Rakchart Traiphol

Perfluorocyclobutane (PFCB) polyaryl ethers: versatile coatings materials

Abstract The cyclopolymerization of aromatic trifluorovinyl ether (TFVE) monomers offers a versatile route to a unique class of linear and network fluoropolymers containing the perfluorocyclobutyl (PFCB) linkage. Polymerization proceeds by a thermal — radical mediated — step-growth mechanism and provides well-defined polymers containing known fluoroolefin end groups. PFCB polymers combine the engineering thermoplastic nature of polyaryl ethers with fluorocarbon segments and exhibit excellent processability, optical transparency, high temperature performance, and low dielectric constants. An intermediate strategy utilizing Grignard and aryllithium reagents has been developed which offers access to a wide variety of hybrid materials amenable to coatings applications. Liquid crystalline examples have recently been achieved in addition to tailoring optical properties by co-polymerization.

Roles of head group architecture and side chain length on colorimetric response of polydiacetylene vesicles to temperature, ethanol and pH.

In this contribution, we report the relationship between molecular structures of polydiacetylene (PDA) vesicles, fabricated by using three monomers, 10,12-tricosadiynoic acid (TCDA), 10,12-pentacosadiynoic acid (PCDA) and N-(2-aminoethyl)pentacosa-10,12-diynamide (AEPCDA), and their color-transition behaviors. The modification of side chain length and head group of the PDA vesicles strongly affects the colorimetric response to temperature, ethanol and pH. A shorter side chain of poly(TCDA) yields weaker inter- and intra-chain dispersion interactions in the bilayers compared to the system of poly(PCDA), which in turn results in a faster color transition upon exposure to all stimuli. A change of head group in poly(AEPCDA) slightly reduces the transition temperature. Interestingly, the colorimetric response of poly(AEPCDA) vesicles to the addition of ethanol is found to occur in a two-step fashion while the response of poly(PCDA) vesicles takes place in a one-step process. The amount of ethanol required for inducing complete color-transition of poly(AEPCDA) vesicles is also much higher, about 87% v/v. The increase of pH to ~9 and ~10 causes a color-transition of poly(TCDA) and poly(PCDA) vesicles, respectively. The poly(AEPCDA) vesicles, on the other hand, change color upon decreasing pH to ~0. The colorimetric response also occurs in a multi-step fashion. These discrepancies are attributed to the architecture of surface layers of poly(AEPCDA), constituting amine and amide groups separated by ethyl linkers.

Stable polydiacetylene/ZnO nanocomposites with two-steps reversible and irreversible thermochromism: The influence of strong surface anchoring

This contribution introduces a versatile method to prepare a new class of polydiacetylene(PDA)-based material. ZnO nanoparticle is used as a nano-substrate for spontaneous assembling of diacetylene monomer, 10,12-pentacosadiynoic acid, on its surface. An irradiation of the organized assemblies by UV light results in PDA/ZnO nanocomposites with deep blue color. Strong ionic interaction and hydrogen bonding at the ZnO surface restrict the dynamics of alkyl side chains and promote the PDA ordering, which in turn drastically affects its thermochromic behaviors. We have found that the PDA/ZnO nanocomposite exhibits two-steps color transition upon increasing temperature. The first transition of the nanocomposite in aqueous suspension, causing the color change from blue to purple, occurs reversibly at ∼90°C. The transition temperature shifts to ∼100°C when the nanocomposite is embedded in polyvinyl alcohol matrix. Further increasing temperature to 145°C induces the second transition, which causes irreversible color change from purple to red.

Controlling the reversible thermochromism of polydiacetylene/zinc oxide nanocomposites by varying alkyl chain length.

