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ATRP的引发剂:
磺酰氯：引发快于增长103-104！磺酰自由基间的
双基终止反应很慢！ -
30
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31
硫氰基
异硫氰基
R-I的问题：光敏！热敏！- CuI不稳定！机理复杂3！2
引发剂与单体间要适当匹配！
卤化苄对MMA不适用：慢引发！引发效率低！
匹配：结构相像!引发剂的平衡与聚合链的平衡相近！
Percec V.; Barboiu B. Macromolecules, 1995,28,7970
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2
Developed in 1995：
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3
Results of ATRP:
The logarithmic conversion data, ln([M]0/[M]), plotted against time t, gave straight lines passing through the
The KATRP, for MMA is among the largest ! Methacrylates > Acrylonitrile > Styrenes > Acrylates > (Meth)acrylamides 快引发的引发剂可用分批\慢- 加方式提高引发效率! 33
官能化引发剂：
The polydispersity indexes were smaller (generally lower than 1.3).

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Results of ATRP:
Kato M, Kamigaito M, Sawamoto M,
Higashimura T. Macromolecules, 1995,28,1721
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16
Kinetics of ATRP:
影响Rp的因素！
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Kinetics of ATRP:
Keq的大与小对聚合的影响分析: 聚合速率和可 控性, Keq大时聚合速率不一定快。
Keq的影响因素：
配体 过渡金属 温度 单体
引发剂 溶剂
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Keq（KATRP)影响因素：
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组成与配比： 通常1:1:2
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ATRP的催化剂
铼钌
-铑
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ATRP的催化剂
Cu system RuCl2(PPh3)3/Al(OiPr)3 NiX2(PPh3)3, Ni[C6H3(CH2NMe2)2]Br FeX2(PPh3)2 过渡金属及配体的筛选匹配十分重要！
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CuX的配位剂:
bpy dNbpy
PMDETA
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13
Kinetics of ATRP:
平衡的建立： persistent radical effect
Ch-em. Rev. 2001, 101, 3581-361104
Kc ktR
平衡的建立： 只需要很短的时间，双基终 止占大分子的比例一般低于5%。 在SFRP ATRP中聚合的初始瞬间均需建立平衡 初始添加Cu（II)：降低终- 止比例，缩短平衡时间1！5
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适宜进行 ATRP的单体:
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25
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？
碘代化合物引发，机理复 杂，有些副反应 丙烯酸和甲基丙烯酸单体不适合：
与过渡金属配位 使配体质子化
用能转变成丙烯酸的单体！盐 和酯！
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不适用于ATRP的单体:
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ATRP的引发剂:
alkyl, allyl, & benzyl halides, α-haloesters, αhaloketones, α-halonitriles, sulfonylhalides•
原子转移自由基聚合
Atom Transfer Radical Polymerization (ATRP)
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1
Developed in 1995：
Wang J S, Matyjaszewski K. J Am Chem Soc, 1995,117,5614
Kato M, Kamigaito M, Sawamoto M, Higashimura T. Macromolecules, 1995,28,1721
origin, which shows constant concentrations of the
growing species during the polymerization.
The number-average molecular weights increased in direct proportion to monomer conversion and agreed well with the calculated values based on the assumption that one molecule of the initiators generated one living polymer chain.
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5
Results of ATRP:
-
Percec V.; Barboiu B. Macromolec ules1995,28, 7970
6
Results of ATRP:
1-PhECl/CuCl/bpy 苯乙烯 130度，本体聚合
Wang J S, Matyjaszewski K. J Am Chem Soc, 1995,117,5614
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低价金属用量可 以很低？
低价金属用量要高
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于双基终止的量！22
死链的比例
DCF decreases for slower rates of polymerization (longer t), lower monomer conversion (smaller p), lower targeted DPT, and higher initial monomer concentration (larger [M]0) and for rapidly propagating monomers (lower kt/(kp)2 value).
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Results of ATRP:
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8
Atom Transfer Radical Addition (ATRA)
1-PhECl/CuCl/bpy - 烯
9
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Mechanism of ATRP:
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OTSU曾经的工作:
本质是ATRP!
可控效果差：没 有采用金属络合 物做催化剂：
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