Dilute solution properties of a polyurethane. I. Linear polymers

A linear polyurethane of high molecular weight was prepared in solution by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). The polymer was fractionated by using a direct sequential extraction procedure, with a solvent–nonsolvent system consisting of N,N′-dimethylformamide (DMF) and acetone (A). The resulting fractions were characterized by viscosity and lightscattering measurements. The relationship between the intrinsic viscosity and molecular weight was found in DMF at 25°C. to be [η] = 3.64 × 10^?4M^0.71. The unperturbed polymer chain dimensions were determined from intrinsic viscosity measurements carried out under experimentally determined theta conditions.     

Styrene-methyl acrylate copolymers and acrylate homopolymers in solution

Molecular weight determinations by light scattering and osmometry and intrinsic viscosity measurements were made in various solvents on fractions of styrene–methyl acrylate copolymers with different compositions and on acrylate homopolymers prepared by free-radical reaction. Relations between intrinsic viscosity [η] and molecular weight M thus established are compared with those reported by other authors. 2-Methylcyclohexanol was found to be a theta solvent for the copolymers and both parent homopolymers, and isoamyl acetate was a theta solvent for poly(methyl acrylate). From theta point viscosity data obtained with these solvents, unperturbed chain dimensions were estimated. The results are compared with the unperturbed dimensions estimated from the [η]–M relations obtained in good solvents. On the basis of the experimental data it was found that the unperturbed dimension depends linearly on the copolymer composition, in contrast to the case of styrene–methyl methacrylate copolymers. Composition dependences of the theta temperature and of the parameter describing the long-range interactions between nonadjacent segments in polymer chains were investigated. The result implies that long-range interactions between monomeric units never disappear even when those between the same monomeric units vanish. The Huggins constant for copolymer is discussed in terms of the excluded volume variable.     

Molecular weight determinations by gel-permeation chromatography and viscometry

The hydrodynamic volume concept can be used effectively with gel-permeation chromatographic (GPC) and viscosity data to estimate the molecular weight of a variety of polymers. Agreement is within ±5–10% of the absolute values and thus is satisfactory for many purposes. An iterative computer technique and a method developed by Funt and Hornof for analyzing GPC–viscosity data were found to be equivalent with respect to estimating the molecular weights for the five cases studied. The latter is easily employed but restricted to the case where the sample of interest and the GPC calibration standards have approximately equal Mark-Houwink parameters. Since GPC measurements are commonly performed in thermodynamically good solvents, the general applicability of the method is not impaired. Using the unperturbed dimensions of the polymer chain to estimate the molecular weight of a variety of polymers was not as satisfactory as the above techniques. This approach generally gave biased molecular weight values (consistently low or consistently high). Agreement with the absolute values ranged from 10 to 30%. We therefore believe that either of the techniques based on the hydrodynamic volume concept can be used more effectively to estimate the molecular weight of a series of polymers than the treatment based on the unperturbed dimension.     

Unperturbed dimensions of poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly(2,6-diphenyl-1,4-phenylene oxide) chains

The unperturbed chain dimensions of unfractionated poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly-(2,6-diphenyl-1,4-phenylene oxide) have been measured by combining molecular weight data from light scattering with intrinsic viscosity data in chloroform. The unperturbed chain dimensions of the former polymer were also measured directly by light scattering dissymmetry in a critical consolute solvent mixture (methyl cyclohexane: 1,4-dioxane 50:50 by volume). The results of these measurements and of measurements reported by other investigators are satisfactorily explained by postulating no dimension-expanding prejudice in azimuthal angle in chain conformers of the 2,6-substituted-1,4-phenylene oxide polymers. This corresponds to equal population of the two chain rotation energy minima at azimuthal angles 90° and 270°. Accepting this postulate, one calculates from the observed chain dimensions that the C? O? C bond angle is 118–120° in these aromatic polyethers in solution.     

