scholarly journals Olefin metathesis in multiblock copolymer synthesis

2019 ◽  
Vol 15 ◽  
pp. 218-235 ◽  
Author(s):  
Maria L Gringolts ◽  
Yulia I Denisova ◽  
Eugene Sh Finkelshtein ◽  
Yaroslav V Kudryavtsev
Keyword(s):  
Olefin Metathesis ◽  
Ring Opening ◽  
Mechanical Characteristics ◽  
Multiblock Copolymers ◽  
Structure Property ◽  
Practical Applications ◽  
Property Relations ◽  
Multiblock Copolymer ◽  
Cross Metathesis ◽  
Synthetic Approaches

Multiblock copolymers constitute a basis for an emerging class of nanomaterials that combine various functional properties with durability and enhanced mechanical characteristics. Our mini-review addresses synthetic approaches to the design of multiblock copolymers from unsaturated monomers and polymers using olefin metathesis reactions and other ways of chemical modification across double C=C bonds. The main techniques, actively developed during the last decade and discussed here, are the coupling of end-functionalized blocks, sequential ring-opening metathesis polymerization, and cross metathesis between unsaturated polymers, or macromolecular cross metathesis. The last topic attracts special interest due to its relative simplicity and broad opportunities to tailor the structure and hence the properties of the copolymer products. Whenever possible, we analyze the structure–property relations for multiblock copolymers and point to their possible practical applications.

scholarly journals Multiblock Copolymers of Norbornene and Cyclododecene: Chain Structure and Properties

Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1756
Author(s):  
Yulia I. Denisova ◽  
Georgiy A. Shandryuk ◽  
Marianna P. Arinina ◽  
Ivan S. Levin ◽  
Vsevolod A. Zhigarev ◽  
...  
Keyword(s):  
First Generation ◽  
Average Length ◽  
Chain Structure ◽  
Random Copolymers ◽  
Multiblock Copolymers ◽  
Structure Property ◽  
Reaction Conditions ◽  
Property Relations ◽  
Cross Metathesis

We investigate the structure–property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state.

scholarly journals Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

2019 ◽  
Vol 15 ◽  
pp. 310-332 ◽  
Author(s):  
Patrycja Żak ◽  
Cezary Pietraszuk
Keyword(s):  
Olefin Metathesis ◽  
Ring Opening ◽  
Polymeric Materials ◽  
Acyclic Diene Metathesis ◽  
Polyhedral Oligomeric Silsesquioxanes ◽  
Ring Opening Metathesis Polymerization ◽  
Metathesis Polymerization ◽  
Cross Metathesis ◽  
Terminal Olefins ◽  
Synthesized Materials

This mini-review summarizes the applications of olefin metathesis in synthesis and functionalization of polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials. Three types of processes, i.e., cross metathesis (CM) of vinyl-substituted POSS with terminal olefins, acyclic diene metathesis (ADMET) copolymerization of divinyl-substituted POSS with α,ω-dienes and ring-opening metathesis polymerization (ROMP) of POSS-substituted norbornene (or other ROMP susceptible cycloolefins) are discussed. Emphasis was put on the synthetic and catalytic aspects rather than on the properties and applications of synthesized materials.

scholarly journals Light-induced olefin metathesis

2010 ◽  
Vol 6 ◽  
pp. 1106-1119 ◽  
Author(s):  
Yuval Vidavsky ◽  
N Gabriel Lemcoff
Keyword(s):  
Olefin Metathesis ◽  
Ring Opening ◽  
Relevant Literature ◽  
Desirable Property ◽  
Light Activation ◽  
Light Olefin ◽  
Cross Metathesis ◽  
Metathesis Reactions ◽  
Catalytic Processes ◽  
The Many

Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to expedite olefin ring-closing, ring-opening polymerisation and cross-metathesis reactions.

Bis-mixed-carbene ruthenium-thiolate-alkylidene complexes: synthesis and olefin metathesis activity

2015 ◽  
Vol 44 (4) ◽  
pp. 1724-1733 ◽  
Author(s):  
Fatme Dahcheh ◽  
Douglas W. Stephan
Keyword(s):  
Olefin Metathesis ◽  
Ring Opening ◽  
Ring Opening Metathesis Polymerization ◽  
Metathesis Polymerization ◽  
Cross Metathesis ◽  
Vinyl Sulfides ◽  
Alkylidene Complexes

A series of bis-carbene Ru-hydride species were prepared and subsequently shown to react with aryl-vinyl-sulfides to give the corresponding biscarbene-alkylidene complexes. The activities of these species for ring-opening metathesis polymerization, ring-closing and cross-metathesis are reported. While these systems are shown to exhibit modest metathesis activities, the reactivity is enhanced in the presence of BCl3.

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