New approach to block copolymerization of ethylene with polar monomers by the unique catalytic function of organolanthanide complexes

Desurmont, Guillaume; Tanaka, Motomi; Li, Yong; Yasuda, Hajime; Tokimitsu, Tohru; Tone, Seiji; Yanagase, Akira

doi:10.1002/1099-0518(20001115)38:22<4095::aid-pola100>3.3.co;2-i

Cited by 23 publications

(32 citation statements)

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“…Cyclopolymerization of 1,5‐hexadiene resulted in the formation of poly(methylene‐1,3‐cyclopentane) with a cis ‐ring content of about 50 % ( M w =28 500 g mol −1 ; M w / M n =1.88). Furthermore, since catalyst 7 operated by a mechanism involving coordination of ethylene to two samarium centers followed by electron transfer to give a telechelic ethylene‐bridged dinuclear species, block copolymerization of ethylene and MMA resulted in formation of the triblock PMMA‐ block ‐PE‐ block ‐PMMA copolymer (Scheme ) 51. Corresponding trivalent lanthanide compounds with bridging bis(Cp) ligands were not found to be superior in polymerization activity 52…”

Section: Rare‐earth Metal Catalysts For Controlled Alkene Polymerimentioning

confidence: 99%

Catalysts for the Living Insertion Polymerization of Alkenes: Access to New Polyolefin Architectures Using Ziegler–Natta Chemistry

Coates

Hustad

Reinartz

2002

Angew. Chem. Int. Ed.

608

369

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Coordination-insertion polymerization systems have long been superior to their anionic, cationic, and radical polymerization counterparts with regard to stereochemical control. However, until five years ago, these metal-based insertion methods were inferior to ionic and radical mechanisms in the category of living polymerization, which is simply a polymerization that occurs with rapid initiation and negligible chain termination or transfer. In the last half decade, the living insertion polymerization of unactivated olefins has emerged as a powerful tool for the synthesis of new polymer architectures. Materials available today by this route range from simple homopolymers such as linear and branched polyethylene, to atactic or tactic poly(alpha-olefins), to end-functionalized polymers and block copolymers. This review article summarizes recent developments in this rapidly growing research area at the interface of synthetic and mechanistic organometallic chemistry, polymer chemistry, and materials science. While special emphasis is placed on polymer properties and novel polymeric architectures, most of which were inaccessible just a decade ago, important achievements with respect to ligand and catalyst design are also highlighted.

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Section: Rare‐earth Metal Catalysts For Controlled Alkene Polymerimentioning

confidence: 99%

Catalysts for the Living Insertion Polymerization of Alkenes: Access to New Polyolefin Architectures Using Ziegler–Natta Chemistry

Coates

Hustad

Reinartz

2002

Angew. Chem. Int. Ed.

608

369

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“…Polyolefin catalysts are typically electrophilic or oxophilic and, therefore, are poisoned by the presence of functionalized olefins 1. Heteroatoms have been incorporated into polyethylene using early metal and metallocene catalysts but often require the following reaction modifications: masking the functionality as an innocuous species (such as a borate), pre‐complexation of functional groups by stoichiometric amounts of Lewis acidic species, and block copolymerization via two reactions 1, 8–15. More promise, however, has been observed with late metal catalysts because they are more tolerant of polar functionalized compounds 16.…”

Section: Introductionmentioning

confidence: 99%

Linear functionalized polyethylene prepared with highly active neutral Ni(II) complexes

Connor

Younkin

Henderson

et al. 2002

J. Polym. Sci. A Polym. Chem.

166

141

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Neutral Ni(II) salicylaldimine catalysts (pendant ligand ϭ NCMe or PPh 3 ) were used to copolymerize ethylene with monomers containing esters, alcohols, anhydrides, and amides and yielded linear functionalized polyethylene in a single step. ␣-Olefins and polycyclic olefin comonomers carrying functionality were directly incorporated into the polyethylene backbone by the catalysts without any cocatalyst, catalyst initiator, or other disturber compounds. The degree of comonomer incorporation was related to the monomer structure: tricyclononenes Ͼ norbornenes Ͼ ␣-olefins. A wide range of comonomer incorporation, up to 30 mol %, was achieved while a linear polyethylene structure was maintained under mild conditions (40°C, 100 psi ethylene). Results from the characterization of the copolymers by solution and solid-state NMR techniques, thermal analysis, and molecular weight demonstrated that the materials contained a relatively pure microstructure for a functionalized polyethylene that was prepared in one step with no catalyst additive.

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“…Block or random copolymerizations of olefins with polar monomers remain an ultimate goal in the polyolefin chemistry because these processes promise to endow the hydrophilic materials with remarkably high adhesive, dyeing, and moisture‐absorption properties. Block copolymerizations of ethylene with polar monomers such as MMA, alkyl acrylate, and ε‐caprolactone with rare‐earth‐metal complexes;27–29 block copolymerization of norbornene with MMA using ROMP techniques;30 block copolymerizations of ethylene with substituted norbornene derivatives using Ni‐salitylaldimine complex,31 and block copolymerization of ethylene with polar olefins initiated by Kaminsky‐type catalysts32, 33 may be the sole examples of this type of sequential addition polymerization. Johnson and coworkers34, 35 reported the random copolymerizations of olefins with alkyl acrylate, but the resulting acrylate unit is located primarily at the terminal end of branches.…”

Section: Resultsmentioning

confidence: 99%

Homopolymerizations and random copolymerizations of olefins with amino‐substituted cyclopentadienylchromium complexes

Ogata

Nakayama

Yasuda

2002

J. Polym. Sci. A Polym. Chem.

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1-(2-N,N-Dimethylaminoethyl)-2,3,4,5-tetramethylcyclopentadienyl-chromium dichloride (1), (2-N,N-dimethylaminoethyl)cyclopentadienylchromium dichloride (6), and (2-N,N-dimethylaminoethyl)indenylchromium dichloride (7) in the presence of modified methylaluminoxane exhibit high catalytic activities for the polymerization of ethylene with random copolymerizations of ethylene with propylene, ethylene with 1-hexene, and propylene with 1-hexene. These initiators conduct polymerizations to give high molecular weight polymers with low polydispersities. However, the stereoregularities are very poor in these reactions.

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New approach to block copolymerization of ethylene with polar monomers by the unique catalytic function of organolanthanide complexes

Cited by 23 publications

References 0 publications

Catalysts for the Living Insertion Polymerization of Alkenes: Access to New Polyolefin Architectures Using Ziegler–Natta Chemistry

Catalysts for the Living Insertion Polymerization of Alkenes: Access to New Polyolefin Architectures Using Ziegler–Natta Chemistry

Linear functionalized polyethylene prepared with highly active neutral Ni(II) complexes

Homopolymerizations and random copolymerizations of olefins with amino‐substituted cyclopentadienylchromium complexes

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