Some properties of poly-α-piperidone

The high molecular weight polymer of α-piperidone, which had been unobtainable with the use of alkali metal, trialkyl aluminum, or Grignard reagent as catalyst, was prepared with M–AlEt₃, (where M is alkali metal), MAlEt₄ or KAlEt₃ (piperidone) as catalyst and N-acyl-α-piperidone as initiator. From the determination of the behavior of the solution viscosity of poly-α-piperidone in m-cresol at 30°C. the value of 0.27 for the Huggins constant was obtained. Examination of the correlation between the number-average molecular weight, determined by endgroup titration, and the intrinsic viscosity gave a somewhat small value for the endgroup COOH. This may be considered due to the consumption of N-acyl-α-piperidone by a propagating polymer in the course of polymerization. The thermal stabilities of the polyamides, nylons 4, 5, and 6, was in the order nylons 6 > 5 > 4 according to differential thermal and thermogravimetric analyses, Poly-α-piperidone, which has a reduced viscosity of 0.7, shows a melting point of 270°C.. which was expected from the zigzag pattern of the correlation between melting points and numbers of CH₂ groups for polyamino-acid polymers.     

Free radicals in γ-irradiated poly-α-methylstyrene

Electron spin resonance (ESR) spectra were observed at ?160°C and at room temperature for γ-irradiated poly-α-methylstyrene. The spectrum observed at room temperature has been attributed to the radical species while that at ?160°C results from the same radical and superposition of the spectrum due to the radical ?H₂-C(CH₃)(C₆H₅)-. The radicals which are stable at room temperature could be used to graft vinyl acetate.     

Stress relaxation of monodisperse poly-α-methylstyrene

The viscoelastic properties of monodisperse poly-α-methylstyrenes of molecular weights of 4 × 10⁴ to 50 × 10⁴ were studied by the tensile stress-relaxation method. The relaxation-time spectra as well as the steady-flow viscosity, the steady-state compliance, the maximum relaxation time, and the modulus associated with the maximum relaxation time were determined. The molecular weight dependences of these quantities were compared with the theory of Rouse and Bueche as modified by Ferry, Landel, and Williams, as well as with data on other polymers reported in the literature.     

Volume recovery of glassy poly-α-methylstyrene

A method for evaluating the relaxation time as a function of both temperature and volume from volume contraction experiments, as proposed by Kovacs, was experimentally examined by using monodisperse poly-α-methylstyrene samples of various molecular weights and blends. It was concluded that his theory can be successfully applied to the present experimental data, though his two different approximations give somewhat different values of the shift factor for the time-temperature superposition of volume contraction data. A difference was observed between the temperature dependence of the shift factor of monodisperse polymers and that of blends.     

Alternating copolymerization of dienes with α-olefins

Alternating copolymerization of butadiene with several α-olefins and of isoprene with propylene were investigated by using a mixture of VO(Acac)₂, Et₃Al, and Et₂AlCl as catalyst. The alternating copolymerization ability of the olefins decreases in the order, propylene > 1-butene > 4-methyl-1-pentene > 3-methyl-1-butene. The study on the sequence of the copolymer of isoprene with propylene by ozonolysis reveals that the polymer chain is reasonably expressed by the sequence \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH}_{\rm 2} \hbox{--} {\rm CH} \hbox{=\hskip-1pt=} {\rm C(CH}_{\rm 3}) \hbox{--} {\rm CH}_{\rm 2} \hbox{--} {\rm CH(CH}_{\rm 3}) \hbox{--} {\rm CH}_{\rm 2} \rlap{--}]_n $\end{document}. NMR and infrared spectra indicate that the chain is terminated with propylene unit, forming a structure of ?C(CH₃)? CH₂? C(CH₃)?CH₂ involving a vinylene group.     

Dynamic mechanical studies of α and β relaxations of polyethylenes

The α and β relaxations of a variety of polyethylenes have been extensively studied using lowfrequency dynamic mechanical methods. The main focus of this work has been both the control and the quantitative measurement of the key structural factors that describe semicrystalline polymer systems. The structural factors that have been examined in detail include the level of crystallinity, the crystallite thickness, the interfacial content, and the supermolecular structure. Consequently a variety of other types of supplementary measurements were made to accomplish the necessary characterization. The location of the α transition is found to depend primarily on the crystallite thickness. There also is the distinct possibility that the interfacial structure exerts an important influence. The level of crystallinity and the supermolecular structure do not play a significant role in the location of T_α. A strong correlation is found with the carbon-13 NMR crystalline T₁, which is reported in a separate paper. From analysis of the influence of the different structural factors on the β transition, it is concluded that this transition results from the relaxation of chain units which are located in the interfacial region. The elusiveness of this transition and the contradictory reports that have existed in the literature are given a ready explanation. The enhancement of this transition by branching and copolymerization follows naturally as does its invariance with counit content.     

Nuclear magnetic resonance of poly-β-alanine

Nuclear magnetic resonance of poly-β-alanine samples differing in solubility in water was studied over a wide temperature range as part of an investigation of their physical properties. Water-soluble poly-β-alanine has more branches and a lower degree of crystallinity than water-insoluble poly-β-alanine. NMR spectra of poly-β-alanine show one component at 77°K. which splits into two components, broad and narrow, at room temperature. Two transition regions were observed in curves for line width and second moment versus temperature. The higher transition temperature, corresponding to the glass transition of the polymer, appears to decrease with increasing water content. The second moment for the water-soluble polymer differs from that of the water-insoluble polymer at 77°K. This is interpreted in terms of the difference in the degree of crystallinity of the polymers.     

