Poly(3,5‐dichloroaniline) Doped with Different Sulfonic Acids

Poly(3,5‐dichloroaniline) was prepared by chemical oxidation in the presence of various sulfonic acids as doping agent, using potassium permanganate as oxidant. 1‐Naphtalene sulfonic acid, 2‐naphatalene sulphonic acid, 1,5‐naphtalene disulfonic acid, and p‐toluenesulfonic acid were the acids of choice. Infrared and UV‐Vis spectroscopy, utilized to characterize the polymers, revealed that the compounds exist in the emeraldine (conductive) oxidation state. The level of doping, conductivity, and morphology were determined as well. The presence of a sulfonic acid produces a morphological change, from granular to microtubule structures, which is responsible for the strong increase in the conductivity of the polymer.     

The side chain effects on TPD-based copolymers: the linear chain leads to a higher jsc

Abstract

Alkyl substituents appended to polymers play the determining role on self-assembly and film-forming properties, and on device performance. In this work, we highlight the effects of the linear and branched flexible chains appended to the acceptor moiety (A) in D-A type copolymers. Two thieno[3,4-c]-pyrrole-4,6-dione (TPD) based copolymers PT1 and PT2 with different alkyl chains, were designed and synthesized. By comparison their UV-vis absorptions, HOMO/LUMO energy levels, as well as the characters in polymer solar cells, the influences of alkyl chains were investigated. Both copolymers showed molecular weights of 21?kDa and similar optical properties with a medium band gap of 1.93?eV, while PT2 with the branched chain exhibited a lower HOMO than that of PT1 (?5.43 vs???5.37?eV). In bulk heterojunction (BHJ) solar cells, PT1 with a linear chain presented a short circuit current (J_sc) of 6.76?mA cm^?2, open circuit voltage (V_oc) of 0.89?V and power conversion efficiency (PCE) of 2.92%. To the contrary, PT2 showed a J_sc of 3.53?mA cm^?2, V_oc of 0.99?V, delivering a relatively lower PCE of 2.05%. The result indicates that appending a linear alkyl chain to the TPD unit could sufficient enhance the J_sc value of the related polymer.     

Benzyl Bromide Functionalized Poly(Phenyleneethynylene)s as Macroinitiators in the Atom Transfer Radical Polymerization of Methyl Methacrylate

Abstract

The behavior of benzyl bromide functionalized poly(phenyleneethynylene)s as macroinitiators in the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was investigated. The ¹H NMR observation of the ATRP using the exclusively para‐linked poly(phenyleneethynylene) macroinitiator PPE1A, and the low molecular weight initiator R‐BzBr, respectively, revealed lower reactivity for the macroinitiator. Comparison of graft copolymers, which were obtained from ATRP of MMA with PPE1A and the partially meta‐linked poly(phenyleneethynylene) PPE1B, showed higher reactivity in the case of PPE1B, expressed by a larger degree of polymerization in the PMMA side chains, as well as higher initiatior efficiency. This might be caused by better solubility of the less symmetric PPE1B. Investigation of the graft copolymers PPE2A and PPE2B was carried out by means of ¹H NMR spectroscopy, gel permeation chromatography (GPC) as well as UV/vis spectroscopy. Impairment of the delocalized π‐electron system of the conjugated polymers during the ATRP was not detectable.     

Rationally Designing Molecularly Imprinted Polymer Toward a High Specific Adsorbent by Using Metal as Assembled Pivot

This article presents an original work aimed at rationally designing molecularly imprinted polymer (MIP) toward a high specific adsorbent. Assembling with cobalt as the pivot, the MIP was prepared by coordinating polymerizable monomers around an inducible template. The use of pivot obviously plays a positive role on increasing the specificity of MIP, so as to adsorb more for the template and less for its analogue. Related studies indicate that these may be a result of increasing specific interaction, which makes the MIP capable of recognizing the imprint species. Further information from thermodynamic analysis reveals that the increasing specific interaction, in logic, can be due to a higher fidelity of imprint, which specifically allures the template to bind.     

Polyurethane Ionomers from Cycloaliphatic Diisocyanate and Polytetramethylene Glycol

Abstract

Segmented polyurethane (PU) ionomers were prepared from cycloaliphatic diisocyanate [methylene bis(4-cyclohexyl isocyanate) (H₁₂MDI) and isophoron diisocyanate (IPDI)] and polytetramethylene glycol (PTMG) by using an anionic-type chain extender, viz., dimethylol propionic acid (DMPA). The effect of ionic content and butanediol (BD) on the state of dispersion and physical properties of emulsion-cast film was determined using Autosizer, transmission electron microscopy (TEM), Instron, and Rheovibron. With increased incorporations of DMPA in PU, particle size of emulsion decreased asymptotically, tensile modulus and strength increased, and the glass transition temperature (T _g) moved toward the higher temperature. On the other hand, with increased incorporation of BD in PU, particle size of emulsion, tensile modulus, and strength of the emulsion cast film increased, and the major transition of soft segment moved toward higher temperature. With regard to the structural effect of the isocyanate, H₁₂MDI gave finer dispersion and better mechanical properties over IPDI.     

