Block and graft copolymers by living ring-opening olefin metathesis polymerization
TL;DR: A review of titanacyclobutane-initiated "living" olefin metathesis polymerization for the preparation of new polymer structures is given in this paper, where the same type of reaction was used to link preformed polymer blocks to give ABA-type triblock copolymers and graft Copolymers.
About: This article is published in Journal of Molecular Catalysis.The article was published on 1991-03-01. It has received 38 citations till now. The article focuses on the topics: Ring-opening metathesis polymerisation & Acyclic diene metathesis.
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TL;DR: A review of living ring-opening metathesis polymerization (ROMP) reactions can be found in this article, along with a discussion of state-of-the-art catalysts for use in living ROMP reactions as well as opportunities for the future.
1,244 citations
515 citations
TL;DR: In this paper, a review of transformation reactions involving living and controlled/living polymerization methods is presented, including step-growth, conventional and controlled free radical, cationic, anionic, group transfer, activated monomer Ziegler-Natta and metathesis reactions.
314 citations
Cites background from "Block and graft copolymers by livin..."
...The first report [172,173] involves changing the mechanism from living metathesis polymerization of cycloalkene to group transfer polymerization of silyl vinyl ether....
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...[172] reported two independent transformation reactions for block copolymer synthesis....
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TL;DR: An overview of the methods developed for different types and generations of metathesis catalysts that are typically used in polymerizations is presented and a 'field guide' of functionalization methods highlighting the factors to be considered when choosing the most appropriate approach is presented.
Abstract: The precise placement of functional groups on the chain-ends of macromolecules is a major focus of polymer research. Most common living polymerization techniques offer specific methods of end-functionalization governed by the active propagating species and the kinetics of the polymerization reaction. Ring-opening metathesis polymerization has established itself as one of the most functional-group-tolerant living polymerization techniques known, but this tolerance has limited the number of available functionalization reactions. Metathesis chemists have therefore been required to develop a variety of end-functionalizations, adapting each of them to the reactivity scheme of the particular catalysts used and the complexity of the group to be attached. This review presents an overview of the methods developed for different types and generations of metathesis catalysts that are typically used in such polymerizations. We also present a 'field guide' of functionalization methods highlighting the factors to be considered when choosing the most appropriate approach.
183 citations
TL;DR: A general method of transformation of living ring-opening metathesis polymerization (ROMP) into controlled/living atom transfer radical polymerization for the preparation of block copolymers is reported in this article.
Abstract: A general method of transformation of living ring-opening metathesis polymerization (ROMP) into controlled/“living” atom transfer radical polymerization (ATRP) is reported for the preparation of block copolymers. For example, the macroinitiators PNB−C6H4−CH2Br (Mn = 30 520, Mw/Mn = 1.09) or PDCPD−C6H4−CH2Br (Mn = 12 100, Mw/Mn = 1.24) were prepared by ROMP of norbornene (NB) or dicyclopentadiene (DCPD) and subsequent Wittig-like reactions with p-(bromomethyl)benzaldehyde. These compounds were used as efficient macroinitiators for homogeneous controlled/“living” ATRP to prepare block copolymers with styrene (St), PNB-b-PSt (Mn = 110 400, Mw/Mn = 1.06) and PDCPD-b-PSt (Mn = 20 100, Mw/Mn = 1.37), and methyl acrylate (MA), PNB-b-PMA (Mn = 85 100, Mw/Mn = 1.07) and PDCPD-b-PMA (Mn = 25 300, Mw/Mn = 1.47).
141 citations
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TL;DR: Mecanisme de la polymerisation par ouverture de cycle, par metathese en presence de ces derives as mentioned in this paper is a common belief in polymerization.
Abstract: Mecanisme de la polymerisation par ouverture de cycle, par metathese en presence de ces derives
311 citations
296 citations
TL;DR: Polymerisation avec le systeme W(CH t Bu)(N Ar) [OCMe(CF 3 ) 2 ] 2, dans le toluene entre −40 et −20 o C
Abstract: Polymerisation avec le systeme W(CH t Bu)(N Ar) [OCMe(CF 3 ) 2 ] 2 , dans le toluene entre −40 et −20 o C
196 citations
76 citations
TL;DR: In this paper, it was shown that the molybdenum catalyst will not react significantly with up to 100 eq of ester functionality during the time of a typical polymerization reaction (approx. 15 m at 25 degs).
Abstract: : Addition of 50-200 eq of norbornene to Mo(CH Superscript t Bu) (NAr) (O Superscript t Bu)2 yields living polymers, Mo?CH(C5H8)CHxCH Superscript t Bu (NAr)(O Superscript t Bu)2 (55% trans), that are stable for days in the absence of water and oxygen with essentially no isomerization of the double bonds in the chain. Addition of benzaldehyde cleaves off the polymer in a Wittig-like reaction to yield polynorbornenens with polydispersities in the range 1.04-1.11. Analogous reactions involving 50-200 eq of endo, endo-5,6-dicarbomethoxynorbornene yields homopolymers with polydispersities in the range 1.11-1.22. Block copolymers containing 50 eq of endo,endo-5,6-dicarbomethoxynorbornene and 200 eq of norbornene prepared by adding one or the other monomer first are virtually identical (polydispersities 1.06 and 1.09 with M sub n 57200 and 59900, respectively). These results suggest that the molybdenum catalyst will not react significantly with up to 100 eq of ester functionality during the time of a typical polymerization reaction (approx. 15 m at 25 degs.).
71 citations