Synthesis of bis(7-octenyl)zinc via heterogeneous Ni catalysts

Chen, Yu; Clark, Thomas P.; Jazdzewski, Brian A.; Klamo, Sara B.; Wenzel, Timothy T.

doi:10.1016/j.poly.2014.05.077

Cited by 6 publications

(6 citation statements)

References 14 publications

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“…24 TMEDA was distilled from sodium/benzophenone and stored over 3 Å molecular sieves. Diethylamino-tert-butyl-chlorophosphine (yield = 98%), 10 BrMgC 8 H 15 , 25 Wilkinson's catalyst, 26 Na[BAr F 4 ], 27 and [Rh(biph)(dtbpm)Cl], 14 were synthesised according to published procedures. All other reagents are commercial products and were used as received.…”

Section: General Methodsmentioning

confidence: 99%

Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands

2020

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Section: General Methodsmentioning

confidence: 99%

Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands

2020

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“…Borane is a catalyst poison and should be completely transformed to zinc species with the use of some excess Et 2 Zn. The syntheses of (7-octenyl) 2 Zn had been attempted by the same routes as those in Scheme a,b at Dow Chemical Company; however, the yields were unsatisfactorily low (14 and 20%, respectively). , The prepared (7-octenyl) 2 Zn was used in chain shuttling polymerization to prepare olefin block copolymers with a comb architecture composed of soft main chain and hard LCBs…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Long-Chain Branched Polyolefins by Coordinative Chain Transfer Polymerization

et al. 2019

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Synthesis of long-chain branched polymers has been a crucial concern in the polyolefin industry. In this study, a method to produce long-chain branches (LCBs) in coordinative chain transfer copolymerization (CCTcoP) is suggested. A dialkylzinc compound bearing vinyl groups ((9-decenyl)2Zn) is prepared, which works well not only as a chain transfer agent but also as a comonomer in CCTcoP, resulting in the generation of LCBs. The generation of LCBs is confirmed by gel permeation chromatography studies and through the analysis of rheology data. The formation of LCBs by connecting the two growing polyolefin chains can facilitate the generation of polymers with molecular weights higher than that expected. Owing to the presence of LCBs, considerable shear thinning behavior is observed. Ethylene/1-octene copolymers can be prepared facilely to show almost the same shear thinning behavior with the commercial grade of low-density polyethylene, which is known to have a substantial amount of LCBs.

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“…Preparation of the dialkylzinc species containing styrene moieties ( 3 ) was carried out through alkyl exchange between Et 2 Zn and the hydroboration product of divinylbenzene ( Scheme 3 ) [ 42 , 48 ]. During the dynamic alkyl exchange process, the transient Et 3 B species was removed by evacuation at 0 °C, eventually leading to formation of the desired product, 3.…”

Section: Resultsmentioning

confidence: 99%

“…In the other way, the styrene signals were observed at 7.2-5.0 ppm region ( Figure S2) in the 1 H NMR spectrum of a low molecular weight poly(ethylene-co-propylene), which was synthesized by feeding a high amount of 3 (Zn = 500 μmol) and by cutting the polymerization at an early stage (5 min). Preparation of the dialkylzinc species containing styrene moieties (3) was carried out through alkyl exchange between Et2Zn and the hydroboration product of divinylbenzene (Scheme 3) [42,48]. During the dynamic alkyl exchange process, the transient Et3B species was removed by evacuation at 0 °C, eventually leading to formation of the desired product, 3.…”

Section: Strategy For the Preparation Of Ps-block-po-block-psmentioning

confidence: 99%

Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

et al. 2017

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Triblock copolymers of polystyrene (PS) and a polyolefin (PO), e.g., PS-block-poly(ethyleneco-1-butene)-block-PS (SEBS), are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH 2 =CHC 6 H 4 CH 2 CH 2 ) 2 Zn) was prepared, from which poly(ethylene-co-propylene) chains were grown via "coordinative chain transfer polymerization" using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me 3 SiCH 2 Li·(pmdeta) (pmdeta = pentamethyldiethylenetriamine). We found that the fraction of the extracted PS homopolymer was low (~20%) and that molecular weights were evidently increased after the styrene polymerization (∆M n = 27-54 kDa). Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.

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Synthesis of bis(7-octenyl)zinc via heterogeneous Ni catalysts

Cited by 6 publications

References 14 publications

Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands

Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands

Synthesis of Long-Chain Branched Polyolefins by Coordinative Chain Transfer Polymerization

Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

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