Polymers , vii

The gum-like co-substituted polymers VI have lower Tg than polymers VII, which form excellent films. The highest ionic conductivity at 25 °C reported for the VI and VII/LiN(S02CF3)2 complexes are 3.5x10" and 2.4x10 S cm" for VI (x=7.3 ) and VII (x=7.3) complexed with 0.328 and 0.5 mol salt/polymer repeat unit, respectively [604]. 

The viscosities were measured with an Ubbelohde Cannon 75-L, 655 viscometer. Formic acid was chosen as the solvent for the viscosity measurement because the polymer (VII) showed very low or no solubility in other common solvents. In a salt free solution, a plot of the reduced viscosity against the concentration of the polymer showed polyelectrolytic behavior, that is, the reduced viscosity ri sp/c increased with dilution (Figure 4). This plot passed through a maximum at 0.25 g/dL indicating that the expansion of the polyions reached an upper limit, and the effects observed on further dilution merely reflected the decreasing interference between the expanded polyions. 

The elemental analysis, IR and lH NMR spectra of polymers VII and VIII are in agreement with the proposed chemical structure for the 1,4-polymerization of N-pheny1-3,4-dimethylenepyrrolidine. 

Solubility - The oxidized polymer (VIII) has a greater solubility than the original polymer (VII). It was found to be soluble in acetone, chloroform, benzene, DMF and DMSO. Unlike the polymer (VII), (VIII) was not soluble in formic acid or trifluoroacetic acid that was expected since the pyrrole moiety is less basic than pyrrolidine. In the oxidized polymer, the pair of unshared electrons on the nitrogen atom are contributing to the pyrrole ring aromaticity, therefore, unavailable for protonation as in the case of polymer (VII). A comparison of the solubilities is given in Table I. 

The DSC and TGA plots of the oxidized polymer (VIII) showed that the Tm is 130°C and the weight loss of 20% and 80% was observed at 455°C and 600°C, respectively, compared to 400° and 482°C for the original polymer VII indicating the oxidized polymer was more stable to heat. This observation was consistent with the chemical structure of the oxidized polymer, which consisted of a repeating aromatic pyrrole structure and, therefore, should be more thermodynamically stable. The thermal data of the polymers are tabulated in Table II. 

Figure 6. General structure for phosphazenes with mesogenic side groups. Example is a mixed substituent polymer (VII) where R represents the trifluoroethoxy group and the mesogen with flexible spacer is represented by the curlicue and rectangular box.

When diethylamine is used in the substitution process, approximately 50% substitution occurs. This polymer (VII) is an elastomer... 

Figure 4. Thermogravimetric analysis of polymer VII (upper curve) with derivative (lower curve) showing two distinct thermal degradations.

Preparation of Polymer VII. A solution of 8.0g (36 moles) 4-(l-phenylethoxy)-styrene and 0.080g AIBN in 16g toluene was heated in an oil bath at 75°C under inert atmosphere. After 48 hours the thick polymer solution was diluted with a minimum amount of toluene to allow its precipitation in 3L of petroleum ether. The recovered polymer (7.1g, 88% yield) had spectral properties in agreement with the proposed structure. 

Fujimura, T., Ryu, J.Y., Imamura, Y., Furuno, T. and Jodai, S. (1993a). Improvement of the durability of wood with acryl-high-polymer VII. Biological resistance of acrylic-copolymer treated wood. Mokuzai Gakkaishi, 39(9), 1042-1048. 

In all cases the anisotropic polymerization mixtures (10% by weight) could be used directly in the formation of dry-jet wet-spun fibers. Monofilament fibers were obtained by coagulation in water, tension dried at 150 °C and heat treated at 500-600 °C with a 30s residence time. The best fibers were obtained from the high molecular weight PBZT polymer (VII) which exhibited modulus values that ranged between 172 GPa and 207 GPa and tenacity values up to 2.4 GPa. Unfortunately, the compressive property as measured by the tensile recoil test was only 380 MPa, showing only a slight improvement over PBZT. 