Configurational characteristics of trans-1,4-polychloroprene: Experimental results on the unperturbed dimensions and their temperature coefficient

Polychloroprene [CCl?CH? CH₂? CH₂? ]_x of approximately 95% trans-1,4 stereochemical structure was prepared by low-temperature emulsion polymerization. Fractions, obtained by liquid–liquid precipitations were studied in toluene solutions at 30°C by viscometry and osmometry. In addition, force–temperature measurements were carried out on networks of the polymer in the amorphous state. The results obtained on the polymer solutions indicate that the unperturbed dimensions of trans-1,4-polychloroprene are essentially the same as those of trans-1,4-polybutadiene of the same molecular weight. This observation, that substitution of a relatively large Cl atom for one of the methine H atoms in the trans-1,4-polybutadiene repeat unit has little effect on the chain dimensions, suggests that this increase in substituent size is offset by the fact that the length of a C? Cl bond is very much greater than that of a C? H bond. The results obtained on the polymer networks indicate that the unperturbed dimensions of trans-1,4-polychloroprene decrease significantly with increasing temperature, as has also been reported for both trans-1,4-polybutadiene and trans-1,4-polyisoprene.     

Correlation between transport and equilibrium properties through the ternary interaction parameter for cosolvent and cononsolvent polymeric systems

A study of the ternary polymer systems dimethyl formamide-ethyl acetate-polystyrene, chloroform-1,4 dioxane-polystyrene and tetrahydrofuran-chloroform-polystyrene was carried out by viscosity and light scattering at 298 K. A good correlation has been found between the excess intrinsic viscosity, unperturbed polymer dimensions, second virial coefficient and the excess Gibbs free energy by using a ternary interaction parameter, dependent on molecular weight. This modification enables the conversion between transport and equilibrium properties.     

Viscometric Estimation of Unperturbed Chain Dimensions of Polymers

A new expression is proposed to determine the unperturbed dimensions of coil-like polymers viscometrically by use of the Flory and Kratky expression. The unperturbed dimensions so estimated are compared with the results obtained by using different expressions available in the literature. The results are comparable even for stiff chain polymers. The data obtained under theta conditions also fit this expression very well. The effect of molecular weight, its distribution, and that of the solvent has also been studied. It is concluded that the unperturbed dimensions are independent of molecular weight and solvent but depend on the heterogeneity of the system.     

Relations entre le second coefficient du viriel A2 et la masse moleculaire,dans le systeme polystyrene-benzene

We present results obtained by osmometry on the polystyrene-benzene system at 24°C as a function of the polymer molecular weight. The variation of the second virial coefficient, as predicted by the Flory-Krigbaum theory of dilute solutions is lower than that obtained by our osmotic measurements: this difference is discussed. Using the Kurata method, we determined the unperturbed dimensions of the macromolecule. Lastly, we established the equation for the variation of the mean square distance with molecular weight for the polystyrene-benzene system.     

Solution properties of poly(dimethyl siloxane)

The solution properties of poly(dimethyl siloxane) (PDMS) were studied with light scattering (LS), gel permeation chromatography/light scattering (GPC/LS), and viscometry methods. PDMS samples were fractionated, and the weight‐average molecular weights, second virial coefficient, and the z‐average radius of gyration of each fraction were found according to the Zimm method with the LS technique. In this work, the molecular weight range studied was 7.5 × 10⁴ to 8.0 × 10⁵. Molecular weights and molecular weight distributions were determined by GPC/LS. The intrinsic viscosities of these fractions were studied in toluene at 30 °C, in methyl ethyl ketone (MEK) at 20 °C, and in bromocyclohexane (BCH) at 26 °C and 28 °C. The Mark–Houwink–Sakurada relationship showed that toluene was a good solvent, and MEK at 20 °C and BCH at 28 °C were θ solvents for PDMS. The unperturbed dimensions were calculated with LS and intrinsic viscosity data. The unperturbed dimensions, expressed in terms of the characteristic ratio, were found to be 6.66 with different extrapolation methods in toluene at 30 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2678–2686, 2000     

Structure and solution properties of radical-initiated poly(vinyl chloride). II. Correlation of solution properties

The results of detailed measurements of osmotic pressure, light scattering, and viscosity of poly(vinyl chloride) solutions are used to establish the molecular weight dependence of [η] and A₂, to estimate the unperturbed dimensions of the poly(vinyl chloride) molecule, and to analyze critically the [η]–M correlations published hitherto.     

