Dramatically Accelerating II-I Crystal Phase Transition of Polybutene­1 by In Situ Incorporation of H-Shape Long-Chain-Branching Structures.

This communication reports an effective strategy helping address the long-troubling melt processing issue of isotactic polybutene-1 (i-PB) caused by its extremely slow II-I crystal phase transition. The solution lies in a facile synthesis of i-PB containing H-shape long-chain-branching structures (LCB-i-PB) by applying a so-called ω-alkenylmethyldichlorosilane copolymerization-hydrolysis (ACH) chemistry to butene-1 polymerization with Ziegler-Natta or metallocene catalysts. It is evident that the H-shape LCB structures effectively enhance chain entanglements of i-PB and induce an over-the-board acceleration of the overall melt crystallization process including nucleation, form II crystallization, and form II-form I phase transition. As i-PB usually requires up to a week to reach equilibrium of the II-I phase transition, it is found that with LCB-i-PB such a transition is almost finished within as short as 24 h to even higher degrees.

Largely Improved Creep Resistance and Thermal-Aging Stability of Eco-Friendly Polypropylene High-Voltage Insulation by Long-Chain Branch-Induced Interfacial Constraints.

Polypropylene (PP)-based composites have attracted numerous attention as a replacement of prevailing cross-linked polyethylene (XLPE) for high-voltage insulation due to their ease of processing, recyclability, and excellent electrical performance. However, the poor resistances against high-temperature creep and thermal aging are obstacles to practical applications of PP-based thermoplastic high-voltage insulation. To address these problems, in this Letter, we synthesized an impact polypropylene copolymer (IPC) containing multifold long-chain branched (LCB) structures in phases, especially the interfaces between the PP matrix and the rubber phase. The results indicated that the structural stability of LCBIPC was significantly enhanced under extreme conditions. In comparison to IPC (without LCB structures), 24.1% less creep strain and 75.2% less unrecoverable deformation are achieved in LCBIPC at 90 °C. In addition, the thermal aging experiments were performed at 135 °C for 48 and 88 days for IPC and LCBIPC, respectively. The results show that the resistance against thermal aging was also enhanced in LCBIPC, which showed a 133% longer thermal aging life compared to IPC. Further results revealed that the interfacial layer between the PP matrix and the rubber phase was constructed in LCBIPC. The two phases are tightly linked by chemical bonds in LCB structures, leading to enforced constraints of the rubber phase at the micro level and better resistance performance against creep and thermal aging at the macro level. Evidently, the reported eco-friendly LCBIPC thermoplastic insulation shows great potential for applications in high-voltage cable insulation.

Assessing 1,9-Decadiene/Ethylene Copolymerization with Ziegler-Natta Catalyst to Access Long Chain-Branched Polyethylene.

1,9-Decadiene/ethylene copolymerization is assessed as a way for Ziegler-Natta catalysts to access long chain-branched polyethylene (PE). A MgCl2/9,9-bis-(methoxymethyl)fluorine/TiCl4 catalyst with triethylaluminium as a cocatalyst is exemplified for the task. 1,9-Decadiene was found to induce a substantial comonomer effect on catalyst activity and continuing decreases of PE molecular weight. Both the double bonds of 1,9-decadiene were poorly reactive during polymerization, of which the polymer chain-attached was even much less reactive than the original one. As a consequence, at decreased feeds, 1,9-decadiene gave small amounts (<0.1 mol %) of pendant vinyl groups to PE without prompting the formation of long-chain branches. Long chain-branching was realized at increased 1,9-decadiene feeds, which was however accompanied by proportional gelation.

Precision Polyolefin Nanoalloy Polypropylene/Poly(ε-caprolactone).

This communication reports the first example of precision polyolefin nanoalloys where an exotic immiscible polymer is nanometrically dispersed with stability in a polyolefin matrix in a highly controlled mode. Following the preparation of polypropylene/multiwalled carbon nanotubes nanocomposites (PP/MWCNTs) by in situ Ziegler-Natta polymerization, the hydroxyl groups on the surfaces of individual MWCNTs are used to initiate ring-opening polymerization of ε-caprolactone, resulting in PP/poly(ε-caprolactone) (PCL) alloy with PCL grafted on MWCNTs. Upon phase formation, the PP/MWCNTs-g-PCL alloys exhibit a unique PCL dispersion morphology, which is stable and solely governed by PCL molecular weight.

Comonomer-induced stereo-selectivity enhancement in a c2 -symmetric metallocene-catalyzed propylene polymerization.

Propylene polymerization is carried out with a C 2 -symmetric metallocene catalyst of rac-Et(Ind)2 ZrCl2 /MAO at 40 °C in the presence of a cyclo-triene of trans,trans,cis-1,5,9-cyclododecatriene ((E,E,Z)-CDT). Comonomer incorporations are rather low (<0.10 mol%). However, it is shown for the first time that the comonomer causes a noticeable increase in poly-propylene -isotacticity (>7% in [mmmm]). (E,E,Z)-CDT is speculated to coordinate to the metal center forming comonomer-complexed active sites in charge of the entire polymerization reaction with decreased activity however increased propylene -enantiomorphic selectivity.

[Investigation of nascent polypropylene in-reactor alloy particles].

Heterogeneous nascent particles were observed in a pilot product of polypropylene in-reactor alloy, which was polymerized by Ziegler-Natta/Metallocene hybrid catalyst using Spheripol technology. Most of the particles in the product are translucent, and opaque particles were observed as well. The differences in morphology, composition, chain structure, thermal properties and mechanical properties between these two kinds of particles were investigated by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), polarized optical microscopy (POM), and differential scanning calorimetry (DSC) techniques. The results of FTIR, NMR and SEM indicate that different morphology of these two different particles is caused by different content of ethylene-propylene copolymers. The results of DSC and POM showed that the translucent particles has higher crystallization rate than opaque particles due to the presence of ethylene-propylene copolymers. The mechanical properties results showed that the impact resistance property of opaque particles is obviously lower than that of translucent particles, while its tensile strength and bending modulus are much higher than that of translucent particles. Based on the process of Spheripol technology, a preliminary explanation for the formation of different nascent PP in-reactor alloy particles is proposed.

Fabrication of nanofillers into a granular "nanosupport" for Ziegler-Natta catalysts: towards scalable in situ preparation of polyolefin nanocomposites.

This communication reports a strategy for scale-up of an in situ polymerization technique for polyolefin-based nanocomposites preparation, taking layered silicate (clay) and multi-walled carbon nanotubes (MWCNTs) as examples of nanofillers. The strategy is realized by transforming the nanofillers into granular "nanosupports" for Ziegler-Natta catalysts. With a catalyst to polymer replication effect on particle morphology, the in situ prepared nanocomposites are of controlled granular particle morphology. With the polymer particle morphology controlled, the in situ polymerization technique becomes suitable for industrial olefin polymerization processes for mass production of polyolefin nanocomposites.