Synthesis and thermal transitional properties of side-chain liquid crystalline polyacrylates containing para-nitroazobenzene as mesogenic groups

The synthesis and characterization of side-chain liquid crystalline (LC) polyacrylates containing para-nitroazobenzene (Pn) as mesogenic groups were described. Homopolymers with 3 and 4 carbon atoms in the spacers were non-LC polymers; for homopolymers with 6 carbon atoms in the spacer, nematic LC behavior was observed. Copolymers with acrylic acid as one component exhibited an S-Ad phase according to the WAXD results which showed the d/l of 1.4-1.54 for the copolymers with 3, 4, and 6 carbon atoms in the spacers. Considering the molecular structure as well as the WAXD results of the copolymers, the possible molecular arrangement in the smectic Sad phase was proposed, in which the smectic layers were composed of the antiparallel mesogens and the antiparallel arrangement was considered to be enhanced due to the H bond between - COOH and - NO2. The stress-induced orientational phenomena of Pn in the LC states was also discussed. (C) 1996 John Wiley & Sons, Inc.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

THE CHAIN STRUCTURE AND LIGHT-SCATTERING-STUDIES FOR ACRYLAMIDE-SODIUM ACRYLIC-ACID (AM-AA) COPOLYMERS

A set of AM-AA copolymer samples with the same comonomer content and different average molecular weight have been characterized by C-13 NMB and light scattering methods in this paper. The chemical composition (comonomer AA, mole content 16.9 +/- 1.1%) of these samples is uniform. the sequence of AA in the macromolecular chain is of alone and random distribution and the light scattering theory from polyelectrolyte in added-salt solutions is suitable for the AM-AA copolymers-0.12 mol/L NaCl water systems. The actual values of M(w), the second Virial coefficient A(2) and the mean square radius of gyration (R(2)), for the studied samples have been obtained. The relationships between the molecular parameters are as follows: A(2)=0.0619 ($) over bar M(w)(-0.24), < R(2) >(1/2)(t)= 0.0210 ($) over bar M(w)(0.54).

LOCAL MAIN-CHAIN DYNAMICS OF PHENOLPHTHALEIN POLYETHERSULFONE

Local main chain dynamics of dissolved phenolphthalein polyethersulfone (PES-C) in solution with chloroform-d(1) were examined through C-13 NMR relaxation measurements. Spin-lattice relaxation times and NOE (nuclear Overhauser effects) factors were measured as a function of temperature. The relaxation data were interpreted in terms of main chain segmental motion by using the damped orientational diffusion model (DAMP) and the conformation jump model (VJGM) derived by Valeur, Jarry, Geny, and Monnerie. The simulation method used is N-SIMPLEX, which gives, in this study, a result of the object function less than 10(-4). Correlation times were obtained for the main chain motion of PES-C with these models and the results indicate that the main chain of PES-C are flexible. The comparison between PES-C and 1,2-polybutadiene is proposed. The distribution of the correlation time for the main chain motion by using VJGM model is discussed. The temperature dependence of correlation times for PES-C indicating the dynamical rigidity of its chains is obtained.

THE EFFECT OF MOBILITY OF MOLECULES ON RADIATION-INDUCED CHAIN SCISSION AND RACEMIZATION OF ISO-POLY(METHYL METHACRYLATE)

The radiation-induced chain-scission and racemization of isotactic poly(methylmethacrylate)(iso-PMMA) in amorphous and semi-crystalline state as well as in solution have been studied with nuclear magnetic resonance and molar mass deter-mination. It is shown that the chain-scission is dominant for iso-PMMA in dilute solution while the racemization reaction is not favorable in this case. On the contrary, the racemization is favorable when iso-PMMA was irradiated in its crystalline state while chain-scission is not. Such experimental results could be well explained by the mobility of molecules and "cage effect". The hypothesis, we proposed previously that the chain-scission, racemization and recombination are in competition and the final result depends on the state of molecular motion at which iso-PMMA was irradiated, has been verified verified once again.

MOLECULAR-GEOMETRY AND CHAIN ENTANGLEMENT - PARAMETERS FOR THE TUBE MODEL

The tube diameter in the reptation model is the distance between a given chain segment and its nearest segment in adjacent chains. This dimension is thus related to the cross-sectional area of polymer chains and the nearest approach among chains, without effects of thermal fluctuation and steric repulsion. Prior calculated tube diameters are much larger, about 5 times, than the actual chain cross-sectional areas. This is ascribed to the local freedom required for mutual rearrangement among neighboring chain segments. This tube diameter concept seems to us to infer a relationship to the corresponding entanglement spacing. Indeed, we report here that the critical molecular weight, M(c), for the onset of entanglements is found to be M(c) = 28 A/([R2]0/M), where A is the chain cross-sectional area and [R2]0 the mean-square end-to-end distance of a freely jointed chain of molecular weight M. The new, computed relationship between the critical number of backbone atoms for entanglement and the chain cross-sectional area of polymers, N(c) = A0,44, is concordant with the cross-sectional area of polymer chains being the parameter controlling the critical entanglement number of backbone atoms of flexible polymers.

DOPING EFFECTS ON THE POLYMER-CHAIN STRUCTURE OF POLY(3-METHYLTHIOPHENE)

The C=C stretching Raman shifts and photoluminescence (PL) for poly(3-methylthiophene) (P3MT) are measured at various doping levels by in situ electrochemical Raman and PL spectroscopic techniques. It is found that the doping for P3MT induces the nonlinear excitations (soliton, Polaron, bipolaron), but also affects the polymer-chain structure, including the conjugated length and the interchain distance.

CONFORMATION OF PHENYL RINGS IN THE HELICAL CHAIN POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The conformation of phenyl rings in the side groups of the helical chain polymer poly(tripenyl-methyl methacrylate) (1) in solution was studied by spectroscopic methods. According to the Raman spectrum the phenyl rings of 1 and triphenylmethyl methacrylate in solution have the same depolarization ratio at 1002 cm-1. The electronic spectra (ultraviolet and fluorescence) of 1 are similar to those of model substances, except for the "red shift" of the spectra of about 5 nm. It was concluded that the phenyl rings can rotate around the phenyl-C bond.

MOLECULAR CHAIN STRUCTURE OF DOPED POLYANILINE

The chain structure of polyaniline doped with HCl or CF_3COOH has been investigated by FTIR, solid state ~(13)CNMR, resonance laser Raman and UV-VIS spectroscopies. The results show that during the protonic acid doping, a partial redox reaction takes place between the quinone-diimine and benzene-diamine units and it leads to a long conjugate system with a certain charge distribution.