Dry-jet wet spinning of aromatic polyamic acid fiber using chemical imidization

A solution of about 15% polyamic acid (PAA) prepared from 4,4′-oxydianiline and pyromellitic dianhyride in N,N-dimethyl acetamide (DMAc) was used for fiber spinning. To obtain a high draw ratio of the PAA fiber during spinning, acetic anhydride or acetic anhydride and pyridine were added to the PAA solution to make it slightly gelled; such gelling contributed to high drawing of the PAA fibers during spinning. Before spinning the properties of the solution after acetic anhydride or acetic anhydride and pyridine were added, and the diffusion property of DMAc into various coagulants were examined. Even though acetic anhydride was only added to the spinning solution, the diffusion rate became slower and the solution viscosity increased, because PAA was converted to the corresponding polyimide (PI). Pyridine affected the rate dramatically. The mechanical properties of the PAA fibers obtained in this system were examined. Solid PI fibers were also obtained by annealing of the PAA fibers. The ultimate stress and initial modulus of the PAA fiber were around 268 MPa and 4.1 GPa, respectively. After the fiber was annealed at 350°C without tension for 30 min under nitrogen, these values increased to around 399 MPa and 5.2 GPa, respectively.     

Polymerization of ionic monomers in polar solvents: kinetics and mechanism of the free radical copolymerization of acrylamide/acrylic acid

A precise data set describing the kinetics of the free radical copolymerization of acrylamide/acrylic acid (AM/AA) in the range of low total monomer concentration as a function of the pH, total monomer concentration, initiator concentration, and comonomer ratio is presented. Strong impact on the reactivity ratios has been identified for the pH and total monomer concentration. Specifically, at constant total monomer concentration of 0.4 mol/l and T=313 K the reactivity ratio of AM increases from 0.54 at pH 1.8 to 3.04 at pH 12. Contrarily, the reactivity ratio of AA decreases from 1.48 to 0.32. The crossover occurs at pH≈4.2. Electrostatic effects due to the variation of the degree of ionization of AA are primarily suggested to influence the kinetics. When the total monomer concentration increases from 0.2 to 0.6 mol/l at constant pH=12, the reactivity ratios of AM and AA decrease from 4.01 to 2.13 and increase from 0.25 to 0.47, respectively. Reduction of electrostatic repulsion between the ionized monomer AA and partially charged growing polymer chain ends due to higher ionic strength at higher total monomer concentration serves as explanation of the effect. The precise data set is the prerequisite for a novel approach to calculate copolymer compositions in case of variable monomer reactivity.     

Lewis acid and base sites at the surface of microcrystalline TiO2 anatase: relationships between surface morphology and chemical behaviour

The relationships between morphology and Lewis acid and base character of surface sites of two types of titania powders (TiO₂ P25 and TiO₂ Merck) were studied by HRTEM and FTIR spectroscopy of adsorbed molecules. Electron micrographs revealed that TiO₂ P25 microcrystals have a prismatic shape, mainly exposing (0 0 1) and (0 1 0) surface planes. TiO₂ Merck powder, which exhibits a significantly lower specific surface area, appeared constituted by large roundish microcrystals. FTIR spectra of adsorbed CO indicated that Ti⁴⁺ ions exposed on (0 0 1) and (0 1 0) faces of TiO₂ P25 particles are Lewis acid centres significantly stronger than those present on the surface of TiO₂ Merck microcrystals. As in both cases the exposed cations are coordinated to five oxygen anions, the observed differences in Lewis acidity are ascribed to some difference in the geometric arrangement of the O²⁻ ligands. Such difference in structure affects the basicity of these centres also. In fact, a fraction of O²⁻ ions on the surface of TiO₂ P25 behave as basic centres toward CO₂ linearly adsorbed on neighbour Ti⁴⁺ centres, and then Lewis acid–base pairs can be recognised. By contrast, no basic activity towards CO₂ was detected for the TiO₂ Merck sample.

The two titania powders exhibited different chemical behaviour in condition of high surface hydration also. Hydroxyl groups on the surface of hydrated TiO₂ P25 are able to transform benzaldehyde molecules in hemiacetalic-like species, whereas C₆H₅CHO molecules are only weakly perturbed by interaction with the OH groups on TiO₂ Merck particles. This feature could be related to the different photocatalytic behaviour in the oxidation of toluene in gas phase, where benzaldehyde was found as a relevant intermediate species.     

Kinetics and reaction mechanism of template polymerization investigated by conductimetric measurements Part 4. Radical polymerization of acrylic acid in the presence of poly(vinyl alcohol): characterization of resulting polymer blends

The radical polymerization of acrylic acid in the presence of poly(vinyl alcohol) as a template in aqueous solution has been studied using conductimetry, which shows template influences on the reaction rate. A comparison is made between data obtained by differential scanning calorimetry and infrared spectroscopy for poly(acrylic acid)–poly(vinyl alcohol) blends prepared either by template polymerization or by casting of the preformed polymers. Evidence for more significant interpolymer interactions in blends prepared by template polymerization than in those obtained by simple mixing is given. © 2001 Society of Chemical Industry     

Synthesis of high molecular weight poly(L‐lactic acid) via melt/solid polycondensation: Intensification of dehydration and oligomerization during melt polycondensation

Melt/solid state polycondensation (MP/SSP) is a cost‐effective route for synthesis of high molecular weight poly(L ‐lactic acid) (PLLA). However, the reaction rates in its four stages need to be enhanced greatly and the reaction times to be shortened largely before the MP/SSP technology can be industrialized. In this study, a new catalyst addition policy, i.e., adding TSA at the dehydration stage and SnCl₂·2H₂O at the MP stage, and more appropriate temperature and pressure programs were presented and applied in the MP process of LLA. The presence of TSA from dehydration appeared very effective for speeding up the dehydration and oligomerization stages as well as depressing racemization in the whole MP process. The polymerization degree (X_n) of oligomer was clearly increased, and the reaction time was shortened to a great extent. Direct using reduced pressure was also very helpful for intensifying the dehydration stage, only leading to LLA loss as little as 2%. A PLLA with M_w of 44,000 and optical purity of 96.8% suitable for subsequent SSP was produced after dehydration for 2 h, oligomerization for 2 h and MP for 4 h under appropriate conditions. And an interesting strong dependence of the M_w of final PLLA product on the X_n of the oligomer was observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011