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Macromoleculaire ligandstructuren op basis van polyethyleenimine voor kopergekatalyseerde reacties

Lies Bonami UGent (2010)
abstract
In organic and polymer chemistry a catalyst is often used to enhance reaction speed, selectivity and/or make milder reaction condition feasible. Many transition metals possess catalytic properties and are frequently used in organic reactions. The drawback is that a catalyst is not consumed during the reaction and remains unchanged in the product as a contaminant. Especially when using a transition metal complex as a catalyst, even the smallest amount can lead to unwanted characteristics (such as colouring, smell, toxicity,…). Removal of the catalyst is therefore necessary, but not always easy. In this work, a new type of macromolecular ligand structure for a copper catalyst, which retains the activity and selectivity of the homogeneous catalysis and allows a rapid and efficient separation of the catalyst and the product, has been developed. The polyamine poly(ethyleneimine) (PEI) was used as basis for a polymeric ligand for a copper catalyst. To improve the solubility in organic solvents and electronic properties of the macroligands, PEI was alkylated. These modified polyamines could be easily crosslinked into an insoluble network. The polyamine network functions as a solid support as well as a ligand for the copper catalyst. In this way, the use of an inert support material is avoided and a high theoretical loading capacity is achieved. In a second stage, these newly synthesized macroligand structures were combined with Cu(I) and used for two copper catalyzed reaction that are currently frequently used in several domains of polymer chemistry: atom transfer radical polymerization (ATRP) and the copper catalyzed azide-alkyne cycloaddition (CuAAC), an example of the so-called ‘click’ chemistry. For both reactions the homogeneous and heterogeneous catalysis with these Cu(I)/macroligand catalytic complexes have been evaluated. Furthermore, the reusability and efficient removal of the heterogeneous catalyst was examined.
Please use this url to cite or link to this publication:
author
promoter
UGent
organization
alternative title
Macromolecular ligand structures based on poly(ethyleneimine) for copper catalyzed reactions
year
type
dissertation (monograph)
subject
keyword
click chemistry, poly(ethyleneimine), ATRP
pages
IX, 223 pages
publisher
Universiteit Gent. Faculteit Wetenschappen
place of publication
Gent
defense location
Gent : Campus Sterre (S4, auditorium A)
defense date
2010-07-02 15:00
language
Dutch
UGent publication?
yes
classification
D1
copyright statement
I have retained and own the full copyright for this publication
id
1078445
handle
http://hdl.handle.net/1854/LU-1078445
date created
2010-11-23 11:08:09
date last changed
2010-12-15 16:22:55
@phdthesis{1078445,
  abstract     = {In organic and polymer chemistry a catalyst is often used to enhance reaction speed, selectivity and/or make milder reaction condition feasible. Many transition metals possess catalytic properties and are frequently used in organic reactions. The drawback is that a catalyst is not consumed during the reaction and remains unchanged in the product as a contaminant. Especially when using a transition metal complex as a catalyst, even the smallest amount can lead to unwanted characteristics (such as colouring, smell, toxicity,{\textellipsis}). Removal of the catalyst is therefore necessary, but not always easy.
In this work, a new type of macromolecular ligand structure for a copper catalyst, which retains the activity and selectivity of the homogeneous catalysis and allows a rapid and efficient separation of the catalyst and the product, has been developed. The polyamine poly(ethyleneimine) (PEI) was used as basis for a polymeric ligand for a copper catalyst. To improve the solubility in organic solvents and electronic properties of the macroligands, PEI was alkylated. These modified polyamines could be easily crosslinked into an insoluble network. The polyamine network functions as a solid support as well as a ligand for the copper catalyst. In this way, the use of an inert support material is avoided and a high theoretical loading capacity is achieved.
In a second stage, these newly synthesized macroligand structures were combined with Cu(I) and used for two copper catalyzed reaction that are currently frequently used in several domains of polymer chemistry: atom transfer radical polymerization (ATRP) and the copper catalyzed azide-alkyne cycloaddition (CuAAC), an example of the so-called {\textquoteleft}click{\textquoteright} chemistry. For both reactions the homogeneous and heterogeneous catalysis with these Cu(I)/macroligand catalytic complexes have been evaluated. Furthermore, the reusability and efficient removal of the heterogeneous catalyst was examined.},
  author       = {Bonami, Lies},
  keyword      = {click chemistry,poly(ethyleneimine),ATRP},
  language     = {dut},
  pages        = {IX, 223},
  publisher    = {Universiteit Gent. Faculteit Wetenschappen},
  school       = {Ghent University},
  title        = {Macromoleculaire ligandstructuren op basis van polyethyleenimine voor kopergekatalyseerde reacties},
  year         = {2010},
}

Chicago
Bonami, Lies. 2010. “Macromoleculaire Ligandstructuren Op Basis Van Polyethyleenimine Voor Kopergekatalyseerde Reacties”. Gent: Universiteit Gent. Faculteit Wetenschappen.
APA
Bonami, L. (2010). Macromoleculaire ligandstructuren op basis van polyethyleenimine voor kopergekatalyseerde reacties. Universiteit Gent. Faculteit Wetenschappen, Gent.
Vancouver
1.
Bonami L. Macromoleculaire ligandstructuren op basis van polyethyleenimine voor kopergekatalyseerde reacties. [Gent]: Universiteit Gent. Faculteit Wetenschappen; 2010.
MLA
Bonami, Lies. “Macromoleculaire Ligandstructuren Op Basis Van Polyethyleenimine Voor Kopergekatalyseerde Reacties.” 2010 : n. pag. Print.