Influence of the Polymer Microstructure on the Thermal Properties of Cycloolefin Copolymers with High Norbornene Contents

Forsyth, John; Pereña, José M.; Benavente, Rosario; Pérez, Ernesto; Tritto, Incoronata; Boggioni, Laura; Brintzinger, Hans‐Herbert

doi:10.1002/1521-3935(20010301)202:5<614::aid-macp614>3.0.co;2-c

Cited by 95 publications

(82 citation statements)

References 9 publications

(13 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The results also show that the microstructures of the copolymers are dependent on the complex used. Tritto and colleagues 69 reported that the stereoregularity of a norbornene sequence affected the T g value of poly(norbornene-co-ethylene) with high norbornene contents. 70 Living polymerization of olefins T Shiono…”

Section: Copolymerization Of Norbornene With 1-alkenementioning

confidence: 99%

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Shiono

2011

Polym J

View full text Add to dashboard Cite

This article reviews the living homopolymerization and copolymerization of propene, 1-alkene and norbornene with ansadimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(g 3 -C 13 H 8 )(g 1 -N t Bu)TiMe 2 and its derivatives, correlating the effects of cocatalysts, solvents, polymerization conditions and the substituents of the fluorenyl ligand with catalytic features, such as livingness, initiation efficiency, propagation rate, syndiospecificity and copolymerization ability. The synthesis of novel olefin block copolymers and their catalytic synthesis are also introduced using this living system. Polymer Journal (2011) 43, 331-351; doi:10.1038/pj.2011 Keywords: cycloolefin copolymer; living polymerization; norbornene; propene; single-site catalyst; syndiospecific polymerization; 1-alkene A living polymerization system, in which neither chain transfer nor deactivation occurs, affords polymers with predictable molecular weights and narrow molecular weight distributions (MWDs). Living polymerization techniques are utilized for the synthesis of terminally functionalized polymers and block copolymers. Another feature of living polymerization is its simple kinetics. Because neither chain transfer nor deactivation occurs in living polymerization, the number of polymer chains (N) is equal to the number of active centers ([C*]), and the number-average molecular weight (M n ) directly reflects the propagation rate. In living polymerization, the propagation rate can be evaluated from the M n value and the polymerization time. As chain transfer via b-elimination and/or transmetalation with trialkylaluminum as a cocatalyst is inevitable in conventional Ziegler-Natta catalytic systems; homogeneous V(acac) 3 /Et 2 AlCl (where acac is acetylacetonate or its analog) had previously been the only catalytic system that produced syndiotactic-rich living polypropylene (PP) atThe development of metallocene catalysts has enabled us to produce a variety of uniform olefin copolymers and to control the stereoregularity of poly(1-alkene)s. 3,4 The success of metallocene catalysts has stimulated research on transition metal complexes for olefin polymerization, 5-7 so-called single-site catalysts, which has also resulted in various transition metal complexes for the living polymerization of olefins. 8,9 We have also developed a living polymerization system using ansa-dimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(Z 3 -C 13 H 8 )(Z 1 -N t Bu)TiMe 2 (1), combined with a suitable cocatalyst. The catalytic system allows not only a syndiospecific living polymerization of propene and a 1-alkene but also a living homopolymerization and copolymerization of norbornene with a 1-alkene. We investigated the effect of cocatalyst, solvent and the ligand of the titanium complex on propene polymerization in terms of the livingness of the system. We also synthesized novel olefin block copolymers with the living system. This article reviews the characteristics of 1-based catalysts for tailor-made polyolefins. SYNTHESIS AND STRUCTURES OF TIT...

show abstract

Section: Copolymerization Of Norbornene With 1-alkenementioning

confidence: 99%

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Shiono

2011

Polym J

View full text Add to dashboard Cite

show abstract

“…the important role played by microstructure on the thermal properties. [2] Copolymers with a high norbornene content do not necessarily have higher glass transition temperatures. Thus, in the case of copolymers with alternating units, the fact that the norbornene rings are mainly isolated leads to low values of T g .…”

Section: Introductionmentioning

confidence: 99%

Stress-Strain Behaviour, Microhardness, and Dynamic Mechanical Properties of a Series of Ethylene-Norbornene Copolymers

Scrivani

Benavente

Pérez

et al. 2001

Macromol. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

“…Most of these reports correlated the composition, microstructure, and thermal properties of ethene-norbornene copolymer [4][5][6][7][8]. A few studies have been made on the influence of chemical structure on the thermal properties of cyclic olefin copolymers.…”

Section: Introductionmentioning

confidence: 99%

Chemical structure and physical properties of cyclic olefin copolymers (IUPAC Technical Report)

Shin

Park

Liu

et al. 2005

Pure and Applied Chemistry

145

101

View full text Add to dashboard Cite

Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without theAbstract: Cyclic olefin copolymers comprise a new class of polymeric materials showing properties of high glass-transition temperature, optical clarity, low shrinkage, low moisture absorption, and low birefringence. There are several types of cyclic olefin copolymers based on different types of cyclic monomers and polymerization methods. In this work, we have analyzed the chemical structure of the currently commercialized cyclic olefin copolymers by 13 C NMR, and investigated their glass-transition temperatures and surface characteristics. It was observed that the glass-transition temperature, T g , of cyclic olefin copolymers depended on the bulkiness of the main chain, and the number of rings had an important role in increasing the bulkiness of cyclic olefin copolymers. Cyclic olefin copolymers with polar substituents such as ester or ether groups showed high surface energy per area and peel strength.

show abstract

Influence of the Polymer Microstructure on the Thermal Properties of Cycloolefin Copolymers with High Norbornene Contents

Cited by 95 publications

References 9 publications

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Stress-Strain Behaviour, Microhardness, and Dynamic Mechanical Properties of a Series of Ethylene-Norbornene Copolymers

Chemical structure and physical properties of cyclic olefin copolymers (IUPAC Technical Report)

Contact Info

Product

Resources

About