Ring-opening metathesis polymerisation

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Ring-opening metathesis polymerization (ROMP) is a type of olefin metathesis chain-growth polymerization. The driving force of the reaction is relief of ring strain in cyclic olefins (e.g. norbornene or cyclopentene). A variety of heterogeneous and homogeneous catalysts have been developed. Most large-scale commercial processes rely on the former while some fine chemical syntheses rely on the homogeneous catalysts. [1] Catalysts are based on transition metals such as W, Mo, Re, Ru, and Ti. [2]

Contents

Heterogeneous catalysis and applications

ROMP reaction giving polynorbornene. Like most commercial alkene metathesis processes, this reaction does not employ a well-defined molecular catalyst. Polynbornene.png
ROMP reaction giving polynorbornene. Like most commercial alkene metathesis processes, this reaction does not employ a well-defined molecular catalyst.

Ring-opening metathesis polymerization of cycloalkenes has been commercialized since the 1970s. [1] Examples of polymers produced on an industrial level through ROMP catalysis are Vestenamer or trans-polyoctenamer, which is the metathetical polymer of cyclooctene. Norsorex or polynorbornene is another important ROMP product on the market. Telene and Metton are polydicyclopentadiene products produced in a side reaction of the polymerization of norbornene. [3]

The ROMP process is useful because a regular polymer with a regular amount of double bonds is formed. The resulting product can be subjected to partial or total hydrogenation, or can be functionalized into more complex compounds. [3]

Homogeneous catalysts

Third-generation Grubbs catalyst large.png

The most common homogeneous catalyst for ROMP is also the best understood. In particular, the third generation Grubbs' catalyst (known as G3) has excellent functional group tolerance, air-stability, and fast initiation and propagation rates. [4] [5] [6] The fast initiation rates of G3 results in a living polymerization with a narrow polymer molecular weight dispersion. This has made ROMP a popular choice for making advanced polymer architectures and functional polymer products. [7] It is common to quench these reactions with ethyl vinyl ether to generate the free polymer chain and an inactive Ru Fischer carbene complex. [8]

Mechanism

The mechanism of ROMP is similar to any olefin metathesis reaction. Initiation occurs by formation of an open coordination site. Propagation occurs via a metallacyclobutane intermediate.

Frontal ring-opening metathesis polymerization

Frontal ring-opening metathesis polymerization (FROMP) is a variation of ROMP in which it is a latent polymerization system that react fast, only upon ignition. [9] One example of this system is the FROMP of dicyclopentadiene with a Grubbs' catalyst initiated by heat. [10]

See also

Related Research Articles

In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar. Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups.

In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization, in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer. The reactive center can be radical, anionic or cationic. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. ROP is a versatile method for the synthesis of biopolymers.

In chemistry, homogeneous catalysis is catalysis where the catalyst is in same phase as reactants, principally by a soluble catalyst a in solution. In contrast, heterogeneous catalysis describes processes where the catalysts and substrate are in distinct phases, typically solid-gas, respectively. The term is used almost exclusively to describe solutions and implies catalysis by organometallic compounds. Homogeneous catalysis is an established technology that continues to evolve. An illustrative major application is the production of acetic acid. Enzymes are examples of homogeneous catalysts.

Grubbs catalysts are a series of transition metal carbene complexes used as catalysts for olefin metathesis. They are named after Robert H. Grubbs, the chemist who supervised their synthesis. Several generations of the catalyst have also been developed. Grubbs catalysts tolerate many functional groups in the alkene substrates, are air-tolerant, and are compatible with a wide range of solvents. For these reasons, Grubbs catalysts have become popular in synthetic organic chemistry. Grubbs, together with Richard R. Schrock and Yves Chauvin, won the Nobel Prize in Chemistry in recognition of their contributions to the development of olefin metathesis.

<span class="mw-page-title-main">Dicyclopentadiene</span> Chemical compound

Dicyclopentadiene, abbreviated DCPD, is a chemical compound with formula C10H12. At room temperature, it is a white brittle wax, although lower purity samples can be straw coloured liquids. The pure material smells somewhat of soy wax or camphor, with less pure samples possessing a stronger acrid odor. Its energy density is 10,975 Wh/l. Dicyclopentadiene is a co-produced in large quantities in the steam cracking of naphtha and gas oils to ethylene. The major use is in resins, particularly, unsaturated polyester resins. It is also used in inks, adhesives, and paints.

