Methylaluminoxane

Last updated
Methylaluminoxane
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 485-360-0
PubChem CID
  • InChI=1S/CH3.Al.O/h1H3;;
    Key: CPOFMOWDMVWCLF-UHFFFAOYSA-N
  • C[Al]=O
Properties
(Al(CH3)xOy)n
AppearanceWhite solid
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Pyrophoric
GHS labelling:
GHS-pictogram-flamme.svg
Warning
H228, H250, H252
P210, P222, P235+P410, P240, P241, P280, P302+P334, P370+P378, P407, P413, P420, P422
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methylaluminoxane, commonly called MAO, is a mixture of organoaluminium compounds with the approximate formula (Al(CH3)O)n. It is usually encountered as a solution in (aromatic) solvents, commonly toluene but also xylene, cumene, or mesitylene, [1] Used in large excess, it activates precatalysts for alkene polymerization. [2] [3] [4]

Contents

Preparation and structure

Structure of Al33O26(CH3)47(Al2(CH3)6), an MAO crystallized by Luo, Younker, Zabula. The highlighted (CH3)2Al sites are proposed to be released during catalyst activation. MAOexxon.svg
Structure of Al33O26(CH3)47(Al2(CH3)6), an MAO crystallized by Luo, Younker, Zabula. The highlighted (CH3)2Al sites are proposed to be released during catalyst activation.

MAO is prepared by the incomplete hydrolysis of trimethylaluminium, as indicated by this idealized equation: [5]

n Al(CH3)3 + n H2O → (Al(CH3)O)n + 2n CH4

After many years of study, single crystals of an active MAO were analyzed by X-ray crystallography. The molecule adopts a ruffled sheet of tetrahedral Al centers linked by triply bridging oxides. [4]

Uses

MAO is well known as catalyst activator for olefin polymerizations by homogeneous catalysis. In traditional Ziegler–Natta catalysis, supported titanium trichloride is activated by treatment with trimethylaluminium (TMA). TMA only weakly activates homogeneous precatalysts, such as zirconacene dichloride. In the mid-1970s Kaminsky discovered that metallocene dichlorides can be activated by MAO (see Kaminsky catalyst). [6] The effect was discovered when a small amount of water was found to enhance the activity in the Ziegler–Natta system.

MAO serves multiple functions in the activation process. First it alkylates the metal-chloride pre-catalyst species giving Ti/Zr-methyl intermediates. Second, it abstracts a ligand from the methylated precatalysts, forming an electrophilic, coordinatively unsaturated catalysts that can undergo ethylene insertion. This activated catalyst is an ion pair between a cationic catalyst and an weakly basic MAO-derived anion. [7] MAO also functions as scavenger for protic impurities.

Previous studies

Diverse mechanisms have been proposed for the formation of MAO and many structures as well.

See also

Related Research Articles

<span class="mw-page-title-main">Metallocene</span> Type of compound having a metal center

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:

<span class="mw-page-title-main">Kaminsky catalyst</span> Ethylene polymerization catalyst

A Kaminsky catalyst is a catalytic system for alkene polymerization. Kaminsky catalysts are based on metallocenes of group 4 transition metals activated with methylaluminoxane (MAO). These and other innovations have inspired development of new classes of catalysts that in turn led to commercialization of novel engineering polyolefins.

A post-metallocene catalyst is a kind of catalyst for the polymerization of olefins, i.e., the industrial production of some of the most common plastics. "Post-metallocene" refers to a class of homogeneous catalysts that are not metallocenes. This area has attracted much attention because the market for polyethylene, polypropylene, and related copolymers is large. There is a corresponding intense market for new processes as indicated by the fact that, in the US alone, 50,000 patents were issued between 1991-2007 on polyethylene and polypropylene.

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

Trimethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name it has the formula Al2(CH3)6 (abbreviated as Al2Me6 or TMA), as it exists as a dimer. This colorless liquid is pyrophoric. It is an industrially important compound, closely related to triethylaluminium.

<span class="mw-page-title-main">Olefin metathesis</span> Organic reaction involving the breakup and reassembly of alkene double bonds

In organic chemistry, 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.

Coordination polymerisation is a form of polymerization that is catalyzed by transition metal salts and complexes.

<span class="mw-page-title-main">Catalytic cycle</span> Multistep reaction mechanism involving a catalyst

In chemistry, a catalytic cycle is a multistep reaction mechanism that involves a catalyst. The catalytic cycle is the main method for describing the role of catalysts in biochemistry, organometallic chemistry, bioinorganic chemistry, materials science, etc.

Walter Kaminsky is a German chemist who specializes in olefin polymerization and plastic recycling. He discovered the high activity of Group 4 metallocene/methylaluminoxane (MAO) mixtures as catalysts for olefin polymerization in 1980.

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

Aluminoxanes are organoaluminium compounds with the formula [RAlO]m[R2AlO0.5]n[R2AlOH]o, where R = organic substituent. The following structural rules apply: Al is tetrahedral and O is three-coordinate.

