Thermal polymerization of arylacetylenes: 2. Study of linear dimers

Gandon, S.; Mison, P.; Sillion, Bernard

doi:10.1016/s0032-3861(97)89718-2

Cited by 12 publications

(5 citation statements)

References 12 publications

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“…In the case of TTF 1 , the first heating DSC curve exhibits a strong and sharp endotherm centered at 149.9 °C, which was unambiguously attributed to the direct melting of the compound into an isotropic fluid by polarized optical microscopy. At higher temperature, a strong and broad exotherm (−58.9 kcal mol –1 ) extending from 225.6 to 271.7 °C and centered at 255.8 °C is also observed and is attributed to an exothermic polymerization of the diacetylenic rod. − The absence of peak on the first cooling curve confirmed that the second process is irreversible. No signals are visible on the second heating process, indicating that all the starting material has been converted into the polymer during the first heating run.…”

Section: Resultsmentioning

confidence: 91%

“…Indeed, enyne derivatives such as diyne structures can undergo polymerization upon thermal treatment. 61 Therefore, the derivatization performed at 90 °C leads to the formation of a multilayered deposit on the Si surface either by the direct grafting of polymeric structures or by additional reaction of TTF 2 with the TTF fragments already grafted onto the Si surface (vide inf ra).…”

Section: Resultsmentioning

confidence: 99%

“…The weaker intensity of the vibration band at 2175 cm –1 can be related to the consumption of the enyne structures during the polymerization process upon light irradiation and heat treatment. Indeed, enyne derivatives such as diyne structures can undergo polymerization upon thermal treatment . Therefore, the derivatization performed at 90 °C leads to the formation of a multilayered deposit on the Si surface either by the direct grafting of polymeric structures or by additional reaction of TTF 2 with the TTF fragments already grafted onto the Si surface ( vide infra ).…”

Section: Resultsmentioning

confidence: 99%

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Controlled Grafting of Tetrathiafulvalene (TTF) Containing Diacetylenic Units on Hydrogen-Terminated Silicon Surfaces: From Redox-Active TTF Monolayer to Polymer Films

et al. 2012

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International audienceA tetrathiafulvalene (TTF)-terminated butadiyne derivative was synthesized and used for the preparation of redox-active TTF-modified hydrogen-terminated oxide-free silicon (Si−H) surfaces. TTF monolayer-modified silicon surfaces were produced when low grafting temperatures were used (typically 45 °C), whereas higher temperatures (90 °C) led to TTF polymer-modified surfaces. IR spectroscopy characterization provided evidence that TTF units bound to the surface through the formation of enyne linkers via hydrosilylation of the terminal alkyne bond. The TTF monolayers prepared at 45 °C were densely packed with a surface coverage of ca. 5.4 × 10−10 mol of TTF per cm2. For such systems, electrochemical measurements showed the redox signature of the bound TTF centers characterized by two reversible one-electron systems at ca. 0.40 and 0.73 V versus saturated calomel electrode (SCE). High values of electron-transfer rate constants were determined (>200 s−1) and ascribed to the presence of the conjugated bridge between the attached redox-active center and the underlying silicon surface. The TTF polymer-modified surfaces prepared at 90 °C resulted from the direct grafting of polymeric structures on Si−H and/or the postattachment functionalization of the preformed TTF monolayer. Polymerization process of the TTF-terminated butadiyne derivative was also investigated in solid state by means of differential scanning calorimetry and diffuse reflectance IR spectroscopy measurements

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Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Controlled Grafting of Tetrathiafulvalene (TTF) Containing Diacetylenic Units on Hydrogen-Terminated Silicon Surfaces: From Redox-Active TTF Monolayer to Polymer Films

et al. 2012

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“…The activation energies of the curing reactions for the PSNP and PSA resins were calculated by DFT to determine if the PSNP resins could be cured at a lower temperature. The dimerization of two alkyne units is the rate-determining step in the curing reactions of the PSNP and PSA resins, such as cyclotrimerization and Diels–Alder reactions (see Figure a). − We, therefore, calculated the activation energies of the dimerization of two alkyne units for the PSNP and PSA resins. The transition states were searched, and the activation energies were obtained (see Figure b).…”

Section: Results and Discussionmentioning

confidence: 99%

Rational Design of Heat-Resistant Polymers with Low Curing Energies by a Materials Genome Approach

et al. 2020

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Designing high-temperature polymers with excellent processability is a long-standing challenge because of the implacable contradiction between high thermal stability and low curing energy. Traditional designs based on scientific intuition and trial-and-error experiments have not been efficient strategies for the discovery of new heat-resistant resins. In this work, we developed a materials genome approach to facilitate the design of new heat-resistant resins with the desired properties. By defining the gene and extracting key features for properties, we proposed a two-step strategy to screen candidate resins obtained from combinations of genes. A new kind of heat-resistant resin was predicted by rapid screening and was further verified by theoretical simulations and experimental studies. The basic framework developed for the present materials genome approach can be generalized for the rapid design of other highperformance materials.

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“…Arylacetylenes were polymerized with Ziegler–Natta catalyst yielding often the cyclotrimer mixture and the polymer with low molecular mass. The polymer/cyclotrimers ratio are dependent on the catalyst, solvent, and the monomer structure 33–35…”

Section: Introductionmentioning

confidence: 99%

Synthesis of poly(p‐methoxyphenylacetylene) with the vanadium acetylacetonate‐aluminum triethyl Ziegler–Natta catalyst system: Cyclotrimers/polymer ratio analysis

Rodriguez

Lafuente

Martı́n-Villamil

2005

J. Polym. Sci. A Polym. Chem.

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Poly(p‐methoxyphenylacetylene) was obtained by the reaction of p‐methoxyphenylacetylene (MOPA) with the vanadium acetylacetonate‐aluminum triethyl V(acac)3‐AlEt3 homogeneous catalyst system. The crude product was always a mixture of 1,2,4‐ and 1,3,5‐tris(p‐methoxyphenyl)benzene and poly(MOPA) of low averaged molecular weight. The 1,2,4‐ and 1,3,5‐cyclotrimers versus poly(MOPA) ratio was analyzed. The poly(MOPA) obtained under different conditions, on the basis of the spectroscopic data, always shows a cis–transoidal stereo‐regular structure. Molecular mass of poly(MOPA) was determined by vapor pressure osmometry, high pressure liquid chromatography (HPLC), and gel permeation chromatography (GPC) techniques. The kinetics of the reaction has been also analyzed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5987–5997, 2005

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Thermal polymerization of arylacetylenes: 2. Study of linear dimers

Cited by 12 publications

References 12 publications

Controlled Grafting of Tetrathiafulvalene (TTF) Containing Diacetylenic Units on Hydrogen-Terminated Silicon Surfaces: From Redox-Active TTF Monolayer to Polymer Films

Controlled Grafting of Tetrathiafulvalene (TTF) Containing Diacetylenic Units on Hydrogen-Terminated Silicon Surfaces: From Redox-Active TTF Monolayer to Polymer Films

Rational Design of Heat-Resistant Polymers with Low Curing Energies by a Materials Genome Approach

Synthesis of poly(p‐methoxyphenylacetylene) with the vanadium acetylacetonate‐aluminum triethyl Ziegler–Natta catalyst system: Cyclotrimers/polymer ratio analysis

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