Copolymerization of ethene with cyclic and other sterically hindered olefins

Kaminsky, Werner; Beulich, Inken; Arndt‐Rosenau, Michael

doi:10.1002/1521-3900(200108)173:1<211::aid-masy211>3.0.co;2-h

Cited by 95 publications

(80 citation statements)

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“…[31]. There have been reports on the copolymerizations using metallocene catalysts [3,[32][33][34][35] [3] were 25 kg-polymer/mol-Zr·h (35 mol %), 31 (85 mol % at 90 • C), 24 (68), 1.3 (40), 0.4 (44), and respectively. Design of molecular catalysts for synthesis of new polymers with specified functions is one of the most attractive targets in the field of catalysis, polymer chemistry, and organometallic chemistry [37][38][39][40][41][42][43][44][45][46][47][48].…”

Section: Copolymerization Of Ethylene With Norbornene (Nbe) Tetracycmentioning

confidence: 99%

“…[9,31]. In contrast to many reports of the ethylene/NBE copolymerization , there have been reports for the copolymerization using metallocene catalysts (Scheme 3) [3,[32][33][34][35] and others [36], however, these catalysts generally exhibited low catalytic activities and/or less efficient TCD incorporation [35]. and others [36], however, these catalysts generally exhibited low catalytic activities and/or less efficient TCD incorporation [35].…”

Section: Copolymerization Of Ethylene With Norbornene (Nbe) Tetracycmentioning

confidence: 99%

“…160 °C, corresponding to ethylene/TCD copolymer containing moderate TCD Scheme 3. Reported metallocene catalysts for copolymerization of ethylene with tetracyclododecene (TCD) [3,[32][33][34][35].…”

Section: Copolymerization Of Ethylene With Norbornene (Nbe) Tetracycmentioning

confidence: 99%

“…Design of molecular catalysts attracts considerable attention in terms of synthesis of new polymers; recent progress in the newly designed catalysts offers several new possibilities. Certain cyclic olefin copolymers (COCs) and cyclic olefin polymers (COPs) are amorphous materials with a promising combination of high transparency in the UV-vis region along with humidityand thermal-resistance (high glass transition temperature, T g ), and extremely low water absorption (excellent water vapor barrier properties) [1][2][3][4][5][6][7]. Due to promising characteristics of COCs, these are used as (i) optical applications such as lenses, liquid crystal display light guide panels, and optical films; (ii) materials in medical and diagnostic equipment and electronic devices; and (iii) packaging applications, and many other uses [8,9].…”

Section: Introductionmentioning

confidence: 99%

“…[31]. There have been reports on the copolymerizations using metallocene catalysts [3,[32][33][34][35] and others [36], however, these catalysts have generally exhibited low catalytic activities and/or less efficient TCD incorporation. For examples, activities (TCD content) by [Et(Ind)2]ZrCl2 [32], [Ph2C(Ind)(Cp)]ZrCl2 [33], [Ph2C(Cp)(Flu)]ZrCl2 [33], [Me2C(3-MeC5H3)(Flu)]ZrCl2 [3], [Me2C(3-t BuC5H3)(Flu)]ZrCl2 [3] were 25 kg-polymer/mol-Zr•h (35 mol %), 31 (85 mol % at 90 °C), 24 (68), 1.3 (40), 0.4 (44), and respectively.…”

Section: Introductionmentioning

confidence: 99%

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Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Zhao

Nomura

2016

Catalysts

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Abstract:Selected results for the synthesis of cyclic olefin copolymers (COCs)-especially copolymerizations of norbornene (NBE) or tetracyclododecene (TCD) with ethylene and α-olefins (1-hexene, 1-octene, 1-dodecene)-using group 4 transition metal (titanium and zirconium) complex catalysts have been reviewed. Half-titanocenes containing an anionic ancillary donor ligand, Cp'TiX 2 (Y) (Cp' = cyclopentadienyl; X = halogen, alkyl; Y = anionic donor ligand such as aryloxo, ketimide, imidazolin-2-iminato, etc.), are effective catalysts for efficient synthesis of new COCs; ligand modifications play an important role for the desired copolymerization. These new COCs possess promising properties (high transparency, thermal resistance (high glass transition temperature), low water absorption, etc.), thus it is demonstrated that the design of an efficient catalyst plays an essential role for the synthesis of new fine polyolefins with specified properties.

