On the thermolysis of poly(chloroalkyl methacrylates) and poly(chloroalkyl acrylates): Part 1-Poly(2,2,2-trichloroethyl methacrylate)
Само за регистроване кориснике
1991
Аутори
Popović, IvankaSong, J.
Fischer, Ch.-H.
Katsikas, Lynne
Höhne, G.
Veličković, Jovan S.
Schnabel, W.
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
The thermal degradation of poly(2,2,2-trichloroethyl methacrylate). PTCMA, in the absence and presence of O2 was studied and compared with that of poly(ethyl methacrylate), PEMA. In the absence of O2 the two polymers behaved quite differently. Apart from unzipping, PTCMA became partially insoluble due to intermolecular crosslinking at T < 240°C in contrast to PEMA which remained soluble. At T > 240°C both polymers degraded effectively by depolymerization. O2 prevented crosslinking of PTCMA and retarded unzipping (shift of onset to higher temperature). It was inferred from product analysis that at T < 240°C the thermolysis of PTCMA is initiated by decomposition of pendant groups. Primary bond cleavage at various positions in the side groups, {A figure is presented} results in the formation of free radicals. In the presence of O2, hydrogen abstraction from CH2 groups in the polymer backbone generates carbon centered radicals {A figure is presented} which can be converted into ox...yl radicals {A figure is presented}. The latter can give rise to main-chain scission. Apart from the monomer, the main volatile compounds formed in the presence of O2 are: 2,2,2-trichloroethyl pyruvate, CH3COCOOCH2CCl3 and 2-methyl-oxirane carbonic acid 2,2,2-trichloroethyl ester, {A figure is presented} Mechanisms concerning the initiation of thermolysis of PTCMA are proposed on the basis of the various thermolysis products.
Извор:
Polymer Degradation and Stability, 1991, 32, 3, 265-283Издавач:
- Elsevier Sci Ltd, Oxford
Финансирање / пројекти:
- This work was financially supported by a grant from Hanns-Seidel-Stiftung to J. Song. Additional financial support was obtained by I. Popovi6 and I. Veli6kovi+ from Internationales Bfiro der Kernforschungsanlage Jfilich operating on behalf of 'Bilateral Cooperation between the Federal Republic of Germany and Yugoslavia'. The authors are grateful also to S. Eichgrtin and T. Libera for their assistance in carrying out various experiments. Moreover, thanks are due to Dr Hassan Rezk for various suggestions regarding the completion of this paper. The identification of the thermolysis products was significantly facilitated thanks to Dr M. Stickler and his coworkers, R6hm GmbH, who provided us with an authentic sample.
DOI: 10.1016/0141-3910(91)90001-8
ISSN: 0141-3910
PubMed:
Scopus: 2-s2.0-0025842726
Институција/група
Tehnološko-metalurški fakultetTY - JOUR AU - Popović, Ivanka AU - Song, J. AU - Fischer, Ch.-H. AU - Katsikas, Lynne AU - Höhne, G. AU - Veličković, Jovan S. AU - Schnabel, W. PY - 1991 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/31 AB - The thermal degradation of poly(2,2,2-trichloroethyl methacrylate). PTCMA, in the absence and presence of O2 was studied and compared with that of poly(ethyl methacrylate), PEMA. In the absence of O2 the two polymers behaved quite differently. Apart from unzipping, PTCMA became partially insoluble due to intermolecular crosslinking at T < 240°C in contrast to PEMA which remained soluble. At T > 240°C both polymers degraded effectively by depolymerization. O2 prevented crosslinking of PTCMA and retarded unzipping (shift of onset to higher temperature). It was inferred from product analysis that at T < 240°C the thermolysis of PTCMA is initiated by decomposition of pendant groups. Primary bond cleavage at various positions in the side groups, {A figure is presented} results in the formation of free radicals. In the presence of O2, hydrogen