Hydrolytic stability and protective properties of polyurethane oligomers based on polyester/ether/polyols

The present study deals with effect of the type and chemical character of incorporated polyester/polyether blocks on the hydrolytic stability of crosslinked polyurethane oligomers. Diffusion parameters of the investigated polyurethane oligomers, giving information concerning chemical changes taking place in neutral, basic and acidic aqueous environments, have also been determined.     

Investigations of surface characterization of silicone rubber due to tracking phenomena under a.c. and d.c. voltages

In the present work, tracking phenomena has been studied with silicone rubber material under the a.c. and d.c. voltages following IEC-587 standards. The surface condition of the tracked zone was analysed using wide angle X-ray diffraction (WAXD) and thermogravimetric differential thermal analysis (TG-DTA) studies. The tracking time was different for a.c. and d.c. voltages.     

Fractionation of partially stereoregular poly(propylene oxide)

Partially stereoregular poly(propylene oxide) samples were synthesized via reactions catalysed by a preformed analytically defined trimethylaluminium hydrolysate. These samples were fractionated into two contrastingly different fractions.

1. (i) D-polymers: This fraction constituted the major part (up to 90%). It mainly contained cyclic low molecular weight oligomers (MW < 1000). The linear chains found in D-polymers had hydroxyl end groups. No double bonds could be detected spectroscopically.

2. (ii) K-polymers: This fraction was high molecular weight stereoregular polymer. Stepwise thermal precipitation from dilute isooctane solution of K-polymers yielded a succession of fractions which differed in melting point. It appears that the phase equilibria during the thermal precipitations were not controlled by the molecular weights of species.

Investigations of surface degradation of high‐density polyethylene materials resulting from tracking,using physicochemical analysis

In the present work tracking phenomena were studied with high‐density polyethylene (HDPE) materials under dc voltage, with NH₄Cl and acid rain as contaminants. It was determined that the tracking time of the material depends on the conductivity and flow rate of the contaminant. Furthermore, physicochemical analysis by wide‐angle X‐ray diffraction studies, differential scanning calorimetry, and luminescence spectroscopy was carried out, whereupon it was concluded that the tracking process is a surface‐degradation process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2843–2849, 2002; DOI 10.1002/app.10260     

Hydrosilylation and dehydrocondensation reactions of methylhydridesiloxane to acrylic and methacrylic acids

The hydrosilylation of α,ω‐bis(trimethylsiloxy) methylhydridesiloxane (degree of polymerization ≈ 53) with acrylic and methacrylic acid with various ratios of the initial compounds, in the presence of platinum hydrochloric acid, has been investigated. In the presence of platinum hydrochloric acid, competitive dehydrocondensation reactions take place with the formation of various oligomers with various chemical links. In the later stages of the reaction, three‐dimensional systems have been obtained. During dehydrocondensation, the reaction order, reaction rate constants, and activation energy have been determined. The structures of the synthesized oligomers have been determined with IR and NMR spectroscopy data. Gel permeation chromatography, differential scanning calorimetry, and X‐ray analyses of the synthesized oligomers have been carried out. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3243–3252, 2007     

Enzyme‐catalyzed hydrolysis of poly(ethylene terephthalate) cyclic trimer

Oligoesters present in poly(ethylene terephthalate) fibers are commonly extracted from the fiber during processing, such as aqueous‐based dyeing. Aqueous, insoluble oligoesters, particularly cyclic trimers that precipitate on processing machinery and on the fiber surface are difficult to remove under benign conditions. Reported is a new method for the efficient removal of cyclic trimer by enzyme‐catalyzed hydrolysis. Almost complete hydrolysis of trimer was accomplished at pH 8 and 60°C. Effects of time, agitation, surfactant, and enzyme and trimer concentrations on the efficiency of hydrolysis are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2545–2552, 2003     

Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

One‐step synthesis and ring‐opening polymerization of novel macrocyclic(arylene multisulfide) oligomers

A series of macrocyclic(arylene multisulfide) oligomers were synthesized under high dilution conditions by reacting diphenyl ether/diphenyl/diphenyl disulfide/diphenyl methane with dichloro disulfide in the presence of a trace amount of iron powder by a one‐step reaction. From MALDI‐TOF mass spectra, it was established that the repeating units of the cyclization ranged from two to seven and the unit of macrocyclic(arylene multisulfide) oligomers had one to seven sulfur atoms. The macrocyclic oligomers readily underwent ring‐opening polymerization in the melt, resulting in linear, high molecular weight polymultisulfides. DSC thermograms demonstrated that the four polymultisulfides, derived from the macrocyclic(arylene multisulfide) oligomers, are amorphous in nature. The macrocyclic(arylene multisulfide) oligomers and polymers were analyzed by MALDI‐TOF‐MS, IR, HPLC, NMR, DSC, and TGA methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 735–741, 2004     

Synthesis and self-assembly of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups

In this article, we described the synthesis of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups via the free radical polymerization. Oligomers obtained were well characterized by MALDI-TOF-MS, ¹H NMR, FT-IR, UV, CD and SEC. These comb oligomers having macrocyclic pendant groups showed very good solubility in common organic solvents at room temperature. Furthermore, the oligomers could self-assemble into different morphologies by dropping their THF solutions of different concentrations on the surface of water. At a relatively low concentration, the oligomers self-aggregated into hollow spheres. When the concentration was increased, the aggregates changed into solid spheres. The morphologies of the hollow or solid spheres were observed by TEM and ESEM.     

Liquid crystal oligo(cyclosiloxanes)

The synthesis and properties of individual liquid crystal oligo(cyclosiloxanes),, wherex=4–8 andR is a 4-methoxyphenyl-4-alkyloxybenzoate type of mesogenic group, is described. Preliminary results concerning the effect of ring size on the mesophase formation are included. X-ray diffraction studies have shown that the cyclosiloxanes form a smectic A₁ phase.