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. 2023 Mar 9;15(6):1378.
doi: 10.3390/polym15061378.

A Hydrocarbon Soluble, Molecular and "Complete" Al-Cocatalyst for High Temperature Olefin Polymerization

Gaia Urciuoli  1   2   3 , Francesco Zaccaria  1   3 , Cristiano Zuccaccia  2   3 , Roberta Cipullo  1   3 , Peter H M Budzelaar  1   3 , Antonio Vittoria  1   3 , Christian Ehm  1   3 , Alceo Macchioni  2   3 , Vincenzo Busico  1   3
Affiliations

A Hydrocarbon Soluble, Molecular and "Complete" Al-Cocatalyst for High Temperature Olefin Polymerization

Gaia Urciuoli et al. Polymers (Basel). .

Abstract

The dinuclear aluminum salt {[iBu2(DMA)Al]2(μ-H)}+[B(C6F5)4]- (AlHAl; DMA = N,N-dimethylaniline) is the prototype of a new class of molecular cocatalysts for catalytic olefin polymerization, its modular nature offering easy avenues for tailoring the activator to specific needs. We report here, as proof of concept, a first variant (s-AlHAl) bearing p-hexadecyl-N,N-dimethylaniline (DMAC16) units, which enhances solubility in aliphatic hydrocarbons. The novel s-AlHAl was used successfully as an activator/scavenger in ethylene/1-hexene copolymerization in a high-temperature solution process.

Keywords: borate activators; catalyst activation; methylaluminoxane; olefin polymerization; soluble cocatalyst.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Structures of AlHAl and its hydrocarbon soluble analogue s-AlHAl.
Scheme 1
Scheme 1
Synthesis of s-Al and s-AlHAl. DIBAL-H is shown as a monomer for simplicity.
Figure 2
Figure 2
(a) Representative 1D diffusion NMR spectra of s-AlHAl at increasing gradient strength in pentane (with acetone-d6 coaxial capillary, 298 K, 33 mM) and (b) DOSY map derived therefrom; (c) trend of the average aggregation number (N) as a function of the analytical concentration of s-AlHAl derived from diffusion NMR measurements (trendline obtained by fitting experimental data based on the IK model; see ESI). *, solvent signals. A 15% and 10% error are assumed on aggregation number and concentration, respectively [43,44].
Figure 3
Figure 3
The ansa-zirconocene precatalyst Cat-Zr employed in polymerization screening.
See this image and copyright information in PMC

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