Browsing by Author "Chen, Show-An"

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Fractal aggregates of conjugated polymer in solution state
(2006-12-19)
Li, Yen-Cheng
;
Chen, Kuei-Bai
;
Chen, Hsin-Lung
;
Hsu, Chain-Shu
;
Tsao, Cheng-Si
Semirigid conjugated polymers have received much scientific and technological interest due to their unique electrical and photonic semiconducting properties. Spectroscopic studies have indicated that these polymers underwent interchain aggregation in the solution state even at large dilution; however, the origin of this event and the structure of the resultant aggregates remained the crucial issues to be resolved. In the present study, we revealed that the interchain aggregation of a conjugated polymer, poly(2,3-diphenyl-5-hexyl-1,4-phenylenevinylene) (DP6-PPV), in solutions with chloroform and toluene generated network aggregates with the hydrodynamic radii of several micrometers. Small angle neutron scattering (SANS) demonstrated that the internal structure of these aggregates could be characterized by the mass fractal dimensions of 2.2-2.7. The networks were looser in chloroform but became highly compact in the poorer toluene solvent due to severe segmental association. Increasing the temperature alleviated the segmental association in toluene while largely retaining the mass fractal dimension of the aggregates. However, the interchain aggregation was never completely dissipated by the heating, suggesting the existence of two types of segmental association with distinct stability. The highly stable segmental association that could neither be solvated by chloroform nor be disrupted thermally in toluene was attributed to the d-d complex already present in the DP6-PPV powder used for the solution preparation. The chains tied firmly by this complex formed network aggregates in the solution and hence reduced the entropy of mixing of the polymer. In the poorer toluene solvent, further segmental association took place within the preexisting aggregates, making the networks more compact. This type of segmental association could be disrupted by moderate heating, and its occurrence was ascribed to the poor affinity of the aliphatic side chains of DP6-PPV for toluene.
Scattering Study of the Conformational Structure and Aggregation Behavior of a Conjugated Polymer Solution
(2009-04-21)
Li, Yen-Cheng
;
Chen, Chun-Yu
;
Chang, Ying-Xun
;
Chuang, Pei-Ying
;
Chen, Jean-Hong
The conformational structure and the interchain aggregation behavior of a semirigid conjugated polymer bearing a decyl side chain, poly(2,3-diphenyl-5-decyl-1,4-phenylenevinylene) (DP10-PPV), in solutions with chloroform and toluene have been investigated by means of small-angle neutron scattering (SANS), static light scattering (SLS) and dynamic light scattering (DLS). The radius of gyration, persistence length, and the second virial coefficient of the polymer in dilute solution as determined by SLS were higher in chloroform than in toluene; consequently, the polymer assumed a more extended wormlike chain conformation in the former. The difference in the strength of interaction in the two solvents gave rise to contrasting aggregation behavior of the polymer in the semidilute regime. While only a minor fraction of the polymer underwent segmental association in chloroform, a considerable fraction of it formed clusters (microgels) with several micrometers in size in toluene. These clusters were further found to consist of sheetlike nanodomains. Compared with the DP-PPV bearing a shorter hexyl side chain, DP6-PPV, the aggregates of DP10-PPV in toluene were weaker as they could be easily disrupted by moderate heating. This was attributed to a lack of strong pi-pi interaction between the DP10-PPV segments due to the greater steric hindrance imposed by the longer decyl side chains.
Supramolecular structures of an amphiphilic hairy-rod conjugated copolymer bearing poly(ethylene oxide) side chain
(2009-07-01)
Liao, Shao-Ching
;
Lai, Chia-Sheng
;
Yeh, Di-Di
;
Rahman, M. Habibur
;
Hsu, Chain-Shu
The structures of an amphiphilic conjugated graft copolymer, poly(2,3-diphenyl-5-(trimethylene-heptadeca(oxyethylene)-methoxy-phenylene vinylene) (denoted as PVEO(17)) composing of a conjugated DP-PPV backbone and PEO side chains, in bulk and solutions with tetrahydrofuran (THF) and water have been investigated by small-angle X-ray scattering (SAXS). In bulk state, the DP-PPV main chains in PVEO(17) stacked to form flat disk microdomains dispersed in the PEO side-chain matrix. The corresponding wide angle X-ray scattering pattern revealed the existence of crystallinity of the PEO side chains. The structure of the polymer in solution was affected by the solvent quality and the polymer concentration. PVEO(17) chains were relatively well dispersed in THF. In aqueous solutions, however, the amphiphilic PVEO(17) chains aggregated significantly over the concentration range of 1-8 wt%, where the polymer was found to self-organize to form cylindrical micelles with the aggregation number increasing with the increase of concentration. The photophysical properties characterized by UV-Vis and photoluminescence spectroscopy were strongly affected by the aggregation state of the polymer. (C) 2009 Elsevier Ltd. All rights reserved.