Unperturbed dimensions of poly(9-vinyladenine)

The effect of base stacking interactions on the conformation of poly(9-vinyladenine) (PVAd) was investigated by osmometry, intrinsic viscosity, and light-scattering measurements. At neutral pH, ideal solution behavior (θ conditions) for this polymer was observed at 26 and 40°C. Intrinsic viscosity measurements revealed a conformational transition on heating from 26 to 40°C, while the ultraviolet absorbance of the solution was insensitive to the change. The transition was accompanied by an inversion in sign of the entropy parameter from negative to positive and an increase in the partial specific volume. At 40°, the variation of intrinsic viscosity with molecular weight corresponded to a random coil conformation, but the characteristic ratio, r?₀²/nl² = 8.6 ± 0.2 indicated that the unperturbed dimensions were smaller than usually observed for comparable vinyl polymers. At 26°, a rare macromolecular phenomenon was found, the intrinsic viscosity–molecular weight relation and the estimated r?₀²/nl² of 6.0–6.8 suggested that the PVAd was in a very highly compacted coil conformation, approaching a semirigid sphere. It is proposed that this effect be named the introversion phenomenon. Unlike polyadenylic acid, whose unperturbed dimensions increase with decreasing temperature due to nearest-neighbor base stacking, the results reported here suggest that both nearest-neighbor and long-range intramolecular base stacking occur in PVAd. The different stereochemical arrangements of bases in PVAd and Poly A are probably responsible for the opposite behavior observed.     

高分子无扰尺寸的测定

本文用GPC-[η]联用仪测定高聚物分子的无扰尺寸,GPC将高聚物分成不同的级分,连用自动粘度计测其相应级分的粘度,并由GPC的标定线或普适标定线,得到各级分的分子量,再用使Mark-Houwink公式线性化的理论方程,图解外推到无扰状态,获得高聚物分子的无扰尺寸,对于聚苯乙烯和聚甲基丙烯酸甲酯,所得结果与直接法、习惯法一致。     

Solution properties of poly(dialkyl-cyclohexyl) itaconates

Di(methyl-), di(ethyl-) and di(propylcyclohexyl) esters of itaconic acid were polymerized radically in bulk. The products were characterized in solution, then fractionated and the limiting viscosity number/molecular weight relations established for toluene at 25°. From extrapolations to θ-conditions, a set of σ-values from 2.75 to about 2.90 was obtained and compared with published results for poly(dicyclohexyl itaconate) [1], the first member of this polymer homologous series. The non-uniform change of unperturbed dimensions and other thermodynamic parameters are discussed in terms of chemical composition and constitution of the monomer residues.     

Solution properties of poly(N-vinyl carbazole)—II. Thermodynamic properties in various solvents

Thermodynamic properties of dilute solutions of Poly-N-vinyl carbazole obtained by cationic polimerization have been studied by viscometry in various solvents. The validities of some excluded volume theories have been tested and the unperturbed dimensions have been calculated. The dependence of molecular dimensions, 〈s²〉, on molecular weight and viscometric equations have also been determined.     

Determination of molecular parameters of hydroxyethyl and hydroxypropyl celluloses by chromatography with dual detection

Hydroxyethylcellulose (HEC) and hydroxypropylcellulose (HPC) were studied by means of size exclusion chromatography with dual detection, i.e. employing simultaneously a refractive index (concentration sensitive) and a multiangle light scattering (molecular weight sensitive) detectors. The eluent was water and water solutions containing different concentrations of ionic salts. Molecular weight distributions and averages, coefficients of the scaling law of molecular dimensions and unperturbed dimensions were thus obtained from a single polydisperse sample of each polymer. Measurements were performed at 25 degrees C and the anomalous chromatographic behaviour, due to a combination of ion and size exclusion mechanisms, found when using pure water as eluent is transformed into a size exclusion mechanism by the addition of ionic salts. However, the two polymers behave on a different way in presence of salts. Thus, HEC, which is of low degree of substitution (DS), is close to theta conditions in the aqueous salt solutions (i.e. the q exponent of the scaling law has a value close to 0.5), whereas in the case of HPC the addition of salt improves the quality of the solvent up to a value of q around 0.6. Unperturbed dimensions are also calculated for both celluloses.     

