Cycloterpolymerization of 1,6-Heptadiene with Ethylene and Styrene Catalyzed by a THF-Free Half-Sandwich Scandium Complex

Guo, Fang; Nishiura, Masayoshi; Koshino, Hiroyuki; Hou, Zhaomin

doi:10.1021/ma200441w

Cited by 61 publications

(32 citation statements)

References 22 publications

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“…As reported previously, the s PS ( rrrr > 99%, M n = 127,000, M w / M n = 1.47, [ η ] inh = 0.86) was efficiently obtained by the polymerization of styrene in the presence of scandium catalyst system [(C 5 Me 4 SiMe 3 )Sc(CH 2 C 6 H 4 NMe 2 ‐o ) 2 ]/[Ph 3 C][B(C 6 F 5 ) 4 ] (Table , entry 1) . To obtain amino‐containing functionalized s PS, the polymerization of the amino‐containing styrenic monomers, such as DMAS, DEAS, and DPAS by the half‐sandwich scandium complex [(C 5 Me 4 SiMe 3 )Sc(CH 2 C 6 H 4 NMe 2 ‐o ) 2 ] in combination with [Ph 3 C][B(C 6 F 5 ) 4 ] as cocatalyst was conducted at room temperature in toluene.…”

Section: Introductionmentioning

confidence: 85%

Synthesis of amino‐containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles

Shi

Guo

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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Amino‐containing functionalized syndiotactic polystyrenes with high melting temperatures and temperature stability are synthesized by the direct polymerization of amino‐containing styrenic monomers in the presence of a half‐sandwich scandium catalyst system [(C5Me4SiMe3)Sc(CH2C6H4NMe2‐o)2]/[Ph3C][B(C6F5)4]. The high syndiotactic poly(N,N‐dimethylamino)styrene (rrrr > 99%), then used as novel polymer supports, effectively anchored Pd nanoparticles (3 wt % of Pd) with a diameter of 4 or 5 nm that were uniformly dispersed on polymer matrix.

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Section: Introductionmentioning

confidence: 85%

Synthesis of amino‐containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles

Shi

Guo

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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“…This can be accounted for by the fact that ethylene is a smaller, less sterically demanding monomer than styrene or β-myrcene and, thus, is more easily inserted. Hence, ethylene acts as a "spacer" that facilitates subsequent insertions of styrene or β-myrcene monomer, resulting in higher overall productivities than in copolymerizations without ethylene [22][23][24]. Under the given conditions, the level of β-myrcene incorporated in terpolymers was equivalent to that observed for styrene/β-myrcene copolymers.…”

Section: Terpolymerizations Of Styrene With β-Myrcene and Ethylenementioning

confidence: 94%

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

et al. 2017

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Abstract:The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene) and from 2.5 to 9.8 mol % (β-farnesene), respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4-and 3,4-poly(terpene) units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined.

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“…The incorporation ratio of ethylene styrene can be varied from 0% to 100%, and the styrenestyrene linkage in the copolymer is controlled in the syndiotactic structure. The scandium complexes can be successfully applied to syndiospecific copolymerization of styrene with butadiene, isoprene (281,282), nonconjugated dienes (283,284), and ε-caprolactone (285). Carpentier and co-workers also reported that the neodymium complex (67) brings about ethylene-styrene copolymerization to afford the copolymer with the narrow molecular weight distribution (260).…”

Section: Syndiospecific Polymerization Of Styrenementioning

confidence: 99%

Stereoregular Polymers

Takeuchi

2013

Encyclopedia of Polymer Science and Technology

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Control of structure of polymers is an important issue in polymer synthesis because it affects properties such as solubility, crystallinity, and thermal properties. The polymers having stereogenic centers on a main chain can be synthesized by vinyl polymerization of olefinic monomers or ring-opening polymerization of cyclic monomers. Control of trans-cis selectivity is also important for the polymers containing C C double bonds in the main chain. The progress of homogeneous metal complex catalysts for coordination and ring-opening polymerization enables tailor-made control of the stereoregularity of the polymers. In this article, general aspects of stereoregular polymers, especially the polymer of monosubstituted vinyl monomers, are described. Recent progress in stereospecific polymerization of propylene, α-olefins, and styrenes is also summarized. Propylene Polymerization.Isospecific Polymerization of Propylene by Ziegler-Natta Catalysts. In 1954, Natta found that TiCl 3 /Et 2 AlCl catalyst is effective for the synthesis of isotactic polypropylene (4,5). Ti(III) is the active species of the polymerization, whereas other Ti species are also included in the catalyst. Moreover, the stereospecific Ti(III) site as well as nonstereospecific Ti(III) site exists in the catalyst.

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Cycloterpolymerization of 1,6-Heptadiene with Ethylene and Styrene Catalyzed by a THF-Free Half-Sandwich Scandium Complex

Cited by 61 publications

References 22 publications

Synthesis of amino‐containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles

Synthesis of amino‐containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

Stereoregular Polymers

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