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Section: Copolymerization Of Ethylene With Norbornene (Nbe) Tetracycmentioning

confidence: 99%

Section: Copolymerization Of Ethylene With Norbornene (Nbe) Tetracycmentioning

confidence: 99%

Section: Copolymerization Of Ethylene With Norbornene (Nbe) Tetracycmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Zhao

Nomura

2016

Catalysts

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Effect of Cyclopentadienyl Fragment in Copolymerization of Ethylene with Cyclic Olefins Catalyzed by Non‐Bridged (Aryloxo)(cyclopentadienyl)titanium(IV) Complexes

et al. 2005

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Dedicated in honor to Prof. Richard R. Schrock on the occasion of his 60th birthday.Abstract: The effect of the cyclopentadienyl fragment in the copolymerization of ethylene with norbornene (NBE) by various non-bridged (aryloxo)(cyclopentadienyl)titanium(IV) complexes of the type, Cp'TiCl 2 -(OAr) [Cp' ¼ indenyl (1), C 5 Me 5 (Cp*, 2), t-BuC 5 H 4 (3), 1,2,4-Me 3 C 5 H 2 (4); OAr ¼ O-2,6-i-Pr 2 C 6 H 3 ], À MAO catalyst systems has been explored. The catalytic activity and the NBE incorporation were highly dependent upon substituent on Cp' employed, and 1 exhibited both a remarkable catalytic activity and an efficient NBE incorporation, affording high molecular weight polymers with unimodal molecular weight distributions. NBE repeat units were observed in the resultant poly(ethylene-co-NBE)s prepared by 1, 3, and 4, and the degree of NBE dyads as well as alternating sequences was strongly influenced by the Cp' employed. These complexes (1,3,4) also exhibited high catalytic activities for ethylene/cyclopentene (CPE) copolymerization, but the CPE incorporation by 1 was less efficient than the NBE incorporation under the same conditions. The ab initio density functional (DF) molecular orbital (MO) methods were utilized to explore the effect of substituents on Cp' toward the catalytic activity, the NBE incorporation and the monomer sequence distribution. Good correlations between the DE coord Et (coordination energy of ethylene) after NBE insertion and the activity, and between DE coord NBE (coordination energy of NBE) after ethylene (or NBE insertion) and NBE content were observed, strongly suggesting that the capability producing NBE repeat units was dependent upon DE coord NBE after NBE insertion.

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Highly Efficient Ethylene/Cyclopentene Copolymerization with Exclusive 1,2‐Cyclopentene Incorporation by (Cyclopentadienyl)(ketimide)titanium(IV) Complex–MAO Catalysts

Liu

Nomura

2007

Adv Synth Catal

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The (cyclopentadienyl)(ketimide)titanium(IV) complex (t‐BuC5H4)TiCl2[N=C(t‐Bu)2] exhibited remarkable catalytic activities (1.99–3.16×104 kg polymer/mol Ti⋅h) with efficient cyclopentene incorporation in ethylene/cyclopentene copolymerization in the presence of methylaluminoxane (MAO). The polymerization took place with exclusive 1,2‐cyclopentene incorporation, affording high molecular weight (alternating) copolymers (cyclopentene<43.6 mol %) with uniform distributions. The effect of the cyclopentadienyl fragment (Cp′) in the copolymerization using Cp′TiCl2[N=C(t‐Bu)2] [Cp′=indenyl, t‐BuC5H4, C5Me5 (Cp*), C5H5 (Cp)] has been explored in the presence of MAO; the Cp′ plays an important key role in terms of both activity and efficient cyclopentene incorporation.

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Copolymerization of ethene with cyclic and other sterically hindered olefins

Cited by 95 publications

References 0 publications

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Effect of Cyclopentadienyl Fragment in Copolymerization of Ethylene with Cyclic Olefins Catalyzed by Non‐Bridged (Aryloxo)(cyclopentadienyl)titanium(IV) Complexes

Highly Efficient Ethylene/Cyclopentene Copolymerization with Exclusive 1,2‐Cyclopentene Incorporation by (Cyclopentadienyl)(ketimide)titanium(IV) Complex–MAO Catalysts

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