Synthesis of high molecular weight poly(methyl methacrylate) with extremely low polydispersity by the unique function of organolanthanide(III) complexes

Yasuda, Hajime; Yamamoto, H.; Yamashita, Masahiro; Yokota, Kazumichi; Nakamura, Akira; Miyake, S.; Kai, Yasushi; Kanehisa, Nobuko

doi:10.1021/ma00078a004

Cited by 266 publications

(184 citation statements)

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“…This difference may reflect the larger ionic radius of lanthanum and is in line with the observations for the polymerisation of ethene 1 and MMA. 3 Precatalyst 1a produces higher molecular weight oligomers, suggesting a less favourable chain transfer compared to 1b.…”

Section: Groningen Centre For Catalysis and Synthesis Department Of mentioning

confidence: 98%

“…Recently, however, examples have been reported on organolanthanide-catalysed polymerisation of functionalised monomers, e.g. living polymerisation of methyl methacrylate (MMA) 3 producing high molecular weight polymers with narrow molecular weight distributions. Here we report the catalytic oligomerisation of cyclic α,β-unsaturated ketones, an observation which opens up interesting opportunities for the synthesis of functionalised (co)polymers.…”

Section: Groningen Centre For Catalysis and Synthesis Department Of mentioning

confidence: 99%

“…Subsequent monomer complexation and 1,4-addition produces oligomers, similar to the organolanthanide-catalysed polymerisation of MMA. 3 Chain transfer can follow through hydrogen abstraction at the α-position of the incoming monomer forming the oligomer and regenerating the catalytically active enolate species (Scheme 1).…”

Section: Groningen Centre For Catalysis and Synthesis Department Of mentioning

confidence: 99%

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Organolanthanide-catalysed oligomerisation of 2-cycloalken-1-ones

Deelman¹,

Bijpost²,

Teuben³

1995

J. Chem. Soc., Chem. Commun.

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Section: Groningen Centre For Catalysis and Synthesis Department Of mentioning

confidence: 98%

Section: Groningen Centre For Catalysis and Synthesis Department Of mentioning

confidence: 99%

Section: Groningen Centre For Catalysis and Synthesis Department Of mentioning

confidence: 99%

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Organolanthanide-catalysed oligomerisation of 2-cycloalken-1-ones

Deelman¹,

Bijpost²,

Teuben³

1995

J. Chem. Soc., Chem. Commun.

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“…Alkyl compounds such as [Cp*2SmH]2 (Cp* = C$Mq$) 9 Cp* 2 LnMe(ether), Cp* 2 LnAlMe 4 , and [Cp 2 LnMe] 2 (Ln = Sm, Y, Yb, Lu; Cp = C5H5) were found to quantitatively and quickly polymerize MMA at temperatures from -115 to 40 °C, giving polymers with PDIs as low as 1.02. The PMMA is very highly syndiotactic when produced at lower temperatures (> 96% rr at -110 °C) (102)(103)(104)(105)(106)(107)(108)(109)(110); tacticity is still quite high under more reasonable conditions (77% rr at 40 °C). Due to the solubilizing effect of the cyclopentadienyl ligands, polymerization may be carried out in a wide range of solvents, although the catalysts are extremely sensitive to air and water.…”

Section: Lanthanide(iii) Initiatorsmentioning

confidence: 99%

“…Interestingly, syndiotacticity decreases with increasing size of the methacrylate side chain (103,105,108). More impressively, living polymerizations of alkyl acrylates (including methyl and ethyl acrylate) have been achieved, although the propagating acrylate enolates are not quite as robust as their methacrylic analogues (111,112).…”

Section: Lanthanide(iii) Initiatorsmentioning

confidence: 99%

The Organometallic Polymerization of (Meth)acrylates: An Overview

Boffa

2000

ACS Symposium Series

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Metal-mediated (meth)acrylate polymerizations provide a good example of the versatility and importance of transition metal catalysis in polymer design. This chapter surveys several of these processes with respect to "living" behavior, experimental condition and monomer restrictions, and types of polymer architectures available.In addition to anionic methods, Group Transfer Polymerization (GTP) with silyl enolates or zirconocenes, organolanthanide-and aluminum porphyrin-initiated polymer ization, and Atom Transfer Radical Polymerization (ATRP) are discussed.Polymethacrylate and polyacrylate materials play an important role in our society. Almost two billion pounds of polymer products based on acrylic esters are produced each year for applications such as window plastics, dental materials, paints, contact lenses, fibers, and viscosity modifiers.Polymethacrylates-particularly poly(methyl methacrylate) (PMMA)-possess high strength, high impact resistance, excellent heat and chemical stability, and a highly amorphous nature which results in excellent optical clarity. For these reasons, they are used widely as building plastics (Plexiglas, Lucite). Polyacrylates are less rigid due to their lower glass transition temperatures, and as latex emulsions form the basis for durable automobile and house paints and coatings. Random copolymers of (meth)acrylates with vinylidene chloride (Sarari), acrylonitrile, and ethylene find applications as clothing fibers, tubing, gaskets, disposable gloves, and heat-and oil-resistant automotive elastomers.Despite the commercial utility of polymethacrylates and polyacrylates, refinements in synthetic methodology these macromolecules have lagged behind that of other polymers. The great majority of acrylic ester products in use today are still produced by radical polymerization, which allows little if any control over the fine points of the polymerization process. This is the result of the traditionally illcontrolled nature of acrylate polymerization. While chain termination and transfer side reactions may be largely eliminated for other monomers, such as styrene and dienes, through the use of controlled anionic polymerization, the (meth)acrylate ester

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