In this work, polydiacetylene (PDA)/ZnO nanocomposites are successfully fabricated by using three types of monomers with different alkyl chain length, 5,7-hexadecadiynoic acid, 10,12-tricosadiynoic acid, and 10,12-pentacosadiynoic acid. The monomers dispersed in aqueous medium spontaneously assemble onto the surface of ZnO nanoparticles, promoted by strong interfacial interactions. The PDA/ZnO nanocomposites obtained via photopolymerization process are characterized by scanning electron microscopy, laser light scattering, infrared spectroscopy, and uv/vis absorption spectroscopy. The strength of interfacial interactions and morphologies of the nanocomposites are found to vary with alkyl chain length of the monomers. The PDA/ZnO nanocomposites also exhibit rather different thermochromic behaviors compared to their pure PDA counterparts. All nanocomposites show reversible blue/purple color transition upon multiple heating/cooling cycles, while the irreversible blue/red color transition is observed in the systems of pure PDAs. The shortening of alkyl side chain in PDA/ZnO nanocomposites leads to a systematic decrease in their color-transition temperatures. Colors of the nanocomposites at elevated temperature also vary with the alkyl chain length. Our results provide a simple route for controlling the reversible thermochromism of PDA-based materials, allowing their utilization in a wider range of applications.

Control over the color transition behavior of polydiacetylene vesicles using different alcohols

In this contribution, we investigate the color transition behavior of polydiacetylene (PDA) vesicles upon exposure to different chemical stimuli. A series of linear and branched alcohols are used as model additives, allowing systematic control of their molecular shape and polarity. The PDA vesicles are fabricated by using three monomers, 10,12-pentacosadiynoic acid (PCDA), 10,12-tricosadyinoic acid (TCDA), and N-(2-amino ethyl)pentacosa-10,12-dyinamide (AEPCDA). When a series of linear alcohols is used, the longer alcohol length causes color transition of all PDA vesicles. In this system, the penetration of linear alcohols into the inner layer of PDA vesicles is dictated by their polarity. The change of -OH position within the alcohol molecule also affects the degree of penetration. It requires a higher amount of the 2-propanol to induce color transitions of the PDAs compared to that of the 1-propanol. The addition of methyl branches into the hydrophobic tail of alcohols causes an increase in steric effect, which hinders the penetration as well. When the 2,2-dimethyl-1-propanol is used as a stimulus, the color transition of PDAs occurs at much higher alcohol concentration compared to 2-methyl-1-butanol, 3-methyl-1-butanol, and 1-pentanol. The variation of PDA structures also affects their ability to interact with the alcohols. The modified head group of poly(AEPCDA) promotes the ability to distinguish between 1-propanol and 2-propanol or 1-propanol and ethanol.

From single molecules to aggregates to gels in dilute solution: Self-organization of nanoscale rodlike molecules

A transition from a fluid to a constrained phase, in dilute solutions of a rodlike molecule, poly(2,5-dinonylparaphenylene ethynylene)s (PPE) in toluene has been studied, exploring the dynamics and the structure of the PPE molecules and the solvent in both phases. The transition is characterized by visual changes in the viscosity of the system and in its color, where a transparent liquid transforms into a yellow glassy phase. Nuclear magnetic resonance relaxation measurements indicated that significant restriction of motion of the solvent and of the polymeric molecule take place as the gel-like phase is formed. Small angle neutron scattering studies have shown that in the liquid phase, PPE forms molecular solutions where the molecules are fully extended. Upon transition into the constrained phase, aggregation of PPE molecules into large flat clusters occurs. When the aggregates are too large to freely move in the solution, a transition into a constrained phase takes place. The interaction between the highly conjugated PPE molecules and the solvent results in constraint of the motion of the solvent as well.

Dual colorimetric response of polydiacetylene/Zinc oxide nanocomposites to low and high pH

This contribution presents our continuation work on the color-transition behaviors of polydiacetylene(PDA)/ZnO nanocomposites prepared by using three types of monomers, 5,7-hexadecadiynoic acid (HDDA), 10,12-tricosadiynoic acid (TCDA) and 10,12-pentacosadiynoic acid (PCDA). The color-transition behaviors of these nanocomposites upon exposure to acid and base are investigated by utilizing UV/vis absorption spectroscopy. We have found that these PDA/ZnO nanocomposites exhibit colorimetric response at both low and high pH regions. The addition of acid causes the poly(HDDA)/ZnO, poly(TCDA)/ZnO and poly(PCDA)/ZnO nanocomposites to change color from blue to red at pH~5, 3.5 and 2, respectively. The color of pure PDA vesicles, on the other hand, is hardly affected at this pH range. At high pH region, the pure poly(TCDA) vesicles change color at pH~8 while it requires much higher pH to induce color transition of the PDA/ZnO nanocomposites. The mechanism responsible for color transition of the PDA/ZnO nanocomposites is explored by various techniques including infrared spectroscopy, zeta potential analyzer and light scattering. Our result provides a new approach for controlling the colorimetric response to pH of PDA-based materials.

