Tuning the synthesis of fully conjugated block copolymers to minimize architectural heterogeneity

2017 ◽  
Vol 5 (38) ◽  
pp. 20412-20421 ◽  
Author(s):  
Youngmin Lee ◽  
Melissa P. Aplan ◽  
Zach D. Seibers ◽  
S. Michael Kilbey ◽  
Qing Wang ◽  
...  

Control of conversion, end group composition, and feed ratio is crucial to minimize homopolymer impurities in the synthesis of conjugated block copolymers for photovoltaics.

2010 ◽  
Vol 11 (9) ◽  
pp. 2432-2439 ◽  
Author(s):  
Florian D. Jochum ◽  
Peter J. Roth ◽  
Daniel Kessler ◽  
Patrick Theato
Keyword(s):  

2013 ◽  
Vol 66 (12) ◽  
pp. 1564 ◽  
Author(s):  
Lily A. Dayter ◽  
Kate A. Murphy ◽  
Devon A. Shipp

A single reversible addition–fragmentation chain transfer (RAFT) agent, malonate N,N-diphenyldithiocarbamate (MDP-DTC) is shown to successfully mediate the polymerization of several monomers with greatly differing reactivities in radical/RAFT polymerizations, including both vinyl acetate and styrene. The chain transfer constants (Ctr) for MDP-DTC for both these monomers were evaluated; these were found to be ~2.7 in styrene and ~26 in vinyl acetate, indicating moderate control over styrene polymerization and good control of vinyl acetate polymerization. In particular, the MDP-DTC RAFT agent allowed for the synthesis of block copolymers of these two monomers without the need for protonation/deprotonation switching, as has been previously developed with N-(4-pyridinyl)-N-methyldithiocarbamate RAFT agents, or other end-group transformations. The thermal properties of the block copolymers were studied using differential scanning calorimetry, and those with sufficiently high molecular weight and styrene composition appear to undergo phase separation. Thus, MDP-DTC may be useful for the production of other block copolymers consisting of monomers with highly dissimilar reactivities.


1996 ◽  
Vol 102 (1) ◽  
pp. 91-98 ◽  
Author(s):  
Eberhard Esselbom ◽  
Jürgen Fock ◽  
Arno Knebelkamp

Polymer ◽  
2016 ◽  
Vol 107 ◽  
pp. 368-378 ◽  
Author(s):  
Daniel Hermida Merino ◽  
Antonio Feula ◽  
Kelly Melia ◽  
Andrew T. Slark ◽  
Ioannis Giannakopoulos ◽  
...  

Materials ◽  
2018 ◽  
Vol 11 (9) ◽  
pp. 1608 ◽  
Author(s):  
Elaine Rahmstorf ◽  
Volker Abetz

The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermo-reversible, supramolecular networks. Several polyisoprene-block-polystyrene-block-polyisoprene (ISI) copolymers—with polystyrene (PS) as the main block, and consequently giving the decisive material characteristics—were synthesized. The novel modification approach to post-functionalize the polyisoprene (PI) end-blocks and to introduce different motifs, which are able to form self-complementary hydrogen bonds, was attained. In the first step, hydroxylation was accomplished using 9-borabicyclo[3.3.1]nonane. Starting from the hydroxylated polymer, esterification with succinic anhydride was implemented to form an ester group with carboxylic end-group (-O-CO-CH2-CH2-COOH). In a second approach, 1,1’-carbonyldiimidazole was used as coupling agent to introduce various types of diamines (diethylenetriamine, triethylentetramine, and 2,6-diaminopyridine) to prepare urethane groups with amine end-group (-O-CO-NH-R-NH2). 1H NMR spectroscopy was used to confirm the successful synthesis and to calculate the degree of functionalization Df. Differential scanning calorimetry (DSC) showed a difference of the glass transition temperature Tg between unfunctionalized and functionalized block copolymers, but no greater influence between the different types of modification, and thus, on the Tg of the PS block. In temperature dependent FTIR spectroscopy, reversible processes were observed.


2015 ◽  
Vol 53 (24) ◽  
pp. 2838-2848 ◽  
Author(s):  
Xu Xiang ◽  
Xiaochu Ding ◽  
Ning Chen ◽  
Beilu Zhang ◽  
Patricia A. Heiden

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