Ligand-Enhanced Aliphatic Carbon−Carbon Bond Activation of Nitroxides by Rhodium(II) Porphyrin
摘要:
Rh(tmp) underwent Ph3P-enhanced aliphatic carbon carbon bond activation with various nitroxides. (Ph3P)Rh(tmp), rapidly formed from Rh(tmp) and Ph3P, enhanced the rate, selectivity, and yield in comparison to Rh(tmp). From kinetic studies, the rate of reaction showed a first-order dependence on both Rh(tmp) and TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) and saturation kinetics on Ph3P. The rate enhancement of (Ph3P)Rh(tmp) over Rh(tmp) was estimated to be about 11 at 70 degrees C.
Ligand-Enhanced Aliphatic Carbon−Carbon Bond Activation of Nitroxides by Rhodium(II) Porphyrin
摘要:
Rh(tmp) underwent Ph3P-enhanced aliphatic carbon carbon bond activation with various nitroxides. (Ph3P)Rh(tmp), rapidly formed from Rh(tmp) and Ph3P, enhanced the rate, selectivity, and yield in comparison to Rh(tmp). From kinetic studies, the rate of reaction showed a first-order dependence on both Rh(tmp) and TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) and saturation kinetics on Ph3P. The rate enhancement of (Ph3P)Rh(tmp) over Rh(tmp) was estimated to be about 11 at 70 degrees C.
PREPARATION OF FUNCTIONALIZED ALKOXYAMINE INITIATOR AND ITS USE
申请人:——
公开号:US20030236368A1
公开(公告)日:2003-12-25
A one-pot process for the preparation of functional alkoxyamines of the general formula (I),
1
is disclosed. The process entails (1) reacting an oxidizing agent with a sterically hindered secondary amine to produce an aqueous phase and a nitroxyl radical (2) removing the aqueous phase and adding to the nitroxyl radical one or more vinyl monomer(s) conforming to a formula and a system which produces free radicals. Also disclosed is a process of polymerizing monomers using the functional alkoxyamine.
In-situ polymerization of monoethylenically unsaturated monomers with secondary amines
申请人:——
公开号:US20040122270A1
公开(公告)日:2004-06-24
A process for the preparation of any of well-defined homopolymers, random and block copolymers is disclosed. The process that entails forming a mixture of monomers, a hindered secondary amine and an oxidizing agent is characterized in the absence of any additional free-radical initiator.
Process for the synthesis for alkoxy amines and their use in controlled radical polymerization
申请人:——
公开号:US20040002606A1
公开(公告)日:2004-01-01
A one-pot process for the preparation of alkoxyamines conforming to formulae (I) or (II), preferably (I)
1
is disclosed. The process entails (1) reacting of an oxidizing agent (A) with a sterically hindered secondary amine of the general formula (III),
2
in a water-containing medium to form a reaction product and an aqueous phase, (2) removing of the aqueous phase, and (3) (adding to the reaction product a free-radical initiator (B) under conditions that promote the decomposition of the initiator to generate free radicals. Also disclosed is a process for polymerizing monomers, the process using the alkoxyamine prepared by the inventive process.
One-pot process for the preparation of functionalized alkoxyamines
申请人:Bayer Aktiengesellschaft
公开号:EP1375457A1
公开(公告)日:2004-01-02
The present invention relates to a new one-pot process for the preparation of functionalized alkoxyamine initiators of the formula (I)
from amines of the formula (II)
and to a process of controlled radical polymerization using the functionalized alkoxyamine as initiators. In the above formulae, R1-R5 have the meanings given in the description.
本发明涉及一种以式(II)胺为原料制备式(I)官能化烷氧胺引发剂的新的一步法工艺
式 (II) 的胺制备功能化烷氧基胺引发剂的新一锅工艺
以及使用功能化烷氧基胺作为引发剂的受控自由基聚合工艺。在上式中,R1-R5 具有说明中给出的含义。
A new process for the synthesis of alkoxyamines active in controlled radical polymerization
申请人:Bayer Aktiengesellschaft
公开号:EP1375476A1
公开(公告)日:2004-01-02
The present invention relates to a new process for the preparation of alkoxyamine initiators and to a process of radical polymerization using the alkoxyamine initiators as intermediates.