Thermal degradation of ladder polymers of diphenylbutadiine

Chauser, M. G.; Cherkashin, Μ. I.; Kushnerev, M.Ya.; Protsuk, T.I.; Берлин, А. А.

doi:10.1016/0032-3950(68)90186-x

Cited by 7 publications

(4 citation statements)

References 5 publications

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“…The groups hanging off the main chain can further react to form a polyacene-like ladder polymer (II). This process is often observed in (liquid or molten) free-radical polymerization, − and not SSTP.…”

Section: Resultsmentioning

confidence: 99%

“…In the literature, two reaction processes are typically used to describe the polymerization of DPB: the 1,2- or 1,4-addition reactions (Scheme S1). ,,,, The 1,2-addition reaction of DPB is asymmetric, where the carbons at the 1 and 2 positions allows for conjugated polymer chains with well-aligned ynyl–phenyl (−CC–Ph) branching (I). The groups hanging off the main chain can further react to form a polyacene-like ladder polymer (II).…”

Section: Resultsmentioning

confidence: 99%

“…The early work on DPB focused on thermal polymerization, , which was also coupled with other conditions including the Ziegler–Natta catalyst ( iso -C4H 9 ) 3 Al–TiCl 4 complex, solvents such as N , N -dimethylformamide and benzene, mild pressures (210 °C and 500 MPa), and gamma irradiation (90 °C) . Most of these studies produced similar results, in which a brown, highly-conjugated DPB oligomer product, soluble in chloroform, was initially formed.…”

Section: Introductionmentioning

confidence: 99%

“…Herein, we report the SSTP of DPB through simple compression of the starting monomers without any additional stimulus (e.g., catalyst, temperature, radiation, templates, or solvents). − The diamond anvil cell (DAC) technique was employed to generate pressures on the gigaPascal (GPa) scale, as described in the Experimental Methods. Well-ordered PDPB was first synthesized at lower pressures near 5 GPa through SSTP, after which a mixed sp 2 /sp 3 nonhexagonally-packed crystalline array was formed upon further compression above 15 GPa.…”

Section: Introductionmentioning

confidence: 99%

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Pressure-Induced Solid-State Polymerization of Optically-Tunable Diphenyl-Substituted Diacetylene

Tang

Strobel

2019

ACS Appl. Polym. Mater.

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Solid-state topochemical polymerization (SSTP) requires well-defined geometries and space symmetries between the starting monomers and resulting polymer, and diacetylenes are excellent precursors, reacting through a 1,4-addition mechanism. The hydrocarbon molecule 1,4-diphenyl-1,3-butadiyne (DPB) has a four-carbon chain with alternating triple/single bonds, capped on each end with a phenyl group, i.e. centrosymmetric with unsaturated π-bonding characteristics. To fully realize its potential for photocatalytic applications, improved control over the assembly process is desirable to form well-ordered poly(diphenylbutadiyne) (PDPB). Here, it is shown that with increasing pressure, DPB undergoes a series of solid-state chemical reactions while maintaining crystalline order related to the starting monomeric structure. Quenchable PDPB compounds begin forming at ca. 5 GPa, which exhibit optically-tunable absorbance and photoluminescence that is controllable through the extent of compression. Above ca. 15 GPa, the system transforms into a nonhexagonally-packed crystalline array with mixed sp2/sp3 character. These stepwise changes with compression are irreversible in nature, as observed by in situ diffraction and spectroscopic methods. For the first time, the simple SSTP synthesis route allows well-aligned DPB molecules to directly transform into a PDPB material via self-assembly solely through pressure generation within a diamond anvil cell without the traditional use of catalysts, temperature, radiation, templates, or solvents.

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