Self-diffusion of poly(ethylene oxide) in aqueous dextran solutions measured using FT-pulsed field gradient n.m.r.

Transport in ternary polymer₁, polymer₂, solvent systems has been investigated using an n.m.r. spin-echo technique. The dependence of the self-diffusion coefficient of poly(ethylene oxide) polymers on the concentration and molecular size of dextran in aqueous solution has been measured. Monodisperse poly(ethylene oxide) fractions ($\text{M}\text{?}{}_{\mathrm{w}}\text{=7.3×10}{}^4$, 2.8·10⁵ and 1.2·10⁶) and dextrans ($\text{M}\text{?}{}_{\mathrm{w}}\text{=2·10}{}^4$, 1·10⁵ and 5·10⁵) have been employed over a range of concentration up to the miscibility limit in each system. It is found that when the molecular size of the diffusant is commensurate with or exceeds that of the matrix polymer, a relationship of the form: $\text{(}\text{D}\text{D}{}_0\text{)}{}_{\mathrm{<mtext>PEO</mtext>}}\text{=}\text{exp}\text{?k(C[η])}$ is applicable, where C[η] refers to the dextran component and is considered to describe the extent of coil overlap in concentrated solution. ($\text{D}\text{D}{}_0$) is independent of the molecular size of the poly(ethylene oxide), at least in the range studied (M_w<300 000).     

Polymerization of poly(dimethylsiloxane) macromers: 1. Copolymerization with styrene

The synthesis and characterization of methacrylate-ended macromers ($\text{M}\text{?}{}_{\mathrm{<mtext>n</mtext>}}$ 500 to 10 000) and their copolymerization with styrene (M₂) is described. The experimental errors in the values of the reactivity ratios r₁ render them meaningless. Values of r₂ can be determined with more precision and increase from 1.06 to 1.55 as the molecular weight of the macromer increases. This behaviour is due to steric effects, not diffusion-controlled propagation. It is shown that the assumptions that $\text{1 > r}{}_1\text{[}\text{M}{}_1\text{]}\text{[}\text{M}{}_2\text{]}$ and $\text{r}{}_2\text{>}\text{[}\text{M}{}_1\text{]}\text{[}\text{M}{}_2\text{]}$ are only valid for macromers of $\text{M}\text{?}{}_{\mathrm{<mtext>n</mtext>}}\text{> ca. 10 000}$.     

Synthesis of electroreactive polymers from poly (m,p-chloromethylstyrene) and copoly (m,p-chloromethylstyrene-styrene)

Polymerization, and copolymerization with styrene, of m,p-chloromethylstyrene have been carried out at 75°C, in chlorobenzene and in the presence of AIBN ($\text{[}\text{AIBN}\text{] ? 6 × 10}{}^{\mathrm{?2}}$, and $\text{12 × 10}{}^{\mathrm{?2}}\text{m}$, respectively). The polymer molecular weights, determined by g.p.c., are: $\text{M}\text{?}{}_{\mathrm{w}}\text{= 8670}$, $\text{M}\text{?}{}_{\mathrm{n}}\text{= 5860}$, and $\text{M}\text{?}{}_{\mathrm{w}}\text{/-M}{}_{\mathrm{n}}\text{= 1.48}$ for the homopolymer, poly(m,p-chloromethylstyrene), (1a); and $\text{M}\text{?}{}_{\mathrm{w}}\text{= 8805}$, $\text{M}\text{?}{}_{\mathrm{n}}\text{= 5144}$, and $\text{M}\text{?}{}_{\mathrm{w}}\text{/-M}{}_{\mathrm{n}}\text{= 1.71}$ for the copolymer, copoly(m,p-chloromethylstyrene-styrene), (2a). A series of phosphine derivatives of both 1a and 2a are prepared by the reaction of the polymers with either chlorodiphenylphosphine/lithium, or diphenylphosphine/potassium tert. butoxide. A number of other potentially electroreactive derivatives of 2a are obtained by reacting the polymer with 2-aminoanthraquinone, 3-N-methylamino-propionitrile, or 2-(2-aminoethyl) pyridine. The phosphinated polymers are reacted with bis-benzonitrilepalladium-(II) chloride to obtain a series of polymer-palladium(II) complexes containing 8.5–12.9% palladium. Similarly, reaction of the last-named bidentate polymeric ligand with cupric acetylacetonate, or cupric sulphate pentahydrate, produces polymer-copper(II) complexes having 5.8, or 3.3% copper, respectively. The inter/intra-chain nature of some of the side reactions during the derivatization of the chloromethylated polymers, and that of the complex formation between transition metal centres and macromolecular ligands, are briefly discussed in view of the experimental results.     

