The Vinyl Homopolymerization of Norbornene

Janiak, Christoph; Lassahn, Paul G.

doi:10.1002/1521-3927(20010401)22:7<479::aid-marc479>3.0.co;2-c

Cited by 210 publications

(148 citation statements)

References 48 publications

Supporting

Mentioning

145

Contrasting

Unclassified

Order By: Relevance

“…In the polymerization of alkyl-substituted 1,6-diene, the new monomer inserts exclusively into the CH 2 …”

Section: Mechanism Of Cyclopolymerizationmentioning

confidence: 99%

See 1 more Smart Citation

Stereo-controlled synthesis of polyolefins with cycloalkane groups by using late transition metals

Takeuchi

2012

Polym J

View full text Add to dashboard Cite

Pd complexes with diimine ligands promoted the controlled cyclopolymerization of 1,6-dienes and 1,6,11-trienes to afford polymers containing 1,2-trans-cyclopentane groups with well-regulated stereochemistry. The polymerization proceeded with quantitative cyclization of the monomer, even under bulk conditions or in copolymerization reactions with ethylene and aolefins. The polymerization of monomers with oligomethylene spacers yielded polymers with five-membered rings that are accurately distributed along the polymer chain. 4-Alkylcyclopentenes and alkenylcyclohexanes were also polymerized by Pddiimine complexes to afford polymers with 1,3-trans-cyclopentane groups and 1,4-trans-cyclohexane groups, respectively. Pd complexes with a C 2 symmetrical structure promoted the isospecific polymerization of 4-alkylcyclopentenes, and the resultant isotactic polymers showed liquid crystalline properties. The mechanism of the polymerization reaction has been revealed.

show abstract

“…In the polymerization of alkyl-substituted 1,6-diene, the new monomer inserts exclusively into the CH 2 …”

Section: Mechanism Of Cyclopolymerizationmentioning

confidence: 99%

“…1 Addition polymerization of cyclic alkenes 2,3 and metathesis polymerization of norbornenes [4][5][6] have been used to synthesize these polymers (Scheme 1). Cyclic groups on the monomer can be introduced into the polymer as cis-fused cycloalkane groups.…”

Section: Introductionmentioning

confidence: 99%

Stereo-controlled synthesis of polyolefins with cycloalkane groups by using late transition metals

Takeuchi

2012

Polym J

View full text Add to dashboard Cite

show abstract

“…Coordination-insertion polymerization of norbornene was studied with TiCl 4 /R 3 Al in the early 1960s, and a number of zirconocenes have been studied since the 1980s. 53,54 All of these catalysts, except for (Z 5 -C 5 H 5 )Ti(OBz) 3 -MAO, have shown very low catalytic activity, and the products produced are insoluble in common organic solvents.…”

Section: Polymerization Of Norbornenementioning

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

“…Not only, this system is already known to be an active catalyst for norbornene homopolymerization, 1,16 it also presents the advantage of being composed of two commercially available and relatively stable components. Table I lists the results of polymerizations which were carried out in toluene at room temperature.…”

Section: Polymerization Of Norbornene With Norbornene Derivativesmentioning

confidence: 99%

Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

2009

View full text Add to dashboard Cite

Vinyl addition copolymerization of norbornene with norbornene derivatives bearing siloxane substituent, three arm-, cyclicand phenyl-siloxane groups, was realized in the presence of the binary Ni(acac) 2 /B(C 6 F 5 ) 3 system. The resulting copolymers show good solubility in common organic solvents and possess a very high grass transition temperature between 265 and 360 C, depending on the content and structure of the siloxane groups. The incorporation of siloxane groups linked to the polymer chain results in a significant increase in the mechanical flexibility of the corresponding films. Furthermore, the gas permeability is also dependent on the content and structure of the siloxane groups, and the films obtained for the polymers with three arm-siloxane group (-Si(OSiMe 3 ) 3 ) display high oxygen permeability in the range of 39 to 239 Barrer.KEY WORDS: Polynorbornene / Siloxane Substituent / Copolymerization / Nickel Catalyst / Norbornene can be polymerized by three different methods: ring opening metathesis polymerization (ROMP), cationic or radical polymerization, and vinyl addition polymerization. 1Among these polymers, addition-type poly(norbornene), presenting the rigid bicyclic structure, is recently attracting strong interest in optical and opto-electronic device applications because of high optical transparency, low birefringence, very high glass transition temperature and low dielectric constant. However, poor solubility in common organic solvents and mechanical brittleness are serious disadvantages for the processing of the polymer materials. These problems can be improved markedly by copolymerizing a small amount of functional norbornene derivatives.So far, many types of poly(norbornene)s with functional groups have been prepared. [2][3][4][5][6][7][8][9][10][11][12][13] Heitz et al. 2,3 investigated the addition-type copolymerizations of norbornene with norbornene carboxylic acid esters, and found that the solubility of the copolymers and the thermal properties, such as glasstransition and decomposition temperatures, were dependent on the content as well as structure of the substituents. Risse et al. [4][5][6] came to the same conclusion by studying poly-(norbornene)s containing hydroxyl, carboxylic acid and ester. Goodall et al.7-9 and Grove et al. 10 prepared alkyl-or alkoxysilyl-substituted poly(norbornene)s, which showed improved mechanical toughness and adhesion to common substrate materials. On the other hand, Dorkenoo et al. 11and Finkelshtein et al.12 investigated the homopolymers of norbornene derivatives bearing alkyl or alkylsilyl substituents, and demonstrated that the chain length and the bulkiness of the substituents played a decisive role in the transport properties, such as gas permeability and permselectivity, for the polymeric membranes. These results show that the nature of substituent and the content in the main chain are an important factor for the regulation of the material properties.Poly(siloxane) is a class of polymers that has practical importance in the consumer and indus...

show abstract

The Vinyl Homopolymerization of Norbornene

Cited by 210 publications

References 48 publications

Stereo-controlled synthesis of polyolefins with cycloalkane groups by using late transition metals

Stereo-controlled synthesis of polyolefins with cycloalkane groups by using late transition metals

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

Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

Contact Info

Product

Resources

About