Gel-permeation chromatography: Examination of universal calibration procedures for polydimethylsiloxane in a poor solvent

Various procedures for universal calibration in gel-permeation chromatography with polystyrene gels are examined for polystyrene and polydimethylsiloxane fractions. For o-dichlorobenzene at 138°C, experimental intrinsic viscosity–molecular weight data show that the Mark-Houwink exponents are 0.70 and 0.57 for polystyrene and polydimethylsiloxane, respectively. In principle, this difference permits a distinction between the various polymer size parameters proposed for universal calibration. An interpretation of the experimental polydimethylsiloxane calibration for o-dichlorobenzene at 138°C requires a consideration of errors in average molecular weights and errors arising from the use of average molecular weight instead of peak molecular weight. When calibration procedures utilizing hydrodynamic volume and unperturbed dimensions are examined, the difference between them is comparable with experimental error. If the Flory-Fox viscosity expression is employed, the perturbed end-to-end distance (or radius of gyration) and the hydrodynamic volume give equivalent universal calibrations. The experimental data are sufficiently accurate to show that the perturbed dimension determined with the Ptitsyn-Eizner relation does not give an adequate universal calibration.     

混合溶剂中高分子的尺寸

三元体系(高聚物／混合溶剂)性质不能简单地直接从相应的两种二元体系(高聚物／单一溶剂)性质来推演，混合溶剂中排除体积效应往往不是两种单一溶剂中排除体积效应的加权平均。高分子的尺寸除了与单一溶剂一高分子间的相互作用有关外。还受到两种溶剂间的相互作用、高分子的自缔合趋势的影响。在不同的θ溶刺中高分子的无扰尺寸往往不同。两种溶剂间的相互作用是重要的影响因素之一。     

Light-scattering study on cellulose diacetate in 2-butanone

Light-scattering measurements were carried out on three well-fractionated samples of cellulose diacetate (degree of substitution = 2.46) in acetone at 25°C and in 2-butanone at 30–60°C. For the system cellulose diacetate-2-butanone, the theta temperature, Θ, has been quoted as 37°C from cloud-point measurements; it was intended to examine further 2-butanone as a theta solvent. The value of Θ, defined as the temperature at which the second virial coefficient vanishes, was found to be 50°C. This difference in Θ was attributed to association of the dissolved polymer molecules. On the other hand, the weight-average molecular weights obtained in 2-butanone at 50°C were in accord with those determined in a good solvent, acetone. It was established that 2-butanone was a theta solvent for cellulose diacetate with Θ = 50°C. The molecular dimensions observed in 2-butanone were however unreasonably large. Therefore, determinations of the unperturbed dimensions and other conformational parameters in this solvent are withheld. Solution stability and association were examined by light scattering. It was deduced that the difficulty in dissolving the polymer in 2-butanone arose from the copolymeric nature of cellulose diacetate.     

MEASUREMENT OF UNPERTUBED DIMENSION 0F POLYMER

The unperturbed dimension of polymer is measured by a gel permeation chromatography (GPC)coupling with viscometer. The intrinsic viscosities of the fractions are measured with an automaticviscometer, and the molecular weight of the fractions are calculated based on the universal calibration.Using a theoretical expression with linearized Mark-Houwink's equation an unperturbed dimensionis obtained by extrapolating to the unperturbed state. The results agree with the values measuredby conventional method comparisons with various theoretical expressions are made.     

Etude des dimensions moleculaires des polymeres dissous dans des melanges binaires de solvants polaires et non polaires—I. Polyvinyl-2 pyridine

We have studied the molecular dimensions of poly-2-vinylpyridine in solution in binary solvent mixtures consisting of a non polar and a polar component, viz. benzene-ethanol and benzene-chloroform. We have also studied the preferential solvation of the same polymer in the above mixtures using light scattering. We have observed a conformational transition of P2VP taking place in a composition region for each solvent mixture. This transition shows as a discontinuity in the unperturbed dimensions, in the long range interactions parameter and in the parameter of preferential solvation of the polymer. We think that this transition is related to the existence of two ordered structures of the polymer chain, one stable before and the other after the transition region.