Preprint Article Version 1 This version is not peer-reviewed

Effect of Configuration of a Bulky Aluminum Initiator on the Structure of Copolymers of L,L-Lactide with Symmetric Comonomer Trimethylene Carbonate

Version 1 : Received: 6 December 2017 / Approved: 7 December 2017 / Online: 7 December 2017 (05:01:27 CET)
Version 2 : Received: 10 January 2018 / Approved: 10 January 2018 / Online: 10 January 2018 (10:45:16 CET)

A peer-reviewed article of this Preprint also exists.

Socka, M.; Szymanski, R.; Sosnowski, S.; Duda, A. Effect of the Configuration of a Bulky Aluminum Initiator on the Structure of Copolymers of l,l-Lactide with Symmetric Comonomer Trimethylene Carbonate. Polymers 2018, 10, 70. Socka, M.; Szymanski, R.; Sosnowski, S.; Duda, A. Effect of the Configuration of a Bulky Aluminum Initiator on the Structure of Copolymers of l,l-Lactide with Symmetric Comonomer Trimethylene Carbonate. Polymers 2018, 10, 70.

Journal reference: Polymers 2018, 10, 70
DOI: 10.3390/polym10010070

Abstract

The effect of configuration of an asymmetric bulky initiator 2,2’-[1,1’-binaphtyl-2,2’-diyl- bis-(nitrylomethilidyne)]diphenoxy aluminum isopropoxide (Ini) on structure of copolymer of asymmetric monomer L,L-lactide (Lac) with symmetric comonomer trimethylene carbonate (Tmc) was studied using polarimetry, dilatometry, SEC and 13C NMR. When the S-enantiomer of Ini was used the distribution in copolymer chains at the beginning of polymerization is statistical, with alternacy tendency, changing next through a gradient region to homoblocks of Tmc. When, however, R-Ini was used, the product formed was a gradient oligoblock one, with Tmc blocks prevailing at the beginning, changing to Lac blocks dominating at end part of chains. Initiation of copolymerization with the mixture of both initiator enantiomers (S:R = 6:94) gave multiblock copolymer, of similar features but shorter blocks. Analysis of copolymerization progress required complex analysis of dilatometric data, assuming different contraction coefficients for units located in different triads. Comonomer reactivity ratios of studied copolymerizations were determined.

Subject Areas

biodegradable copolyesters; copolymerization kinetics; copolymer microstructure; simulation; reactivity ratios; dilatometry

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