Viscometric Estimation of Unperturbed Chain Dimensions of Polymers

A new expression is proposed to determine the unperturbed dimensions of coil-like polymers viscometrically by use of the Flory and Kratky expression. The unperturbed dimensions so estimated are compared with the results obtained by using different expressions available in the literature. The results are comparable even for stiff chain polymers. The data obtained under theta conditions also fit this expression very well. The effect of molecular weight, its distribution, and that of the solvent has also been studied. It is concluded that the unperturbed dimensions are independent of molecular weight and solvent but depend on the heterogeneity of the system.     

Polymerization of N,N-Dimethylaminopropyl-Acrylamide Through Hydrogen Transfer Induced by the Propagation of the Polyacrolein Anion

The anionic polymerization of acrolein (AL) with N, N-dimethylamino-propylacrylamide (DMAPA) in the presence of water was investigated in tetrahydrofuran, benzene, and ethanol at 0°C in a nitrogen atmosphere. The resulting polymers were found to be essentially vinyl polymers with one DMAPA attached and an aldehyde side chain. From observations of the polymerization process by ¹H NMR, we find that polymerization was initiated by the hydroxyl anion formed in the thermodynamic equilibrium between the amine of DMAPA and water. The hydrogen transfer reaction of DMAPA was caused by the propagating poly-AL anion. On the other hand, the monomer reactivity ratios and the Q₂-e₂values of DMAPA were determined by the free-radical copolymerization of styrene (St, M₁) with DMAPA and AIBN as initiator.     

Preparation and Characterization of PMMA/MMT Organic-Inorganic Hybrid Materials via RAFT Polymerization

In this article, the poly(methyl methacrylate)/montmorillonite (PMMA/MMT) organic-inorganic hybrid materials were prepared by conventional free radical polymerization and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. The kinetics comparison of these two polymerizations was studied. The PMMA/MMT hybrid materials were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). According to these results, we knew that the polymerization behavior of MMA showed controlled/living radical polymerization (CLRP) characteristics under the control of RAFT agent. The incorporation of RAFT agent and MMT nanoparticles improved the thermal properties of polymers, and the thermal stability of polymers increased with increasing content of MMT nanoparticles. The structures and morphologies of PMMA/MMT hybrid materials were characterized by FT-IR, XRD and TEM. These results showed that the MMA monomer can be initiated and propagated in the clay layers of MMT via the control of RAFT agent, and then the exfoliated structure was obtained for the hybrid materials.     

Rheological Behavior of Dope Solutions of Poly(acrylonitrile‐co‐itaconic acid) in N,N‐dimethylformamide: Effect of Polymer Molar Mass

The rheological behavior of dope solutions of poly(acrylonitrile‐co‐itaconic acid) or poly(AN‐co‐IA) is important from the point of view of deriving the spinning conditions for good quality special acrylic fibers. The viscosity of the resin dope is dictated by the polymer concentration, molar mass, temperature and shear force. The dynamic shear rheology of concentrated poly(AN‐co‐IA) polymer dope solutions in N, N‐dimethylformamide, in the molar mass (M¯_v) range of 1×10⁵ to 1×10⁶ g/mol, was investigated in the shear rate (γ′) range of 1×10¹ to 5×10⁴ min^?1. An empirical relation between η and M¯_v was found to exist at constant shear rate. The dope viscosity was dependent on the molar mass and the shear rate at a given temperature (T) and concentration. The polymer molar mass index of dope viscosity (m) was calculated as functions of concentration (c), shear rate and temperature. The m values increased with shear rate and temperature. A master equation relating m, with shear rate and temperature was derived for a given dope concentration. At higher shear rates, m tends to the value of 3.4, which is close to the molar mass index of viscosity reported for molten thermoplastics. m increased significantly with shear rate and nominally with temperature, while an increase in concentration decreased it. The onset of shear thinning of the dope shifted to a lower shear rate regime with an increase in polymer concentration and the molar mass. For a given value of molar mass, the increase in viscosity of the dope solution with polymer concentration was dependent on the shear rate.     

NOTE: Synthesis and Characterization of a Poly(acrylamide) with Pendant 1,4-piperazine-2,5-dione Moieties via Post-polymerization Cyclization

A poly(acrylamide) was synthesized from N ^α -Boc-N ^? -acrolyl-l-lysylglycine methyl ester via radical polymerization. This polymer typically had Mn ～ 100,000 g/mol, Mw ～ 300,000 g/mol, and a T_g of 93°C. Removal of Boc with TFA and cyclization with DABCO? in DMSO at 65°C afforded a soluble piperazinedione-containing polymer that had a T_g of 157°C and thermal stability up to 300°C. These results demonstrate a viable and efficient synthetic route to piperazinedione-containing polyacrylamides of high molecular weight. Related polymers that incorporate substituted indane moieties could be useful high T_g materials for fabrication of LC and NLO devices.