|
|
|
|
| LEADER |
01000naa a22002652 4500 |
| 001 |
NLM341704040 |
| 003 |
DE-627 |
| 005 |
20231226012401.0 |
| 007 |
cr uuu---uuuuu |
| 008 |
231226s2022 xx |||||o 00| ||eng c |
| 024 |
7 |
|
|a 10.1002/jcc.26943
|2 doi
|
| 028 |
5 |
2 |
|a pubmed24n1138.xml
|
| 035 |
|
|
|a (DE-627)NLM341704040
|
| 035 |
|
|
|a (NLM)35648394
|
| 040 |
|
|
|a DE-627
|b ger
|c DE-627
|e rakwb
|
| 041 |
|
|
|a eng
|
| 100 |
1 |
|
|a Abdullayev, Yusif
|e verfasserin
|4 aut
|
| 245 |
1 |
0 |
|a Computational mechanistic studies on persulfate assisted p-phenylenediamine polymerization
|
| 264 |
|
1 |
|c 2022
|
| 336 |
|
|
|a Text
|b txt
|2 rdacontent
|
| 337 |
|
|
|a ƒaComputermedien
|b c
|2 rdamedia
|
| 338 |
|
|
|a ƒa Online-Ressource
|b cr
|2 rdacarrier
|
| 500 |
|
|
|a Date Revised 13.06.2023
|
| 500 |
|
|
|a published: Print-Electronic
|
| 500 |
|
|
|a Citation Status PubMed-not-MEDLINE
|
| 520 |
|
|
|a © 2022 Wiley Periodicals LLC.
|
| 520 |
|
|
|a p-Phenylenediamine (p-PDA) is a monomer of many important polymers such as kevlar, twaron, poly-p-PDA. Most of the noticed polymers formation is initiated by a free-radical, but their polymerization mechanism is not elucidated computationally. The proposed study helps to fully understand the frequently utilized initiator/oxidant, potassium persulfate (K2 S2 O8 ) role in the aromatic diamines polymerization, which support experimental protocols, and a polymer scope. The formation of the poly-p-PDA is studied with the density functional theory (DFT) B3LYP-D3 functional using experimental polymerization parameters (0°C and aqueous media). K2 S2 O8 initiated free-radical polymerization of p-PDA is studied in detail, taking into account sulfate free-radical (SO4 - )· , SFR, persulfate anion (S2 O8 )2- , PA and K2 S2 O8 cluster, PP. The reaction mechanism is calculated as the conversion of p-PDA to free-radical, the p-PDA free-radical attack to the next p-PDA (dimerization), ammonia extrusion from the dimer adduct, the dimer adduct conversion to the free-radical (completion of p-PDA polymerization cycle) for the polymer chain elongation. Calculations show that the dimerization step is the rate-limiting step with a 29.2 kcal/mol energy barrier when SFR initiates polymerization. In contrast, the PA-assisted dimerization energy barrier is only 12.7 kcal/mol. PP supported polymerization is calculated to have very shallow energy barriers completing the polymerization cycle, i.e., dimerization (TS2K, ∆G‡ = 11.6 kcal/mol) and ammonia extrusion (TS3K, ∆G‡ = 6.7 kcal/mol)
|
| 650 |
|
4 |
|a Journal Article
|
| 650 |
|
4 |
|a DFT
|
| 650 |
|
4 |
|a energy barrier
|
| 650 |
|
4 |
|a noncovalent interaction
|
| 650 |
|
4 |
|a p-phenylenediamine
|
| 650 |
|
4 |
|a polymerization
|
| 650 |
|
4 |
|a potassium persulfate
|
| 650 |
|
4 |
|a transition state
|
| 700 |
1 |
|
|a Rzayev, Ramil
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Autschbach, Jochen
|e verfasserin
|4 aut
|
| 773 |
0 |
8 |
|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 43(2022), 19 vom: 15. Juli, Seite 1313-1319
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
|
| 773 |
1 |
8 |
|g volume:43
|g year:2022
|g number:19
|g day:15
|g month:07
|g pages:1313-1319
|
| 856 |
4 |
0 |
|u http://dx.doi.org/10.1002/jcc.26943
|3 Volltext
|
| 912 |
|
|
|a GBV_USEFLAG_A
|
| 912 |
|
|
|a SYSFLAG_A
|
| 912 |
|
|
|a GBV_NLM
|
| 912 |
|
|
|a GBV_ILN_350
|
| 951 |
|
|
|a AR
|
| 952 |
|
|
|d 43
|j 2022
|e 19
|b 15
|c 07
|h 1313-1319
|