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Bio-Olefins prepared by acyclic diene metathesis

  • 166 Pages
  • 4.58 MB
  • English
Statementby Timothy Edward Hopkins
The Physical Object
Paginationxvi, 166 leaves :
ID Numbers
Open LibraryOL25905461M

Acyclic diene metathesis is a well-defined polycondensation reaction enabling the synthesis of unique polymer architectures by simple monomer design ().Thus, ADMET can be used to prepare macromolecules inaccessible by common polymerization techniques.We have recently reported the polymerization of various protected amino acid/peptide branched dienes, yielding Cited by: 5.

A series of “N-terminus” amino acid and peptide branched, chiral polyolefins, termed bio-olefins, have been prepared using acyclic diene metathesis (ADMET) polycondensation chemistry, using a minimal amount of solvent and Bio-Olefins prepared by acyclic diene metathesis book second generation catalyst.

The carboxylic acid functional groups were protected with methyl, benzyl, and tert-butyl esters to enhance both the polymerizability Cited by: The process of acyclic diene metathesis (ADMET) polymerization of an α,ω‐diene begins with the metathesis of a terminal olefin and a metal methylidene complex, which produces a molecule of ethylene and a metal alkylidene via the α‐substituted metallacyclobutane, where the terminal olefin can be a monomer, an oligomer, or a polymer.

Bio-olefins via condensation metathesis chemistry. A new class of polymers bearing amino acids and dipeptides has been prepared using acyclic diene metathesis (ADMET) to create copolymers of. An illustration of an open book.

Books. An illustration of two cells of a film strip. Video. An illustration of an audio speaker. Audio. An illustration of a " floppy disk. Full text of "Acyclic diene metathesis, a new equilibrium step propagation, condensation polymerization". Acyclic Diene Metathesis Polymerization (ADMET) ADMET n ADMET.

Intramolecular metathesis of a diene to form a cyclic olefin Ring Closing Metathesis (RCM) M M M MCH2-H 2CCH RCM n. Reaction pathway of diene depends on catalyst, dilution, ring size, and substrate (functional groups and sterics) Catalyst: Si O Si Re2O7/Al2O3-SnBu4 dilute.

tion of acyclic alkenes,28 Therefore, is considered to be ‘the date of birth’ of the term ‘alkene metathesis’, which was introduced for the first time by Calderon29 to describe the process of disproportionation (transalkylide-nation) of unsaturated hydrocarbons.


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Mechanisms, types and catalysts of alkene metathesis. A powerful methodology for the synthesis of unsaturated polyphosphoesters (UPPEs) relying on acyclic diene metathesis (ADMET) polymerization is described. A facile two-step protocol gives fast access to structurally versatile and potentially degradable and biocompatible materials.

For the first time this allows to control the microstructure of either backbone and/or side chains of. A series of “N-terminus” amino acid and peptide branched, chiral polyolefins, termed bio-olefins, have been prepared using acyclic diene metathesis (ADMET) polycondensation chemistry, using a.

Synthesis of new polyesters by acyclic diene metathesis (ADMET) polymerization of α,ω-diene, 4-allylmethoxyphenyl undecenoate (M1), prepared from bio-renewable eugenol and castor oil (undecenoate), have been ium-carbene (called second generation Grubbs) catalyst afforded polymers with unimodal molecular weight distributions (M n = 12M w /M n = ).

Olefin metathesis polymerization can be subdivided in two important polymerization reaction classes: the chain‐growth polymerization technique ring‐opening metathesis polymerization (ROMP) and the step‐growth condensation polymerization acyclic diene metathesis (ADMET).

telechelic polymers are efficiently prepared by ROMP with the use of chain transfer agents.5 In addition to ROMP, there are two other metathesis polymerization methods, acyclic diene metathesis polymerization (ADMET) and cyclopolymerization.

ADMET is a step-growth polymerization where dienes are polymerized by continuous cross metathesis. acyclic diene metathesis (ADMET) polymerization. This ap-proach was implemented for the preparation of fluorene-con-taining multiblock copolymers [62,63].

Poly(9,9-di-n-octylfluo-rene-2,7-vinylene, PFV) obtained by ADMET polymerization of 2,7-divinyl-9,9-di-n-octylfluorene in the presence of Gr2. Olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) by the scission and regeneration of carbon-carbon double bonds.

Because of the relative simplicity of olefin metathesis, it often creates fewer undesired by-products and hazardous wastes than alternative organic reactions. For their elucidation of the reaction mechanism and their.

opening metathesis polymerization (ROMP),27,28 The olefin metathesis reaction of two linear olefins provides the linear products of cross metathesis,30 Finally, repeated cross-metathesis reactions of α,ω-dienes produces polymeric products in a process referred to as acyclic diene metathesis polymerization (ADMET),31,32 Scheme Gity Mir Mohamad Sadeghi, Mahsa Sayaf, in Nanostructured Polymer Blends, Block Copolymers by Ring-Opening Metathesis Polymerization.

