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.

A practical and simple method for the preparation of ABA-type olefin triblock copolymers, e.g., PE-b-poly­(ethylene-co-propylene)-b-PE, has been described. The performance of the so-called “coordinative chain transfer polymerization” (CCTP) by sequential feed of ethylene and ethylene/propylene mixed gas generated a Zn-bound diblock copolymer (i.e., (PE-b-poly­(ethylene-co-propylene)­yl)2Zn). Treatment of the Zn-bound diblock copolymer with lauroyl peroxide (CH3(CH2)10C­(O)­O-OC­(O)­(CH2)10CH3) led to a C­(sp3)–C­(sp3) coupling reaction between the two diblock chains bound on the zinc site and an ABA-type olefin triblock copolymer, PE-b-poly­(ethylene-co-propylene)-b-PE, was formed. Upon the treatment with lauroyl peroxide, the number-average molecular weight increased by 1.5–1.7 times. The occurrence of the coupling reaction was verified using a model compound, (Oct)2Zn. The ABA-type triblock copolymer exhibited thermoplastic elastomeric properties and dramatically improved mechanical properties (twice the tensile strength and 10-fold increase in the elongation at break) as compared to the diblock congener.

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.

The demand for poly(α-olefin)s (PAOs), which are high-performance group IV lubricant base oils, is increasingly high. PAOs are generally produced via the cationic oligomerization of 1-decene, wherein skeleton rearrangement inevitably occurs in the products. Hence, a transition-metal-based catalytic process that avoids rearrangement would be a valuable alternative for cationic oligomerization. In particular, transition-metal-catalyzed selective trimerization of α-olefins has the potential for success. In this study, (N,N′,N″-tridodecyltriazacyclohexane)CrCl3 complex was reacted with MAO-silica (MAO, methylaluminoxane) for the preparation of a supported catalyst, which exhibited superior performance in selective α-olefin trimerization compared to that of the corresponding homogeneous catalyst, enabling the preparation of α-olefin trimers at ~200 g scale. Following hydrogenation, the prepared 1-decene trimer (C30H62) exhibited better lubricant properties than those of commercial-grade PAO-4 (kinematic viscosity at 40 °C, 15.1 vs. 17.4 cSt; kinematic viscosity at 100 °C, 3.9 vs. 3.9 cSt; viscosity index, 161 vs. 123). Moreover, it was shown that 1-octene/1-dodecene mixed co-trimers (i.e., a mixture of C24H50, C28H58, C32H66, and C36H74), generated by the selective supported Cr catalyst, exhibited outstanding lubricant properties analogous to those observed for the 1-decene trimer (C30H62).

Synthetic biodegradable polyesters tend to undergo slow biodegradation under ambient natural conditions and, hence, have been rejected or even banned recently in ecofriendly applications. Here, we demonstrate the preparation of polyesters exhibiting enhanced biodegradability, which were generated through a combination of old controversial macromolecules and aggregate theories. H 3 PO 4 -catalyzed diacid/diol polycondensation afforded polyester chains bearing chain-end −CH 2 OP(O)(OH) 2 and inner-chain (−CH 2 O) 2 P(O)(OH) groups, which were subsequently treated with M(2-ethylhexanoate) 2 (M = Zn, Mg, Mn, and Ca) to form ionic aggregates of polyesters. The prepared ionic aggregates of polyesters, which were constructed with fertilizer ingredients (such as M 2+ and phosphate), exhibit much faster biodegradability than that of the conventional polyesters under controlled soil conditions at 25 °C, while displaying comparable or superior rheological and mechanical properties.