The Cossee–Arlman mechanism in polymer chemistry is the main pathway for the formation of C–C bonds in the polymerization of alkenes. The mechanism features an intermediate coordination complex that contains both the growing polymer chain and the monomer (alkene). These ligands combine within the coordination sphere of the metal to form a polymer chain that is elongated by two carbons.

<span class="mw-page-title-main">Organonickel chemistry</span> Branch of organometallic chemistry

Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds. They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)4, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.

<span class="mw-page-title-main">Organozirconium and organohafnium chemistry</span>

Organozirconium chemistry is the science of exploring the properties, structure, and reactivity of organozirconium compounds, which are organometallic compounds containing chemical bonds between carbon and zirconium. Organozirconium compounds have been widely studied, in part because they are useful catalysts in Ziegler-Natta polymerization.

<span class="mw-page-title-main">Organomolybdenum chemistry</span> Chemistry of compounds with Mo-C bonds

Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common.

<i>Ansa</i>-metallocene Organometallic compound

An ansa-metallocene is a type of organometallic compound containing two cyclopentadienyl ligands that are linked by a bridging group such that both cyclopentadienyl groups are bound to the same metal. The link prevents rotation of the cyclopentadienyl ligand and often modifies the structure and reactivity of the metal center. Some ansa-metallocenes are active in Ziegler-Natta catalysis, although none are used commercially. The term ansa-metallocene was coined by Lüttringhaus and Kullick to describe alkylidene-bridged ferrocenes, which were developed in the 1950s.

In organometallic chemistry, bent metallocenes are a subset of metallocenes. In bent metallocenes, the ring systems coordinated to the metal are not parallel, but are tilted at an angle. A common example of a bent metallocene is Cp2TiCl2. Several reagents and much research is based on bent metallocenes.

Diiminopyridines are a class of diimine ligands. They featuring a pyridine nucleus with imine sidearms appended to the 2,6–positions. The three nitrogen centres bind metals in a tridentate fashion, forming pincer complexes. Diiminopyridines are notable as non-innocent ligand that can assume more than one oxidation state. Complexes of DIPs participate in a range of chemical reactions, including ethylene polymerization, hydrosilylation, and hydrogenation.

<span class="mw-page-title-main">Phillips catalyst</span> Ethylene polymerization catalyst

The Phillips catalyst, or the Phillips supported chromium catalyst, is the catalyst used to produce approximately half of the world's polyethylene. A heterogeneous catalyst, it consists of a chromium oxide supported on silica gel. Polyethylene, the most-produced synthetic polymer, is produced industrially by the polymerization of ethylene:

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">Transition metal phosphinimide complexes</span>

Transition metal phosphinimide complexes are metal complexes that contain phosphinimide ligands of the general formula NPR3 (R = organic substituent). Several coordination modes have been observed, including terminal and various bridging geometries. In the terminal bonding mode the M-N=P core is usually linear but some are quite bent. The preferred coordination type varies with the oxidation state and coligands on the metal and the steric and electronic properties of the R groups on phosphorus. Many transition metal phosphinimide complexes have been well-developed and, more recently, main group phosphinimide complexes have been synthesized.

References

  1. "MAO Datasheet" (PDF). Albemarle. Archived from the original (PDF) on 2004-04-11.
  2. Kaminsky, W.; Laban, A. (2001). "Metallocene catalysis". Applied Catalysis A: General. 222 (1–2): 47–61. doi:10.1016/S0926-860X(01)00829-8.
  3. Kaminsky, Walter (1998). "Highly active metallocene catalysts for olefin polymerization". Journal of the Chemical Society, Dalton Transactions (9): 1413–1418. doi:10.1039/A800056E.
  4. 1 2 Luo, Lubin; Younker, Jarod M.; Zabula, Alexander V. (2024). "Structure of Methylaluminoxane (MAO): Extractable [Al(CH3)2]+ for Precatalyst Activation". Science. 384 (6703): 1424–1428. Bibcode:2024Sci...384.1424L. doi:10.1126/science.adm7305.
  5. Process for the preparation of aluminoxanes – Patent EP0623624
  6. A. Andresen; H.G. Cordes; J. Herwig; W. Kaminsky; A. Merck; R. Mottweiler; J. Pein; H. Sinn; H.J. Vollmer (1976). "Halogen-free Soluble Ziegler-Catalysts for the Polymerization of Ethylene". Angew. Chem. Int. Ed. 15 (10): 630. doi:10.1002/anie.197606301.
  7. Hansjörg Sinn; Walter Kaminsky; Hans-Jürgen Vollmer; Rüdiger Woldt (1980). "'Living Polymers' on Polymerization with Extremely Productive Ziegler Catalysts". Angewandte Chemie International Edition in English . 19 (5): 390–392. doi:10.1002/anie.198003901.