Ranucci, K. and Femui, P., New basic multifunctional polymers. VII. A polyfaniino-thiocther-phenol) by polycondcasalion of 2,2 -( 1.4-piperazincdiyl)diclhanclhiol with 2,6-bis(dimethylamin(Mnelhyl)-4-mcth-ylphenol, Chan. Ind.. 72, 795, 1990. 

CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES TABLE 68. Co-polymers of VI i h diols polymers VII... 

Golemba, F. J., Guillet, J. E., Photochemistry of Ketone Polymers. VII. Polymers and Copolymers of Phenyl Vinyl Ketone, Macromolecules 1972, 5, 212 216. 

When this same tetrol was condensed with 1,4-cyclohexanedione in n-butyl ether in the presence of a trace of jv-toluenesulfonic acid, a nearly quantitative yield of a white polymer VII was obtained. This material did not melt, but was soluble in hexa-fluoroisopropanol and had an [n] of 0.04 dl/g (25 , hexafluoro-isopropanol). This polymer VII was found to be highly crystalline by X-ray powder pattern and had a T. in the DTA apparatus of 400°. 1/Z... 

Polymer VII from 1,4-Cyclohexanedione and 1,2,4,5-Tetrakis-(hydroxymethvl) cyclohexane. Into a 100—ml flask equipped with a mag. stirrer, a Dean-Stark trap, a reflux condenser and a drying tube were added 50 ml of dry n-butyl ether, 2.04 g of 1,2,4,5-tetrakis(hydroxymethyl)cyclohexane and 1.12 g of 1,4-cyclohexanedione. The solution-suspension was heated under reflux for 12 hours followed by the addition of 0.1 g of -toluenesulfonic acid. After the mixture was heated overnight, it was cooled to room temperature. The mixture was filtered with suction and the resulting solid was washed well with n-butyl ether. After most of the ether was removed, the solid was washed with water, acetone and finally ether. The solid, which was dried over P2O5 and under 0.2 mm pressure, weighted 3.1 g (99%). The solid was soluble only in hexafluoroisopropanol and had an [T ] of 0.04 dl/g at 25°c. The polymer was found to be crystalline by X-ray and did not melt. 

No detailed experiments have been carried out yet to determine the usefulness of these polymers as chelating agents or drug carriers. However, preliminary tests with ethanolic solutions of metal acetates show that polymers VII, VIII, and XIV give colored complexes with some of the common transition elements. In the case of VIII, a green complex is formed with cupric acetate and a yellow complex with oobaltic acetate. More complete experiments will be reported in a latter communication. 

A linear high polymer can also be represented by the spaghetti-like strand shown in V and, in these terms, we can recognize branched polymers (VI) and random crosslinked polymers (VII). Ladder polymers (VIII) are also known ... 

Linear, branched and cyclolinear polymers are usually soluble. Lightly crosslinked polymers (VII) are swelled by, but are insoluble in liquids. Highly crosslinked or cyclomatrix polymers are insoluble in all media. Oligomers dissolve in liquids to give non-viscous solutions. High polymers dissolve to give highly viscous solutions. 

B.S. Kaith, and A.S. Singha, "Modification of natural polymers-VII Ceric ion induced grafting of methylacrylate onto Flax fibre" International Congress of Chemistry and Environment, 2001. 

Polymer VII belongs to a group of conjugated polymers containing porphyrin or phthalocyanine complexes synthesized by Lu et al. [16]. Here, the polymer backbone consists of phenylene vinylene moieties, which facilitate hole trans-... 

Polymer VII Poly(GVGVP GVGFP GEGFP GVGVP GVGVP GVGVP) E/2F... 

Polymer VII (GVGVP GVGVP GKGVP GVGVP GVGVP GVGVP) (GVGVP) K/OF... 

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