 publications

(33 citation statements)

References 4 publications

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“…Examples are the Wessling, [26] sulfinyl, [27][28][29][30][31][32][33][34] sulfonyl, [35,36] xanthate, [37][38][39] dithiocarbamate, [40] Gilch, Heck, [69][70][71][72][73] Suzuki, [74,75] McMurry, [76] ring-opening metathesis, [77,78] acyclic diene metathesis, [79][80][81] Wittig, [82][83][84] Horner-Emmons, [85] Knoevenagel, [86] chemical vapor deposition, [87][88][89][90][91] and electropolymerization [92] methods. By assessing the pros and cons of all these approaches, the Gilch route stands out as one of the most powerful, versatile, and economically efficient approaches: simply by the treatment of a,a 0 -dihalogenated p-xylene derivatives 1 with potassium tert-butoxide (KO t Bu), high-molecular-weight PPVs 2 can be obtained in good to excellent yields (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

The Gilch Synthesis of Poly(p‐phenylene vinylenes): Mechanistic Knowledge in the Service of Advanced Materials

Schwalm

Wiesecke

Immel

et al. 2009

Macromol. Rapid Commun.

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A consistent picture is presented of the mechanistic details and intermediates of the Gilch polymerization leading to poly(p-phenylene vinylenes) (PPVs). In-situ generated p-quinodimethanes are shown to be the real monomers, and spontaneous formation of the initiating radicals is effected by dimerization of some of these monomers to dimer diradicals, the latter also being the reason why significant amounts of [2.2]paracyclophanes are formed as side-products. Chain propagation predominantly proceeds by radical chain growth, occasionally interrupted by polyrecombination events between the growing α,ω-macro-diradicals. Based on this knowledge, oxygen is identified as a very efficient molar-mass regulating agent, and the temporary gelation of the reaction mixtures is interpreted to be the consequence of a very high entanglement of the polymers immediately after their formation. Last but not least, it is rationalized why the usually considered constitutional defects in Gilch PPVs might not be the only and most relevant ones with respect to the efficiency and durability of the organic light emitting devices produced thereof, and why cis-configurated halide-bearing vinylene moieties should be perceived as being among the most critical candidates. These considerations result in the recommendation of straightforward measures that should lead to clearly improved PPVs.

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Section: Introductionmentioning

confidence: 99%

The Gilch Synthesis of Poly(p‐phenylene vinylenes): Mechanistic Knowledge in the Service of Advanced Materials

Schwalm

Wiesecke

Immel

et al. 2009

Macromol. Rapid Commun.

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“…A drawback is the restriction to soluble PPX derivatives and a decrease in molecular weight upon oxidation. It has been shown before that the heterogeneous oxidation of PPX with DDQ is not successful [29]. An additional drawback which has SCHEME 4.…”

Section: Poly(arylene Vinylene)smentioning

confidence: 99%

Design and synthesis of polymers for light-emitting diodes

Greiner

1998

Polym. Adv. Technol.

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Polymers with aromatic ϕ‐conjugated moieties were utilized as electroluminescent materials. In order to meet the requirements for light‐emitting diodes (LED), the design and synthesis of electroluminescent polymers had to be developed and viewed in this review. Focus is on polymers with arylene vinylene, arylene ethinylene, phenylene, thiophene and arylene amine moieties as light‐emitting, hole‐transporting and electron‐transporting materials in LED devices. An attempt has been made to arrange a structural classification of electroluminescent polymers in nonsegmented and segmented polymers. © 1998 John Wiley & Sons, Ltd.

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“…This method does not require the use of solvents and is eas ily compatible with the processes used in the micro In [23], 1,9 dichloro [2,2] paracyclophane was used to prepare the precursor polymer in accordance with the Gorham technique [22]; then, this polymer was annealed in a nitrogen atmosphere and trans formed into PPV. As was shown in [24,25], the pyrol ysis of halo derivatives via the Szwarc method [21] involves dehydrohalogenation and yields the PPV pre cursor.…”

Section: Introductionmentioning

confidence: 99%

Structure and properties of p-phenylenevinylene-p-xylylene copolymers prepared by vapor-deposition polymerization

et al. 2012

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Films based on the p phenylenevinylene-p xylylene precursor are prepared via vapor deposition polymerization during the pyrolysis of α, α' dichloro p xylene on a copper grid in vacuum at substrate tem peratures -196, 25, and 50°C. Subsequent annealing of the precursor at 250°C yields the final material: the copolymer of p phenylenevinylene and p xylylene. The structure, surface morphology, and optical properties of the copolymer are studied at different substrate temperatures and copper amounts in the pyrolysis zone. It is found that p phenylenevinylene units mostly occur in trans configurations. The thermal treatment of the precursor is accompanied by an increase in the mean square surface roughness and a decrease in roughness coefficient α from 0.84 ± 0.05 to 0.79 ± 0.05. As the content of copper in the pyrolysis zone increases, the concentration of p xylylene fragments in the copolymer tends to increase; the band gap increases from -2.5 to 3.1 eV. Depending on synthesis conditions, the copolymer is characterized by a shift of the fluorescence spectrum maximum that achieves 150 nm in the visible spectral region.

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New Method for Preparation of Poly(phenylene-vinylene) Film

Abstract: Poly(phenylene-chloroethylene) film was prepared by the vapor deposition polymerization of 1,9-dichloro[2.2]paracyclophane and was converted into fully extended π-conjugated poly (phenylene-vinylene) by thermal dehydrochlorination at 300 °C under nitrogen for 1 h.

Cited by 51 publications

References 4 publications

The Gilch Synthesis of Poly(p‐phenylene vinylenes): Mechanistic Knowledge in the Service of Advanced Materials

The Gilch Synthesis of Poly(p‐phenylene vinylenes): Mechanistic Knowledge in the Service of Advanced Materials

Design and synthesis of polymers for light-emitting diodes

Structure and properties of p-phenylenevinylene-p-xylylene copolymers prepared by vapor-deposition polymerization

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