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.

Polystyrene (PS)-block-poly(ethylene-co-1-butene)block-PS (SEBS), produced by PS-block-polybutadiene-block-PS hydrogenation, is a high-performance thermoplastic elastomer. Hydrogenation is costly and tedious, making SEBS market expansion difficult. Thus, we envisioned a new one-pot SEBS-like triblock copolymer synthetic scheme to grow PO chains from styrene moiety-carrying diorganozinc compounds by coordinative chain transfer polymerization (CCTP), followed by anionic styrene polymerization using a specially designed initiator, allowing PS chain growth from not only the styrene moieties but also the Zn−C sites. Large-scale preparation of highly pure styrene moiety-carrying diorganozinc compounds was one of the main challenges we faced, but we overcame it by synthesizing (CH 2 CHC 6 H 4 CH 2 CH 2 CH 2 ) 2 Zn (4), a stable and crystalline solid that worked well as a CCTP agent. This enabled the preparation of PS-block-poly(ethylene-co-1-hexene)-block-PS (SEHS), which exhibited a stress−strain curve similar to that of the commercial-grade SEBS. The SEHS dispersed better in a polypropylene (PP) matrix, allowing it to act as a better toughening agent for PP blending than the commercial-grade SEBS. Moreover, SEHS was less viscous, exhibiting better workability.

Polyolefins (POs) are the most abundant polymers. However, synthesis of PO-based block copolymers has only rarely been achieved. We aimed to synthesize various PO-based block copolymers by coordinative chain transfer polymerization (CCTP) followed by anionic polymerization in one-pot via conversion of the CCTP product (polyolefinyl)2Zn to polyolefinyl-Li. The addition of 2 equiv t-BuLi to (1-octyl)2Zn (a model compound of (polyolefinyl)2Zn) and selective removal or decomposition of (tBu)2Zn by evacuation or heating at 130 °C afforded 1-octyl-Li. Attempts to convert (polyolefinyl)2Zn to polyolefinyl-Li were unsuccessful. However, polystyrene (PS) chains were efficiently grown from (polyolefinyl)2Zn; the addition of styrene monomers after treatment with t-BuLi and pentamethyldiethylenetriamine (PMDTA) in the presence of residual olefin monomers afforded PO-block-PSs. Organolithium species that might be generated in the pot of t-BuLi, PMDTA, and olefin monomers, i.e., [Me2NCH2CH2N(Me)CH2CH2N(Me)CH2Li, Me2NCH2CH2N(Me)Li·(PMDTA), pentylallyl-Li⋅(PMDTA)], as well as PhLi⋅(PMDTA), were screened as initiators to grow PS chains from (1-hexyl)2Zn, as well as from (polyolefinyl)2Zn. Pentylallyl-Li⋅(PMDTA) was the best initiator. The Mn values increased substantially after the styrene polymerization with some generation of homo-PSs (27–29%). The Mn values of the extracted homo-PS suggested that PS chains were grown mainly from polyolefinyl groups in [(polyolefinyl)2(pentylallyl)Zn]−[Li⋅(PMDTA)]+ formed by pentylallyl-Li⋅(PMDTA) acting onto (polyolefinyl)2Zn.

The pyridylamido hafnium complex (I) discovered at Dow is a flagship catalyst among postmetallocenes, which are used in the polyolefin industry for PO-chain growth from a chain transfer agent, dialkylzinc. In the present work, with the aim to block a possible deactivation process in prototype compound I, the corresponding derivatives were prepared. A series of pyridylamido Hf complexes were prepared by replacing the 2,6-diisopropylphenylamido part in I with various 2,6-R2C6H3N-moieties (R = cycloheptyl, cyclohexyl, cyclopentyl, 3-pentyl, ethyl, or Ph) or by replacing 2-iPrC6H4C(H)- in I with the simple PhC(H)-moiety. The isopropyl substituent in the 2-iPrC6H4C(H)-moiety influences not only the geometry of the structures (revealed by X-ray crystallography), but also catalytic performance. In the complexes bearing the 2-iPrC6H4C(H)-moiety, the chelation framework forms a plane; however, this framework is distorted in the complexes containing the PhC(H)-moiety. The ability to incorporate α-olefin decreased upon replacing 2-iPrC6H4C(H)-with the PhC(H)-moiety. The complexes carrying the 2,6-di(cycloheptyl)phenylamido or 2,6-di(cyclohexyl)phenylamido moiety (replacing the 2,6-diisopropylphenylamido part in I) showed somewhat higher activity with greater longevity than did prototype catalyst I.

Cycloolefin copolymers (COCs, which are produced via ethylene/cycloolefin copolymerization) and cycloolefin polymers (COPs, which are synthesized by a rather complicated two‐step process via ring‐opening metathesis polymerization and subsequent hydrogenation) are commercialized materials used especially widely in optical applications. Although a COP can be used after processing into a film, films made from conventional COCs are too brittle. Optical‐grade COCs and COPs are generally known as amorphous polymers. By contrast, here, a quasi‐alternating ethylene/norbornene copolymer (norbornene content 56 mol%), prepared from a constrained‐geometry Hf complex, shows some melting (Tm) signals in a broad temperature range (150–200°C) in the first heating scan of differential scanning calorimetry (DSC) when the samples are prepared by precipitation from a toluene solution. In the second heating scan, only glass transition (Tg) signals are observed at ~140°C with disappearance of Tm signals. The quasi‐alternating ethylene/norbornene copolymer has better mechanical properties (greater elongation at break) than random congeners, which do not show any melting signal, though elongation at break is still inferior to that of the COP which shows the melting signal in the first heating scan of DSC. The enhanced mechanical properties of the quasi‐alternating ethylene/norbornene copolymer and commercial‐grade COP may be ascribed to semicrystallinity observed in the first heating scan.