Fine tuning the color-transition temperature of thermoreversible polydiacetylene/zinc oxide nanocomposites: The effect of photopolymerization time.

An ability to control the thermochromic behaviors of polydiacetylene (PDA)-based materials is very important for their utilization. Recently, our group has developed the PDA/zinc oxide (ZnO) nanocomposites, which exhibit reversible thermochromism (Traiphol et al., 2011). In this study, we present our continuation work demonstrating a rather simple method for fine tuning their color-transition temperature. The PDA/ZnO nanocomposites are prepared by varying photopolymerization time, which in turn affects the length of PDA conjugated backbone. We have found that the increase of photopolymerization time from 1 to 120min results in systematically decrease of the color-transition temperature from about 85 to 40°C. These PDA/ZnO nanocomposites still exhibit reversible thermochromism. The PDA/ZnO nanocomposites embedded in polyvinyl alcohol films show two-step color-transition processes, the reversible blue to purple and then irreversible purple to orange. Interestingly, the increase of photopolymerization time causes an increase of the irreversible color-transition temperature. Our method is quite simple and cheap, which can provide a library of PDA-based materials with controllable color-transition temperature.

Influences of structural mismatch on morphology, phase transition temperature, segmental dynamics and color-transition behaviors of polydiacetylene vesicles

In this contribution, we report a systematic study of polydiacetylene (PDA) vesicles fabricated by mixing two types of monomers, 10,12-tricosadiynoic acid (TCDA) and 10,12-pentacosadiynoic acid (PCDA). These diacetylene (DA) monomers constitute the same head group but different alkyl chain length, which in turn causes structural mismatch within the PDA layers. The PCDA:TCDA ratios are 100, 75, 50, 25 and 0mol%. Morphologies and properties of these PDA vesicles are explored by utilizing laser light scattering, transmission electron microscopy, differential scanning calorimetry, temperature-dependent nuclear magnetic resonance spectroscopy (NMR) and spin-lattice relaxation time (T1) measurements. An increase in DA mole ratio to 50mol% leads to significant increase in particle size. The mixed PDA vesicles also exhibit irregular shape with rather rough surface. The mismatch of alkyl side chain causes the drop of phase transition temperature. For the system of mixed poly(PCDA50:TCDA50), its transition temperature is lower than those of the pure PDAs. The NMR line shape analysis detects an abrupt change of proton signal adjacent to the PDA head group during the blue/red color-transition process. The T1 measurements also reveal different local environments of PDA alkyl side chains in the blue and red phases. The mismatch of PDA side chains causes significant drop of the color-transition temperature.

Solvent-Induced Photoemissions of High-Energy Chromophores of Conjugated Polymer MEH-PPV: Role of Conformational Disorder

This study examined the photoemission behaviors of isolated chains of poly[2-methoxy, 5-(2′-ethylhexyloxy)-1,4-phenylenevinylene](MEH-PPV) dispersed in various solvents including dichloromethane, chloroform and tetrahydrofuran(THF). A change in polymer-solvent interactions in these solutions caused the MEH-PPV chains to adopt different local conformations, which in turn affected their radiative de-excitation pathways. For the polymer in dichloromethane and chloroform, in which the conjugated chains are relatively extended, photoemission occurs mostly at the long chromophores with lowest HOMO-LUMO energy gap. Their emission spectra showed a main peak at ∼560 nm. Dual photoemission of high- and low-energy chromophores was observed when the conjugated chains were forced to partially collapse in a poor solvent THF. Novel high-energy peaks and a typical low-energy peak were detected at ∼414 nm and ∼554 nm, respectively. The observation of the high-energy peaks indicates significant suppression of the intrachain energy transfer process, which was attributed to the increase in conformational disorder in the partially collapsed coils. An analysis of the excitation spectra suggests that the high-energy peaks belong to short chromophores constituting of one or two repeat units. This study systematically investigated the effects of polymer concentration, temperature and single bond defects along the backbone on the photoemission of the high-energy chromophores.