Abstract
Polymerization reactions of α,α + ′-bis(tetrahydrothiophenio)-p-xylene dichlorides with OH in H2O have been studied kinetically. The reactions proceeded via the α-tetrahydrothiophenio-p-xylylene intermediates. Results of the H-D exchange experiments and kinetic studies reveal that the 1,6-elimination forming the intermediates proceeds reversibly via the ylide intermediate. The observed rate of disappearance of the intermediate was increased by the addition of OH-, tetrahydrothiophene, and S2O82- as well as by the photoirradiation with a tungsten lamp in the presence of Rose Bengal and was inhibited by TEMPO. However, the rate was found to be independent of ylide concentration. From these results, an elimination-free radical polymerization mechanism is proposed. The microscopic rate constants for each step of this mechanism were calculated from the change in the intermediate concentration with time. All of the rate data showed excellent correlations with the substituent constants in the Hammett plot.
| Original language | English |
|---|---|
| Pages (from-to) | 2098-2106 |
| Number of pages | 9 |
| Journal | Macromolecules |
| Volume | 31 |
| Issue number | 7 |
| Publication status | Published - 1998 Apr 7 |
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- Materials Chemistry
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Kinetics of polymerization reaction of α,α + ′-bis(tetrahydrothiophenio)-p-xylene dichloride. / Cho, Bong-Rae; Kim, Yong Kwan; Han, Man S.
In: Macromolecules, Vol. 31, No. 7, 07.04.1998, p. 2098-2106.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Kinetics of polymerization reaction of α,α + ′-bis(tetrahydrothiophenio)-p-xylene dichloride
AU - Cho, Bong-Rae
AU - Kim, Yong Kwan
AU - Han, Man S.
PY - 1998/4/7
Y1 - 1998/4/7
N2 - Polymerization reactions of α,α + ′-bis(tetrahydrothiophenio)-p-xylene dichlorides with OH in H2O have been studied kinetically. The reactions proceeded via the α-tetrahydrothiophenio-p-xylylene intermediates. Results of the H-D exchange experiments and kinetic studies reveal that the 1,6-elimination forming the intermediates proceeds reversibly via the ylide intermediate. The observed rate of disappearance of the intermediate was increased by the addition of OH-, tetrahydrothiophene, and S2O82- as well as by the photoirradiation with a tungsten lamp in the presence of Rose Bengal and was inhibited by TEMPO. However, the rate was found to be independent of ylide concentration. From these results, an elimination-free radical polymerization mechanism is proposed. The microscopic rate constants for each step of this mechanism were calculated from the change in the intermediate concentration with time. All of the rate data showed excellent correlations with the substituent constants in the Hammett plot.
AB - Polymerization reactions of α,α + ′-bis(tetrahydrothiophenio)-p-xylene dichlorides with OH in H2O have been studied kinetically. The reactions proceeded via the α-tetrahydrothiophenio-p-xylylene intermediates. Results of the H-D exchange experiments and kinetic studies reveal that the 1,6-elimination forming the intermediates proceeds reversibly via the ylide intermediate. The observed rate of disappearance of the intermediate was increased by the addition of OH-, tetrahydrothiophene, and S2O82- as well as by the photoirradiation with a tungsten lamp in the presence of Rose Bengal and was inhibited by TEMPO. However, the rate was found to be independent of ylide concentration. From these results, an elimination-free radical polymerization mechanism is proposed. The microscopic rate constants for each step of this mechanism were calculated from the change in the intermediate concentration with time. All of the rate data showed excellent correlations with the substituent constants in the Hammett plot.
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M3 - Article
AN - SCOPUS:0032492519
VL - 31
SP - 2098
EP - 2106
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 7
ER -