<span class="mw-page-title-main">Olefin metathesis</span>

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 discovery of a variety of highly active catalysts, Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock were collectively awarded the 2005 Nobel Prize in Chemistry.

<span class="mw-page-title-main">Norbornene</span> Chemical compound

Norbornene or norbornylene or norcamphene is a highly strained bridged cyclic hydrocarbon. It is a white solid with a pungent sour odor. The molecule consists of a cyclohexene ring with a methylene bridge between carbons 1 and 4. The molecule carries a double bond which induces significant ring strain and significant reactivity.


Dynamic covalent chemistry (DCvC) is a synthetic strategy employed by chemists to make complex molecular and supramolecular assemblies from discrete molecular building blocks. DCvC has allowed access to complex assemblies such as covalent organic frameworks, molecular knots, polymers, and novel macrocycles. Not to be confused with dynamic combinatorial chemistry, DCvC concerns only covalent bonding interactions. As such, it only encompasses a subset of supramolecular chemistries.

<span class="mw-page-title-main">Robert H. Grubbs</span> American chemist and Nobel Laureate (1942–2021)

Robert Howard GrubbsForMemRS was an American chemist and the Victor and Elizabeth Atkins Professor of Chemistry at the California Institute of Technology in Pasadena, California. He was a co-recipient of the 2005 Nobel Prize in Chemistry for his work on olefin metathesis.

<span class="mw-page-title-main">Yves Chauvin</span>

Yves Chauvin was a French chemist and Nobel Prize laureate. He was honorary research director at the Institut français du pétrole and a member of the French Academy of Science. He was known for his work for deciphering the process of olefin metathesis for which he was awarded the 2005 Nobel Prize in Chemistry along with Robert H. Grubbs and Richard R. Schrock.

Ring-closing metathesis (RCM) is a widely used variation of olefin metathesis in organic chemistry for the synthesis of various unsaturated rings via the intramolecular metathesis of two terminal alkenes, which forms the cycloalkene as the E- or Z- isomers and volatile ethylene.

Acyclic diene metathesis or 'ADMET' is a special type of olefin metathesis used to polymerize terminal dienes to polyenes:

<span class="mw-page-title-main">Maurice Brookhart</span>

Maurice S. Brookhart is an American chemist, and professor of chemistry at the University of Houston since 2015.

<span class="mw-page-title-main">Polydicyclopentadiene</span> Chemical compound

Polydicyclopentadiene (PDCPD) is a polymer material which is formed through ring-opening metathesis polymerization(ROMP) of dicyclopentadiene (DCPD). PDCPD exhibits high crosslinking, which grants its properties, such as high impact resistance, good chemical corrosion resistance, and high heat deflection temperature. PDCPD is frequently used in the automotive industry to make body panels, bumpers, and other components for trucks, buses, tractors, and construction equipment. PDCPD is being investigated for the creation of porous materials for tissue engineering or gas storage applications, as well as for self-healing polymers.

<span class="mw-page-title-main">Herbert S. Eleuterio</span> American industrial chemist

Herbert S. Eleuterio was an American industrial chemist noted for technical contributions to catalysis, polymerization, industrial research management, and science education. In particular, he discovered the olefin metathesis reaction and several novel fluoropolymers. Additionally, he explored techniques for research leadership, especially methods for fostering collaboration, globalization, and scientific creativity.

Functionalized polyolefins are olefin polymers with polar and nonpolar functionalities attached onto the polymer backbone. There has been an increased interest in functionalizing polyolefins due to their increased usage in everyday life. Polyolefins are virtually ubiquitous in everyday life, from consumer food packaging to biomedical applications; therefore, efforts must be made to study catalytic pathways towards the attachment of various functional groups onto polyolefins in order to affect the material's physical properties.

<span class="mw-page-title-main">Zhan catalyst</span> Chemical compound

A Zhan catalyst is a type of ruthenium-based organometallic complex used in olefin metathesis. This class of chemicals is named after the chemist who first synthesized them, Zheng-Yun J. Zhan.