Viscosity of heparin in formamide and glycerol

The viscosity of heparin was examined in pure glycerol, formamide and in mixtures of the two solvents. This study confirms that the equation $\text{η}{}_{\mathrm{sp}}\text{c}\text{= [η]}{}_{\mathrm{\infty }}\text{[1 +}\text{k}\text{(c)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{]}$, where [η]_∞ is the shielded intrinsic viscosity, adequately describes the concentration dependence of the reduced viscosity of the polyelectrolyte, heparin. The [η]_∞ linearly increases with the dielectric constant of the solvent.     

The θ-behaviour of heterogeneous macromolecules

A polymer chain consisting of N_r segments with a repulsive interaction (binary cluster integral β_r) and N_a ? N_r segments with a stronger, attractive and pairwise saturable interaction (β_a), which is at the averaged θ-point N²_rβ_r + N²_aβ_a = 0 deviations from the predictions of the two parameter theory: $\text{α}{}^2{}_{\mathrm{<mtext>R</mtext>}}\text{? 1 ～ δz}{}_{\mathrm{<mtext>r</mtext>}}\text{< 0}$ and A₂ ～ δz_r > 0 with $\text{δz}{}_{\mathrm{<mtext>r</mtext>}}\text{～ β}{}_{\mathrm{<mtext>r</mtext>}}\text{(}\text{N}{}_{\mathrm{<mtext>a</mtext>}}\text{N}{}_{\mathrm{<mtext>r</mtext>}}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. It is shown that the deviations from the universal behaviour are due to the existence of an intermediate length scale $\text{～}\text{N}{}_{\mathrm{<mtext>a</mtext>}}\text{N}{}_{\mathrm{<mtext>r</mtext>}}$.     

Sedimentation velocity measurements close to the upper critical solution temperature and at θ-conditions: polystyrene in cyclopentane over a large concentration interval

Sedimentation velocity measurements on polystyrene (M = 110 000) in cyclopentane over an extended concentration region and from 5°C (close to the upper critical solution temperature) to 40°C are reported. The concentration dependence parameter (k_s)_w increases from 2 to 5°C to 27 at 40°C. For all temperatures except 5°C, $\text{s}{}_0\text{s}$ vs. w[η]_w shows an upward curvature at w[η]_w ≈ 1; at 5°C, on the other hand, $\text{s}{}_0\text{s}$ is independent of concentration over the region considered. Furthermore, measurements have also been performed at 20°C (θ-conditions) over a large concentration interval for the molecular weights M = 20 400, 390 000 and 950 000. The parameters s₀ and (k_s)_w were both found to be proportional to $\text{M}\text{?}{}^{\mathrm{1/2}}{}_{\mathrm{w}}$. In the ‘hydrodynamically normalized’ plot $\text{s}{}_0\text{s}$ vs. w[η]_w the sedimentation behaviour can approximately be represented by a single curve for all the molecular weights.     

Polymerization of N,N′-methylenebisacrylamide initiated by CEIV-thiourea redox system

The kinetics of polymerization of the symmetrical non-conjugated divinyl monomer N,N′-methylenebisacrylamide has been studied using Ce^IV-thiourea redox system as initiator. The rate of polymerization, R_p is proportional to $\text{[}\text{Ce}{}^{\mathrm{<mtext>IV</mtext>}}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, $\text{[}\text{thiourea}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{[}\text{monomer}\text{]}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$. A cyclopolymerization mechanism fits in with the experimental results.     

Formation and transformation of SrGeO3

The reaction of an equimolar mixture of SrCO₃ and GeO₂ proceeds in five stages, [1]–[5]. The overall reaction of [1], [2], and [3]