abstraction from CH2 groups in the polymer backbone generates carbon centered radicals {A figure is presented} which can be converted into oxyl radicals {A figure is presented}. The latter can give rise to main-chain scission. Apart from the monomer, the main volatile compounds formed in the presence of O2 are: 2,2,2-trichloroethyl pyruvate, CH3COCOOCH2CCl3 and 2-methyl-oxirane carbonic acid 2,2,2-trichloroethyl ester, {A figure is presented} Mechanisms concerning the initiation of thermolysis of PTCMA are proposed on the basis of the various thermolysis products. PB - Elsevier Sci Ltd, Oxford T2 - Polymer Degradation and Stability T1 - On the thermolysis of poly(chloroalkyl methacrylates) and poly(chloroalkyl acrylates): Part 1-Poly(2,2,2-trichloroethyl methacrylate) EP - 283 IS - 3 SP - 265 VL - 32 DO - 10.1016/0141-3910(91)90001-8 ER -
@article{ author = "Popović, Ivanka and Song, J. and Fischer, Ch.-H. and Katsikas, Lynne and Höhne, G. and Veličković, Jovan S. and Schnabel, W.", year = "1991", abstract = "The thermal degradation of poly(2,2,2-trichloroethyl methacrylate). PTCMA, in the absence and presence of O2 was studied and compared with that of poly(ethyl methacrylate), PEMA. In the absence of O2 the two polymers behaved quite differently. Apart from unzipping, PTCMA became partially insoluble due to intermolecular crosslinking at T < 240°C in contrast to PEMA which remained soluble. At T > 240°C both polymers degraded effectively by depolymerization. O2 prevented crosslinking of PTCMA and retarded unzipping (shift of onset to higher temperature). It was inferred from product analysis that at T < 240°C the thermolysis of PTCMA is initiated by decomposition of pendant groups. Primary bond cleavage at various positions in the side groups, {A figure is presented} results in the formation of free radicals. In the presence of O2, hydrogen abstraction from CH2 groups in the polymer backbone generates carbon centered radicals {A figure is presented} which can be converted into oxyl radicals {A figure is presented}. The latter can give rise to main-chain scission. Apart from the monomer, the main volatile compounds formed in the presence of O2 are: 2,2,2-trichloroethyl pyruvate, CH3COCOOCH2CCl3 and 2-methyl-oxirane carbonic acid 2,2,2-trichloroethyl ester, {A figure is presented} Mechanisms concerning the initiation of thermolysis of PTCMA are proposed on the basis of the various thermolysis products.", publisher = "Elsevier Sci Ltd, Oxford", journal = "Polymer Degradation and Stability", title = "On the thermolysis of poly(chloroalkyl methacrylates) and poly(chloroalkyl acrylates): Part 1-Poly(2,2,2-trichloroethyl methacrylate)", pages = "283-265", number = "3", volume = "32", doi = "10.1016/0141-3910(91)90001-8" }
Popović, I., Song, J., Fischer, Ch.-H., Katsikas, L., Höhne, G., Veličković, J. S.,& Schnabel, W.. (1991). On the thermolysis of poly(chloroalkyl methacrylates) and poly(chloroalkyl acrylates): Part 1-Poly(2,2,2-trichloroethyl methacrylate). in Polymer Degradation and Stability Elsevier Sci Ltd, Oxford., 32(3), 265-283. https://doi.org/10.1016/0141-3910(91)90001-8
Popović I, Song J, Fischer C, Katsikas L, Höhne G, Veličković JS, Schnabel W. On the thermolysis of poly(chloroalkyl methacrylates) and poly(chloroalkyl acrylates): Part 1-Poly(2,2,2-trichloroethyl methacrylate). in Polymer Degradation and Stability. 1991;32(3):265-283. doi:10.1016/0141-3910(91)90001-8 .
Popović, Ivanka, Song, J., Fischer, Ch.-H., Katsikas, Lynne, Höhne, G., Veličković, Jovan S., Schnabel, W., "On the thermolysis of poly(chloroalkyl methacrylates) and poly(chloroalkyl acrylates): Part 1-Poly(2,2,2-trichloroethyl methacrylate)" in Polymer Degradation and Stability, 32, no. 3 (1991):265-283, https://doi.org/10.1016/0141-3910(91)90001-8 . .