Corinna S. Schindler is a Professor of Chemistry at the University of Michigan. She develops catalytic reactions with environmentally benign metals such as iron, towards the synthesis of biologically active small molecules. For her research in the development of new catalysts, Schindler has been honored with several early-career researcher awards including the David and Lucile Packard Foundation Fellowship in 2016, the Alfred P. Sloan Fellowship in 2017, and being named a member of the C&EN Talented 12 in 2017. Schindler has served on the Editorial Board of Organic and Bimolecular Chemistry since 2018.

Carbonyl olefin metathesis is a type of metathesis reaction that entails, formally, the redistribution of fragments of an alkene and a carbonyl by the scission and regeneration of carbon-carbon and carbon-oxygen double bonds respectively. It is a powerful method in organic synthesis using simple carbonyls and olefins and converting them into less accessible products with higher structural complexity.

Jennifer Ann Love is an American professor of chemistry at the University of Calgary. She is a Fellow of the Chemical Institute of Canada.

References

  1. 1 2 Lionel Delaude; Alfred F. Noels (2005). "Metathesis". Kirk-Othmer Encyclopedia of Chemical Technology. Weinheim: Wiley-VCH. doi:10.1002/0471238961.metanoel.a01. ISBN   978-0-471-23896-6.
  2. Grant), Cowie, J. M. G. (John McKenzie (2008). Polymers: chemistry and physics of modern materials. Arrighi, V. (Valeria) (3rd ed.). Boca Raton: CRC Press. ISBN   978-0-8493-9813-1. OCLC   82473191.{{cite book}}: CS1 maint: multiple names: authors list (link)
  3. 1 2 Mol, J.C. (2004). "Industrial applications of olefin metathesis". Journal of Molecular Catalysis A: Chemical . 213 (1): 39–45. doi:10.1016/j.molcata.2003.10.049.
  4. Love, Jennifer A.; Morgan, John P.; Trnka, Tina M.; Grubbs, Robert H. (2002). "A Practical and Highly Active Ruthenium‐Based Catalyst that Effects the Cross Metathesis of Acrylonitrile". Angewandte Chemie International Edition. 41 (21): 4035–4037. doi:10.1002/1521-3773(20021104)41:21<4035::aid-anie4035>3.0.co;2-i. ISSN   1521-3773. PMID   12412073.
  5. Walsh, Dylan J.; Lau, Sii Hong; Hyatt, Michael G.; Guironnet, Damien (2017-09-25). "Kinetic Study of Living Ring-Opening Metathesis Polymerization with Third-Generation Grubbs Catalysts". Journal of the American Chemical Society. 139 (39): 13644–13647. doi:10.1021/jacs.7b08010. ISSN   0002-7863. PMID   28944665.
  6. Slugovc, Christian (2004-07-21). "The Ring Opening Metathesis Polymerisation Toolbox". Macromolecular Rapid Communications. 25 (14): 1283–1297. doi:10.1002/marc.200400150. ISSN   1022-1336.
  7. Sveinbjörnsson, Benjamin R.; Weitekamp, Raymond A.; Miyake, Garret M.; Xia, Yan; Atwater, Harry A.; Grubbs, Robert H. (2012-09-04). "Rapid self-assembly of brush block copolymers to photonic crystals". Proceedings of the National Academy of Sciences. 109 (36): 14332–14336. Bibcode:2012PNAS..10914332S. doi: 10.1073/pnas.1213055109 . PMC   3437898 . PMID   22912408.
  8. Grubbs, R.H.; Tumas, W. (1989). "Polymer Synthesis and Organotransition Metal Chemistry". Science . 243 (4893): 907–915. Bibcode:1989Sci...243..907G. doi:10.1126/science.2645643. PMID   2645643.
  9. Ruiu, Andrea; Sanna, Davide; Alzari, Valeria; Nuvoli, Daniele; Mariani, Alberto (2014-07-15). "Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene". Journal of Polymer Science Part A: Polymer Chemistry. 52 (19): 2776–2780. Bibcode:2014JPoSA..52.2776R. doi:10.1002/pola.27301. ISSN   0887-624X.
  10. Moneypenny, Timothy P.; Liu, Huiying; Yang, Anna; Robertson, Ian D.; Moore, Jeffrey S. (2017-04-13). "Grubbs-inspired metathesis in the Moore group". Journal of Polymer Science Part A: Polymer Chemistry. 55 (18): 2935–2948. Bibcode:2017JPoSA..55.2935M. doi: 10.1002/pola.28592 . ISSN   0887-624X.