Stereocontrolled styrene–isoprene copolymerization and styrene–ethylene–isoprene terpolymerization with a single-component allyl ansa-neodymocene catalyst

Rodrigues, Anne‐Sophie; Kirillov, Evgueni; Vuillemin, Bruno; Razavi, Abbas; Carpentier, Jean‐François

doi:10.1016/j.polymer.2008.02.043

Cited by 49 publications

(50 citation statements)

References 29 publications

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“…On the other hand, all poly(S-co-Fa) samples were white powders. The catalyst productivity decreased with an increase of the cases of styrene/β-myrcene and styrene/farnesene copolymerization, respectively, entries 4-10 and entries [13][14][15][16][17]; this is consistent with the fact that 1 is poorly active towards β-myrcene and farnesene homopolymerization (entries 1-2 and 11-12). On the other hand, as the [terpene] 0 /[St] 0 feed ratio was raised, the terpene content in the resulting copolymers increased as expected; thus, a wide range of compositions was obtained (My content = 5.6-30.8 mol % and Fa content = 1.5-9.8 mol %).…”

Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenesupporting

confidence: 70%

“…In addition, the presence of both 1,4-and 3,4-units for both copolymers confirms that complex 1 is not regioselective towards β-myrcene or β-farnesene. The non-regioselectivity of 1 in those St/My and St/Fa copolymerizations contrasts with styrene/isoprene copolymers containing regular trans-1,4-polyisoprene units obtained in the presence of {CpCMe 2 Flu}Nd(C 3 H 5 )(THF) [17]. We assume that this arises from the more sterically hindered C 3 =C bond in the higher β-myrcene and β-farnesene monomers and/or from the presence of 2,7-tert-butyl substituents on the fluorenyl moiety of catalyst 1.…”

Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenementioning

confidence: 81%

“…Previous work conducted by our group also demonstrated syndioselective styrene/isoprene (/ethylene) co(ter)polymerizations using the neutral {(Me 2 C(Cp)(Flu)}Nd(C 3 H 5 )(THF) complex [17]. In this paper, we report on the copolymerization of styrene with β-myrcene or farnesene with such catalyst systems.…”

Section: Introductionmentioning

confidence: 82%

“…The T g values significantly decreased with the increase of β-myrcene and β-farnesene contents (Figure 4), and poly(S-co-My) materials incorporating between 10 and 20 mol % of β-myrcene units were completely amorphous. As compared with isoprene-based copolymers [17], a wider range of thermal properties is potentially available using these terpenes as comonomers. As shown in Figure 4, the T g values of the three copolymers were similar at low comonomer incorporation levels (T g = 70-77 • C for 3-9 mol % of comonomer inserted).…”

Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenementioning

confidence: 99%

“…Figure 4. Variation of the glass transition temperature (Tg) of poly(S-co-My), poly(S-co-Fa) and poly(S-co-1,4-trans-IP) [17] copolymers as a function of diene (terpene) comonomer content (Table 1, entries 3, 4, 6, 8, 10, 13, 15, 16). …”

Section: Terpolymerizations Of Styrene With β-Myrcene and Ethylenementioning

confidence: 99%

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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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Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenesupporting

confidence: 70%

Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenementioning

confidence: 81%

Section: Introductionmentioning

confidence: 82%

Section: Copolymerizations Of Styrene With β-Myrcene and Farnesenementioning

confidence: 99%

Section: Terpolymerizations Of Styrene With β-Myrcene and Ethylenementioning

confidence: 99%

See 3 more Smart Citations

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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Rare‐Earth Metal Complexes as Catalysts for Syndiospecific Styrene Polymerization

Beckerle

Okuda

2009

Syndiotactic Polystyrene

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Chain‐Shuttling Polymerization at Two Different Scandium Sites: Regio‐ and Stereospecific “One‐Pot” Block Copolymerization of Styrene, Isoprene, and Butadiene

et al. 2011

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The development of new generations of polymerization catalysts and technology for efficient, selective synthesis of novel polymer materials having well-controlled microstructures and desired properties has been a long-standing research subject of both academic and industrial scientists. In this endeavor, exploring the potential of untapped elements is an important strategy. Recently, the chainshuttling copolymerization of two different monomers by two Group 4 metal catalysts that show different monomer selectivities has emerged as a powerful technology for the preparation of olefin block copolymers with different segments. [1] In contrast, the potential of rare-earth catalysts in such chain-shuttling copolymerization has remained unexplored to date. [2,3] Moreover, the success of chain-shuttling copolymerization reported to date has been limited mostly to the copolymerization of ethylene and propylene (or 1-hexene), while the chain-shuttling copolymerization of styrene and a conjugated diene such as isoprene or butadiene has not been reported.We report herein the first example of chain-shuttling copolymerization of styrene, isoprene, and butadiene by two different scandium catalysts. In the presence of scandium catalyst 1 (Scheme 1), which shows high activity and high selectivity for the syndiotactic polymerization of styrene but low activity and low selectivity for isoprene, [4a-c] and scandium catalyst 2, which shows high activity and high cis-1,4selectivity for the polymerization of isoprene [4c] but low activity and low selectivity for styrene, together with a chainshuttling agent, the copolymerization of styrene and isoprene has been achieved regio-and stereoselectively at each monomer, affording for the first time block copolymers with perfect syndiotactic polystyrene (sPS) and highly regulated cis-1,4-polyisoprene (PIP) blocks. In a similar manner, the terpolymerization of styrene, isoprene, and butadiene has also been achieved for the first time to give terpolymers containing perfect sPS, highly regulated cis-1,4-PIP and highly regulated cis-1,4-PBD blocks. By replacement of the catalyst 2 with a catalyst 3, [4d] which showed high 3,4-selectivity for the polymerization of isoprene in the chain-shuttling polymerization of styrene and isoprene, novel styrene-isoprene block copolymers with sPS and 3,4-PIP blocks have been obtained for the first time.Some representative results of the polymerization and copolymerization of styrene and isoprene by three different Sc catalysts 1, 2, and 3 (Scheme 1) under various conditions are summarized in Table 1. As reported, the half-sandwich scandium dialkyl complex 1 bearing the sterically demanding C 5 Me 4 SiMe 3 ligand in combination with [Ph 3 C][B(C 6 F 5 ) 4 ] showed high activity and high syndiospecific selectivity (rrrr > 99 %) for the polymerization of styrene (Table 1, run 1), [4a] but low activity and poor regio-and stereoselectivity for the polymerization of isoprene (Table 1, run 4). [4b,c] The smaller C 5 H 5 -bound Sc analogue 2 exhibited much lower ...

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Stereocontrolled styrene–isoprene copolymerization and styrene–ethylene–isoprene terpolymerization with a single-component allyl ansa-neodymocene catalyst

Cited by 49 publications

References 29 publications

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

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

Rare‐Earth Metal Complexes as Catalysts for Syndiospecific Styrene Polymerization

Chain‐Shuttling Polymerization at Two Different Scandium Sites: Regio‐ and Stereospecific “One‐Pot” Block Copolymerization of Styrene, Isoprene, and Butadiene

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