화학공학소재연구정보센터
Journal of Polymer Science Part A: Polymer Chemistry, Vol.55, No.15, 2467-2476, 2017
Polypropylene and poly(ethylene-co-1-octene) effective synthesis with diamine-bis(phenolate) complexes: Effect of complex structure on catalyst activity and product microstructure
A series of group 4 metal complexes bearing amine-bis(phenolate) ligands with the amino side-arm donor: (-O)[Me2N(CH2)(2)N(CH2-2-O-3,5-tBu(2)-C6H2)(2)ZrCl](2) (1a), R2N(CH2)(2)N(CH2-2-O-3-R-1-5-R-2-C6H2)(2)TiCl2 (R=Me, R-1, R-2=tBu (2a), R=iPr, R-1, R-2=tBu (2b), R=iPr, R-1=tBu, R-2=OMe (2c)), and Me2N(CH2)(2)N(CH2-2-O-3,5-tBu(2)-C6H2)(CH2-2-O-C6H4)TiCl2 (2d) are used in ethylene and propylene homopolymerization, and ethylene/1-octene copolymerization. All complexes, upon their activation with Al(iBu)(3)/Ph3CB(C6F5)(4), exhibit reasonable catalytic activity for ethylene homo- and copolymerization giving linear polyethylene with high to ultra-high molecular weight (600x 10(3)-3600x 10(3) g/mol). The activity of 1a/Al(iBu)(3)/Ph3CB(C6F5)(4) shows a positive comonomer effect, leading to over 400% increase of the polymer yield, while the addition of 1-octene causes a slight reduction of the activity of the complexes 2a-2d. The complexes with the NMe2 donor group (2a, 2d, 1a) display a high ability to incorporate a comonomer (up to 9-22 mol%), and the use of a bulkier donor group, N(iPr)(2) (2b, 2c), results in a lower 1-octene incorporation. All the produced copolymers reveal a broad chemical composition distribution. In addition, the investigated complexes polymerized propylene with the moderate (1a, 2a) to low (2b-2d) activity, giving polymers with different microstructures, from purely atactic to isotactically enriched (mmmm=28%). (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2467-2476