$\text{2SrCO}{}_3\text{+}\text{GeO}{}_2\text{→}\text{Sr}{}_2\text{GeO}{}_4\text{+}\text{2CO}{}_2\text{[1]}\text{SrCO}{}_3\text{+}\text{4GeO}{}_2\text{→}\text{SrGe}{}_4\text{O}{}_9\text{+}\text{CO}{}_2\text{[2]}\text{SrCO}{}_3\text{+}\text{GeO}{}_2\text{→}\text{β-SrGeO}{}_3\text{+}\text{CO}{}_2\text{[3]}\text{β-SrGeO}{}_3{}^{\mathrm{<mtext>transformation</mtext>}}\text{α-SrGeO}{}_3\text{[4]}\text{3Sr}{}_2\text{GeO}{}_4\text{+}\text{SrGe}{}_4\text{O}{}_9\text{→7(}\text{α-SrGeO}{}_3\text{)}\text{[5]}$

is best described by the Jander equation, the apparent activation energy being 47.6 kcal mol^?1 irrespective of the ball-milling time. β-Strontium metagermanate is formed directly at lower temperatures from amorphous material prepared by the simultaneous hydrolysis of strontium and germanium alkoxides. Kinetic studies of β-SrGeO₃ formation and β- → α-SrGeO₃ transformation are carried out by means of X-ray diffraction.     

Generalization of correlation between polymer glass transition Tg and an e.s.r. parameter T50G

The tumbling of five nitroxide spin probes (molecular weights between 172–486 g/mol) in a standard unfractionated polyisobutylene [$\text{M}\text{?}{}_{\mathrm{v}}\text{= (1.26 ± 0.18) × 10}{}^6\text{g/mol}$] has been studied by means of the electron spin resonance (e.s.r.) technique. The temperature at which the separation of the outermost peaks of the e.s.r. spectrum is 50 G (T_50G) attained a limiting value T′_50G = 330K at probe M_W = 332 g/mol. This temperature coincided with the temperature of the loss maximum of the merged glass transition (T_g) and segmental relaxations at the corresponding frequency (3 × 10⁷ Hz). A literature survey indicated that an analogous situation exists in the case of poly(vinylidene fluoride) and polyamide-6,10 while T′_50G values of poly(2,6-dimethyl phenylene oxide) and polycarbonate are correlated only to segmental relaxations of polymer chains. It is concluded that the equation:

$\text{T}{}_{\mathrm{<mtext>50</mtext><mtext>G</mtext>}}\text{= T}{}_{\mathrm{g}}\text{[1 + (}\text{exp}\text{T}{}_{\mathrm{g}}\text{/T}{}_{\mathrm{c}}\text{)}{}^{\mathrm{?1}}\text{]}$

describes generally the temperature shift between glass transitions at low and high frequencies and can be applied to determine experimentally low frequency T_g values from T′_50G values if T_g and T < T_g relaxations (if any are present) are already merged at this temperature.     

Interpretation of hydrogenation kinetics of spent oil distillate from u.v. spectroscopy

Hydrotreatment of spent oil distillate was carried out on a commercial Ni-Mo-alumina catalyst in the temperature range 260–340 °C, with a liquid hourly space velocity (LHSV) of 0.7–2.0 h^?1, pressure of 4.5 MPa and $\text{H}{}_2\text{oil}$ ratio of 300 NL L^?1 (normal litre of H₂ per litre of feedstock). U.v. spectra of hydrogenated and original spent oil distillates (measured in normal hexane) gave a band with a maximum at 230 nm. The change in absorbance at three selected wavelengths for original oil distillate and hydrotreated oil at different operating conditions was taken as a guide for the determination of hydrogenation reaction rates (including partial saturation of aromatics and sulphur compound hydrogenolysis). The rate constants of hydrogenation reactions (k) using a second-order equation and a model of two parallel first-order reactions (k₁ and k₂) were calculated. Finally, the apparent activation energy (E_a), enthalpy of activation ($\text{ΔH}{}^1$) and entropy ($\text{ΔS}{}^1$) were calculated based on the values of k, k₁, and k₂. The calculated values of E_a based on k, k₁ and k₂ were 81.479, 71.188 and 62.882 kJ mol^?1, respectively. The values of $\text{ΔH}{}^1$ based on the same rate constants were 76.670, 66.564 and 58.433 kJ mol^?1, while the values of $\text{ΔS}{}^1$ were ?117.150, ?133.779 and ?150.823 J mol^?1 K^?1, respectively.     

