Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901-7910
11
Iniferter试剂 氮氧自由基 引发剂,催化剂/配体 链转移剂(RAFT试剂)
引发-转移-终止剂法聚合
（Initiator-Transfer agent-Terminator, Iniferter )
G. K. Hamer, Macromolecules 26, 2987 (1993).
10
Iniferter试剂 氮氧自由基
引发-转移-终止剂法聚合
（Initiator-Transfer agent-Terminator, Iniferter )
稳定自由基聚合
（Stable Free Radical Polymerization, SFRP)
Vol. 38, 2121–2136 (2000)
4
Dr. Takayuki Otsu is a Professor Emeritus, Osaka City University. He was born in Osaka in 1929 and received his B.Sc. degree from the Osaka Institute of Science and Technology in 1951. He then was appointed as an instructor at Osaka City University and started his research work on radical polymerization under the late Professor Minoru Imoto.
This being the case, I had an interest in new initiators and their mechanisms, and I focused my attention on the unique reaction behavior of organic sulfur compounds, which have been used as a thiyl radical source, an accelerator, a modifier, a terminator for vinyl or diene polymerization, and an accelerator for vulcanization in the rubber industry.
的实施乙烯基类单体的自由基 聚合，实现聚合物合成设计。
合物的分子量随转化率线性增长，
可合成具有预定结构的嵌段共聚
物。反应条件比较苛刻，工艺复
杂，工业化成本高，单体覆盖面
较窄，分子结构的可设计性较小。
2
Iniferter试剂
引发-转移-终止剂法聚合
（Initiator-Transfer agent-Terminator, Iniferter )
重要的“活性” 自由基聚合方法
3
Iniferter试剂
引发-转移-终止剂法聚合
（Initiator-Transfer agent-Terminator, Iniferter )
重要的“活性” 自由基聚合方法
N O
2,2,6,6-四甲基哌啶氧自由基 (TEMPO)
T. Otsu, J. Polym. Sci. Part A: Polym. Chem.,
引发剂,催化剂/配体
原子转移自由基聚合
（Atom Transfer free Radical Polymerization, ATRP)
引发剂如：
Br OC2H5 2-溴-2-甲基丙酸乙基酯
O
催化剂如：CuBr
溴化亚铜
配体如：
N
N
N
五甲基二乙烯基三胺
Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 1721-1723
In 1954, we began to examine the initiating ability of these compounds in radical polymerization of St and MMA and found in 1956 that various sulfides and disulfides (e.g., phenyl, benzoyl, benzothiazoyl, thiuram, and dithiocarbamate derivatives) could serve as efficient photoinitiators. (Otsu, T. J Polym Sci 1956, 21, 559; Otsu, T.; Nayatani, K.; Muto, I.; Imai, M. Makromol Chem 1958, 27, 142.)
In 1951, I started to work under Professor M. Imoto at Osaka City University, on the radical polymerization of vinyl chloride (VC) with BPO/dimethylaniline as an initiator, and I published two articles on the initiation mechanism in 1955. In those days, two new polymers, high-density polyethyleneand isotactic polypropylene,were discovered with novel initiators, and the initiation mechanism for radical polymerization was also discussed by several workers. In 1953, the definition of block and graft copolymers was clarified by Mark, who emphasized that some physical properties were different from those of random and alternating copolymers. After that, the synthesis of these polymers has been attempted with several methods in which the block copolymer of St and MMA is prepared with polymeric radical initiators and the living polymer discovered by Szwarc in 1956.
活性自由基聚合
自由基聚合
传统的自由基聚合具有单体广泛、 合成工艺多样、操作简便、工业 化成本低等优点,不能控制聚合 物分子的结构和大小，通常聚合 物分子量分布宽。
“活性”自由基聚合
引发速率远大于增长速率，不存 在链终止和链转移，分子量分布
结合两者的长处，可以方便
很(M窄w/，M即n≈具活1)有，性单可聚分控合散制性聚合度，聚
In 1956, he found that polymers derived from thiuram disulfides could induce photopolymerization to give block and graft copolymers. This discovery became the foundation for this highlight. For his work, he was awarded a D.Sc. degree from Osaka University in 1959 and went to the USA to work as a research associate with Professor Carl S. Marvel at the University of Illinois for a year. Then, he returned to Osaka City University and was appointed Associate Professor. In 1965, he accepted the position of Full Professor of Polymer Chemistry and worked there for 26 years.
9
Iniferter试剂 氮氧自由基
重要的“活性” 自由基聚合方法
引发-转移-终止剂法聚合
（Initiator-Transfer agent-Terminator, Iniferter )
稳定自由基聚合
（Stable Free Radical Polymerization, SFRP)
M. K. Georges, R.P.N. Veregin, P. M. Kazmaier, and
After his retirement in 1992, he moved to Kinki University as Professor until his retirement in 1999. The main topics of his research are the various fields of radical polymerization: basic studies of rates and mechanisms, new monomers and initiators, monomer structure–reactivity relationships, controlled polymer syntheses with the iniferter and living radical polymerization techniques. He is the author or coauthor of more than 550 original papers, 120 review articles, 10 books, 30 book chapters, and more than 100 patents. Dr. Otsu was invited abroad to more than 40 International Symposiums, universities, and laboratories to give various lectures. He was also a chairman of the Japanese side of the Japan–China Symposium on Radical Polymerization (now the Asia Polymer Symposium) from 1980 to 1990.