Detail of "7669-54-7"

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Polymer modification and synthesis using sulfenyl derivatives, 7

Polymer modification and synthesis using sulfenyl derivatives, 7. Mechanism of blocky sequence formation in adducts of benzene- and toluenesulfenyl chlorides with 1,4-polybutadiene. Buchan, Gavin M.; Cameron, G. Gordon; Chishti, S. Asif A. (Dep. Chem., Univ. Aberdeen, Aberdeen, Scot.). Makromol. Chem., 179(6), 1409-17 (English) 1978. CODEN: MACEAK. ISSN: 0025-116X. DOCUMENT TYPE: Journal CA Section: 35 (Synthetic High Polymers) PhSCl (I) [931-59-9] reacts with cis-1,4-polybutadiene (II) [9003-17-2] at 55-60° to give a 50% blocky adduct having a 2-phase morphol. comprising domains of modified units in a matrix of II, similar to that previously obsd. for the adduct of p-MeC6H4SCl (III) [933-00-6] with II. The formation of such a blocky structure can be attributed to the activation of an olefinic bond by interaction with the S atom of an adjacent, previously reacted monomeric unit. Kinetic and model compd. studies on the addns. of I and III to polybutadienes support this explanation. The activating mechanism does not operate during addn. of 2-O2NC6H4SCl [7669-54-7] and 2,4-(O2N)2C6H3SCl [528-76-7], which, therefore, yield adducts with a single-phase morphol.

Polymer modification and synthesis using sulfenyl derivatives

Polymer modification and synthesis using sulfenyl derivatives. 5. Adducts with cis-1,4-polybutadiene. Brydon, Albert; Cameron, G. Gordon; Muir, Robert B. (Dep. Chem., Univ. Aberdeen, Aberdeen, Scot.). Makromol. Chem., 178(6), 1739-44 (English) 1977. CODEN: MACEAK. DOCUMENT TYPE: Journal CA Section: 38 (Elastomers, Including Natural Rubber) P-toluenesulfenyl chloride (I) [933-00-6] readily reacts with cis-1,4-polybutadiene (II), but the electron-withdrawing NO2 groups in 2-nitrobenzenesulfenyl chloride [7669-54-7] and 2,4-dinitrobenzenesulfenyl chloride [528-76-7] slow down the addn. reaction and forcing conditions are required. 2-Nitrobenzenesulfenyl benzoate (III) [39164-10-8] reacts with I readily but only a negligible degree of reaction is achieved with 2,4-dinitrobenzenesulfenyl benzoate [19277-09-9]. The glass-transition temp. of II modified with I and III increases as the degree of satn. increases, owing to the combined effects of loss of unsatn. and the increase in the no. of polar groups along the polymer backbone. I-II adducts have a block-type structure while the III-II adducts have a more random distribution. The tensile strength at break of I-II adducts increases as the degree of satn. increases, reflecting the no. of bulky polar side groups on the polymer backbone.