Influence of microstructure on the hydrodynamic behavior of poly-α-methylstyrene

The theta temperature of poly-α-methylstyrene in cyclohexane has been found to vary with the stereostructure of the polymer. The observed values range from 305.5°K. for highly syndiotactic material (0.95 syndiotactic diads) to 310.0°K. for anio ically polymerized samples (0.67 syndiotactic diads). Results indicate that the unperturbed dimensions of the polymer increase with increasing isotacticity of the chain, whereas the entropy parameter ψ₁, measured in cyclohexane, decreased as the structure became more isotactic. Measurements of the second virial coefficient in toluene showed an increasing interaction with the solvent as the polymer became more syndiotactic.     

Synthesis and properties of new polyimides containing flourinated alkoxy side chains

A series of new polyimides containing fluorinated alkoxy side chains are prepared from novel fluorinated alkoxy diamines. The dieletric constant at 1 kHz in the fluorinated polyimides decreases from 3.3 to 2.6 as fluorine content increases. The refractive index also changes from 1.58 to 1.48, dependent on the fluorine content. In addition, the fluorinated polyimides exhibit lower water absorption than the reference polyimides prepared from m-phenylenediamine.     

Structure and properties of functionalized polyfluorenone containing hetero aromatic side chains

The optical properties of substituted fluorenones with diverse structures have been analyzed using molecular orbital calculations in order to understand the structure-property relations. Based on theoretical predictions, synthesis of some model compounds has been attempted. The experimentally obtained optical properties are in close agreement with the theoretically obtained results.     

Co- and terpolymerizations of ethene and α-olefins with metallocenes

The suitability of the (n-butCp)₂ZrCl₂/methylaluminoxane (MAO) catalyst system for the copolymerization of ethene with propene, hexene, and hexadecene was studied and Ind₂ZrCl₂/MAO was tested as a catalyst for ethene/propene and ethene/hexene copolymerizations. The synergistic effect of longer α-olefin on propene incorporation in ethene/propene/hexene and ethene/propene/hexadecene terpolymerizations was investigated with Et(Ind)₂ZrCl₂MAO and (n-butCp)₂ZrCl₂/MAO catalyst systems. The molar masses, molar mass distributions, melting points, and densities of the products were measured. The incorporation of comonomer in the chain was further studied by segregation fractionation techniques (SFT), by differential scanning calorimetry (DSC), studying the β relaxations by dynamic mechanical analysis (DMA) and by studying the microstructure of some copolymers by ¹³C-NMR. In this study (n-butCp)₂ZrCl₂ and Ind₂ZrCl₂ exhibited equal response in copolymerization of ethene and propene and both catalysts were more active towards propene than longer α-olefins. A nearly identical incorporation of propene in the chain was found for the two catalysts when a higher propene feed was used. A lower hexene feed gave a more homogeneous comonomer distribution curve than a higher hexene feed and also showed the presence of branching. In terpolymerizations catalyzed with (n-butCp)₂ZrCl₂, the hexadecene concentrations of the ethene/propene/hexadecene terpolymers were always very low, and only traces of hexene were detected in ethene/propene/hexene terpolymers. With hexene no clear synergistic effect on the propene incorporation in the terpolymer was detected and with hexadecene the effect of the longer α-olefin was even slightly negative. With an Et(Ind)₂ZrCl₂/MAO catalyst system both hexene and hexadecene were incorporated in the chain in the terpolymerizations. © 1997 John Wiley & Sons, Inc.     

Thermal decomposition and volatilization of poly(α-olefins)

The thermal decomposition of normal alkanes and linear poly(α-olefins) was found to occur predominately by random scissions, followed by volatilization into an open system. To show these processes the fragment distribution from high molecular weight linear polyethylene (fragments to C₅₅), n-alkanes, polypropylene, and polyisobutylene (fragments to C₆₀) are reported and discussed in depth. Based on the results, a mechanism of random scissions followed by volatilization is postulated for polyethylene and n-alkanes as well as for polyisobutylene and polypropylene. Polystyrene is shown not to follow the same mechanism, for little evidence for fragments above trimers was found. In addition, temperature rise–time measurements at the pyrolyzer probe are reported and explained.     

Dynamic mechanical and thermal behavior of liquid-crystalline polybutadiene-diols with mesogenic groups in side chains

Liquid-crystalline polybutadiene-diols (LCPBDs) with the comb-like architecture were synthesized by reaction of a LC thiol with the double bonds of telechelic HO-terminated polybutadiene (PBD). LCPBDs with various initial molar ratios of thiol to double bonds of PBD, R₀, in the range from 0.15 to 1, were prepared by the radical reaction at temperature 60 °C for 48 h. The experimentally obtained degree of modification, R_e, after the reaction and purification, was determined from elemental analysis - from the amount of sulphur bounded in LCPBDs, GPC and from ¹H NMR spectra. The physical properties were investigated by differential scanning calorimetry and dynamic mechanical spectroscopy. With increasing R_e ratio the glass transition temperature of LCPBDs, T_g, increases from ∼ − 45 °C (neat PBD) to ∼20 °C (R_e ∼ 0.5). LC transition starts at R_e ∼ 0.27 (the transition temperature T_m ∼ 27 °C). With increasing R_e temperature T_m increases and for R_e ∼ 0.5 reaches the value T_m ∼ 74 °C; at the same time also the change in enthalpy at LC transition increases. The LC transition could be detected also by the dynamic mechanical spectroscopy; especially shape and position of mechanical functions on frequency and free volume parameters strongly depend on degree of modification.