Peroxy radicals as motional probes at the end of isolated polystyrene chains and on the cellulose surfaces in vacuum
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- 作者：Toshiyuki Motokawa ; Masakazu Makino ; Masato Sakaguchi
- 关键词：Peroxy radical ; Mechanochemical polymerization ; Motional probe ; Isolated polystyrene chain ; Cellulose ; Surface of cellulose
- 刊名：Cellulose
- 出版年：2016
- 出版时间：April 2016
- 年：2016
- 卷：23
- 期：2
- 页码：1123-1135
- 全文大小：1,058 KB
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Masakazu Makino (2)
Masato Sakaguchi (2)
1. Corporate Engineering Center, Corporate Production Management and Engineering Division, Sumitomo Bakelite Co., Ltd., 2100, Takayanagi, Fujieda, Shizuoka, 426-0041, Japan
2. Department of Food and Nutritional Sciences, Graduate School of Nutritional and Environmental Sciences, University of Shizuoka, 52 Yada, Suruga-ku, Shizuoka, 422-8526, Japan - 刊物类别：Chemistry and Materials Science
- 刊物主题：Chemistry
Bioorganic Chemistry
Physical Chemistry
Organic Chemistry
Polymer Sciences - 出版者：Springer Netherlands
- ISSN：1572-882X
文摘
The isolated polystyrene chains spin-labeled with peroxide radical at the free end (IPSOO) in which the chain roots were covalently bonded to the surface of microcrystalline cellulose (MCC) powder were produced by mechanochemical polymerization of styrene initiated by MCC mechanoradicals. The IPSOO was used as motional probes at the ends of isolated polystyrene chains tethered on the surface of MCC powder. Two modes for the molecular motion of IPSOO were observed. One was a tumbling motion of IPSOO on the MCC surface, defined as a train state, and another was a free rotational motion of IPSOO protruding out from the MCC surface, defined as a tail state. The temperature of tumbling motion (T tum ) of IPSOO at the train state was at 90 K with anisotropic correlation times. T tum (90 K) is extremely low compared to the glass transition temperature (T g b ; 373 K) of polystyrene in the bulk. At temperatures above 219 K, the IPSOO was protruded out from the MCC surface, and freely rotated at the tail state. The train–tail transition temperature (T train–tail ) was estimated to be 222 K. T tum (90 K) and T train–tail (222 K) are due to the extremely low chain segmental density of IPSOO on the MCC surface under vacuum. The interaction between IPSOO and the MCC surface is a minor contributing factor in the mobility of IPSOO on the surface under vacuum. It was found that peroxy radicals are useful probes to characterize the chain mobility reflecting their environmental conditions.