TY - JOUR
T1 - Well-Defined Non-Linear Polyethylene-Based Macromolecular Architectures
AU - Alshumrani, Reem
AU - Hadjichristidis, Nikos
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Research reported in this publication was supported by the King Abdullah University of Science and Technology (KAUST).
PY - 2018/8/7
Y1 - 2018/8/7
N2 - Polyethylene (PE)-based 3- and 4-miktoarm star [PE(PCL)2, PE(PCL)3] and H-type [(PCL)2PE(PCL)2] block copolymers [polycaprolactone (PCL)] were synthesized by a combination of polyhomologation, chlorosilane chemistry, and ring opening polymerization (ROP). The following steps were used for the synthesis of the miktoarm stars: (a) reaction of a hydroxy-terminated polyethylene (PE-OH), prepared by polyhomologation of dimethylsulfoxonium methylide with a monofunctional boron initiator followed by oxidation/hydrolysis, with chloromethyl(methyl)dimethoxysilane or chloromethyltrimethoxysilane; (b) hydrolysis of the produced ω-di(tri)methoxysilyl-polyethylenes to afford ω-dihydroxy-polyethylene (difunctional initiator) and ω-trihydroxy-polyethylene (trifunctional initiator); and (c) ROP of ɛ-caprolactone with the difunctional (3-miktoarm star) or trifunctional macroinitiator (4-miktoarm star), in the presence of 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-BuP2). The H-type block copolymers were synthesized using the same strategy, but with a difunctional polyhomologation initiator. All intermediates and final products were characterized by HT-GPC, 1H NMR and FTIR analyses. Thermal properties of the PE precursors and all final products were investigated by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018
AB - Polyethylene (PE)-based 3- and 4-miktoarm star [PE(PCL)2, PE(PCL)3] and H-type [(PCL)2PE(PCL)2] block copolymers [polycaprolactone (PCL)] were synthesized by a combination of polyhomologation, chlorosilane chemistry, and ring opening polymerization (ROP). The following steps were used for the synthesis of the miktoarm stars: (a) reaction of a hydroxy-terminated polyethylene (PE-OH), prepared by polyhomologation of dimethylsulfoxonium methylide with a monofunctional boron initiator followed by oxidation/hydrolysis, with chloromethyl(methyl)dimethoxysilane or chloromethyltrimethoxysilane; (b) hydrolysis of the produced ω-di(tri)methoxysilyl-polyethylenes to afford ω-dihydroxy-polyethylene (difunctional initiator) and ω-trihydroxy-polyethylene (trifunctional initiator); and (c) ROP of ɛ-caprolactone with the difunctional (3-miktoarm star) or trifunctional macroinitiator (4-miktoarm star), in the presence of 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-BuP2). The H-type block copolymers were synthesized using the same strategy, but with a difunctional polyhomologation initiator. All intermediates and final products were characterized by HT-GPC, 1H NMR and FTIR analyses. Thermal properties of the PE precursors and all final products were investigated by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018
UR - http://hdl.handle.net/10754/630476
UR - https://onlinelibrary.wiley.com/doi/full/10.1002/pola.29173
UR - http://www.scopus.com/inward/record.url?scp=85052445025&partnerID=8YFLogxK
U2 - 10.1002/pola.29173
DO - 10.1002/pola.29173
M3 - Article
SN - 0887-624X
VL - 56
SP - 2129
EP - 2136
JO - Journal of Polymer Science Part A: Polymer Chemistry
JF - Journal of Polymer Science Part A: Polymer Chemistry
IS - 18
ER -