Ring opening metathesis polymerization (ROMP) has emerged in recent years, as a valuable tool for the polymerization of a wide variety of strained cyclic alkene monomers [64].ROMP, which is a transition-metal-mediated polymerization.

Olefin metathesis is a popular and useful the presence of certain transition-metal compounds, including various metal carbenes, olefins exchange the groups around the double bonds, resulting in several outcomes: straight swapping of groups between two acyclic olefins (cross-metathesis), closure of large rings (ring-closing metathesis), formation of dienes from cyclic and acyclic.

This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, ).Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic Manufacturer: Academic Press.

Acyclic diene metathesis (ADMET) polymerization has shown to be a clean route to silicon-based unsaturated polymers possessing the Si-Cl functionality.

The Si-Cl bond remains inert during metathesis, and the use of Schrock's well-defined molybdenum alkylidene catalyst affords unsaturated chlorofunctionalized carbosilane polymers with known.

Acyclic Diene Metathesis (ADMET) Nobel Prize in Chemistry. Inthe Royal Swedish Academy of Sciences awarded the Nobel Prize in Chemistry to Dr. Robert H. Grubbs, Yves Chauvin, and Dr.

Richard R. Schrock for the development of the metathesis method in organic synthesis. This achievement further highlights the practical and scientific. A series of conjugated, symmetrical, and ferrocene-containing main-chain monomers was prepared following a gentle coupling reaction.

Ferrocene-containing oligomers with all-trans-configured vinylene bonds could be synthesized via acyclic diene metathesis (ADMET) polymerization. These oligomers had a larger Stokes shift ( to cm−1) and both exhibited stable and reversible.

This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, ). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic Format: Paperback.

Shape-persistent arylenevinylene macrocycles (AVMs) were successfully prepared in one step from readily available aromatic diene monomers through olefin metathesis in good yields. 1H NMR, UV-Vis absorption and fluorescence studies revealed the aggregation behavior of.

Cross-Metathesis Between Cyclic and Acyclic Olefins: End-Groups and Telomers. Dependence of Molecular Weight on [M2]/[M1].

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Kinetic Data. Degradation of UnsaturatedPolymers by Metathesis: Degradation by Intramolecular Metathesis. Applications of the Olefin Metathesis Reaction: The Phillips Triolefin Process.

The Neohexene Process. Cross Metathesis (CM) Acyclic Diene Metathesis Polymerization (ADMET) Applications. Olefin metathesis opened up new industrial pathways for petrochemicals, polymers, and so much more.

In the petrochemical field, olefin metathesis is used for the Olefins Conversion Technology (OCT) Process and the Shell Higher Olefins Process (SHOP). General Information. The olefin metathesis reaction (the subject of Nobel Prize in Chemistry) can be thought of as a reaction in which all the carbon-carbon double bonds in an olefin (alkene) are cut and then rearranged in a statistical fashion.

If one of the product alkenes is volatile (such as ethylene) or easily removed, then the reaction shown above can be driven completely to the right. Synthesis and characterization of unsaturated thermotropic polyesters prepared via acyclic diene metathesis polymerization. Authors. HH Qin BJ Chakulski IA Rousseau JZ Chen XQ Xie PT Mather GS Constable EB Coughlin.

Publication Date. Journal or Book. Main-Chain Ferrocene-Containing Polymers Prepared by Acyclic Diene Metathesis Polymerization: A Review, - Ye Sha*, Zhihua Shen, Huan Jia and Zhenyang Luo* DOI: / ×. ABSTRACT Acyclic diene metathesis polymerization will be employed in the pursuit of 4 research objectives: to define structure property relationships in branched polyethylene and related (functionalized) materials, to create a set of "Bio-Olefins" for tissue engineering and other bioapplications, to explore solid state metathesis chemistry, and to continue to expand the catalyst base for this.

Application of metathesis in chemistry of unsaturated deriva-tives of POSS is limited to 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.

Polymerization of alkenes is a reaction that yields polymers of high industrial value at great economy, such as the plastics polyethylene and rs from alkene monomers are referred to in a general way as polyolefins or in rare instances as polyalkenes.A polymer from alpha-olefins is called a polyalphaolefin (PAO).

Polymerization can proceed via either a free-radical or an.intramolecular reaction of an acyclic diene to form a ring (Fig. 1), while cross metathesis brings two olefins together in an intermolecular reaction to give an olefin product bearing substituents from each of the starting olefins (Fig.


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+ metathesis catalyst Figure 1. Ring-closing metathesis (RCM) + metathesis catalyst Figure 2. Cross.Acyclic (pentadienyl)iron(1+) cations 2 are most commonly prepared by ionization of (pentadienol)- or (pentadienyl ether)iron complexes under protic or Lewis acid conditions (Scheme 4).[2, 4] Ionization of the hydroxyl group occurs with anchimeric assistance from iron to generate the transoid pentadienyl cation 21; subsequent isomerization of.