Properties of extremely high molecular weight polystyrene in solution

Extremely high molecular weight polystyrenes with a $\text{M}\text{?}{}_{\mathrm{w}}$ in the range 10.8 × 10⁶ to 2.2 × 10⁷ were prepared by emulsion polymerization initiated with a heterogeneous initiator at 30°C, which has a ‘living character’. Samples of polystyrene were characterized by light scattering and viscometry in toluene and benzene at 25°C, and in θ-solvent cyclohexane at 34.8°C. Also determined were the relationships of mean-square radius of gyration 〈s²〉 (m²) and the second virial coefficient A₂ (m³ mol kg^?2) on the molecular weight, which for toluene and benzene are described in equations: Toluene (25°C) $\text{〈s}{}^2\text{〉=1.59 × 10}{}^{\mathrm{?23}}\text{M}\text{?}{}_{\mathrm{w}}{}^{1.23}$; $\text{A}{}_2\text{=4.79 × 10}{}^{\mathrm{?3}}\text{M}\text{?}{}_{\mathrm{w}}{}^{\mathrm{?0.63}}$; Benzene (25°C) $\text{〈s}{}^2\text{〉=1.23 × 10}{}^{\mathrm{?22}}\text{M}\text{?}{}_{\mathrm{w}}{}^{1.20}$; $\text{A}{}_2\text{=2.59 × 10}{}^{\mathrm{?3}}\text{M}\text{?}{}_{\mathrm{w}}{}^{\mathrm{?0.59}}$. The parameters in the Mark-Houwink-Sakurada equation were established, for extremely high molecular weight polystyrene in toluene and in benzene, at 25°C into the form giving for $\text{[η] (}\text{m}{}^3\text{kg}{}^{\mathrm{?1}}\text{): [η] = 8.52 × 10}{}^{\mathrm{?5}}\text{M}\text{?}{}_{\mathrm{w}}{}^{0.61}$; $\text{[η] = 1.47 × 10}{}^{\mathrm{?4}}\text{M}\text{?}{}_{\mathrm{w}}{}^{0.56}$. The mentioned relations, as well as the obtained values of Flory parameter ?₀ and of ratio $\text{[η]}\text{M}\text{?}{}_{\mathrm{w}}{}^{0.5}$ were compared with solution properties of high molecular weight polystyrene with narrow molecular weight distribution prepared by anionic polymerization by Fukuda et al.     

Studies of cyclic and linear poly(dimethyl siloxanes): 10. Calculations of radii of gyration

A Monte Carlo method has been devised for calculating the conformation-dependent properties of cyclic poly(dimethyl siloxanes) (PDMS), using Flory, Crescenzi and Mark's rotational isomeric state model. Calculated values of the mean-square radii of gyration 〈s²_r〉 of ring molecules unperturbed by excluded volume effects and containing 8–100 skeletal atoms are compared with the 〈s²_l〉 values for the corresponding unperturbed chain molecules. Exact enumeration methods were also employed for rings $\text{[(}\text{CH}{}_3\text{)}{}_2\text{SiO}\text{]}{}_{\mathrm{<mtext>w</mtext><mtext>2</mtext>}}$ with w ? 24 and the results found to be in close agreement with those obtained by the Monte Carlo method. The ratio $\text{〈s}{}^2{}_{\mathrm{l}}\text{〉}\text{〈s}{}^2{}_{\mathrm{r}}\text{〉}$ was found to attain limiting values close to 2.0 for w > 30, in agreement with theoretical predictions.     

Non-classical free-radical polymerization: 3. Diffusion-control in degradative addition

The different kinetic features associated with polymerizations in which retardation arises through degradative transfer and degradative addition processes are considered. Reasons are given for believing that in reactions retarded by degradative transfer neglect of the interaction between ‘inactive’ radicals is justifiable, while with degradative addition this is not so. A kinetic treatment of the latter is developed in which all three termination reactions between propagating and inactive radicals are assumed to be diffusion-controlled with a single rate coefficient and equations are derived which permit from experimental data on rates of polymerization estimation of the definitive kinetic parameters $\text{k}{}_{\mathrm{p}}\text{k′}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{t}}$, $\text{k}{}_{\mathrm{pm}}\text{k′}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{t}}$ and $\text{k}{}_{\mathrm{fm}}\text{k′}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{t}}$ (k_p, k′_t, k_pm, k_fm are the rate coefficients of propagation, termination, reinitiation and degradative additions, respectively). The kinetic equations are satisfactorily consistent with ew experimental data on the polymerization of 1-vinylimidazole in ethanol solution at 70°C, for which there is strong evidence for the occurrence of degradative addition. A modified procedure for processing data for polymerizations with degradative transfer is put forward which is convenient for estimating the kinetic parameters and reveals in a simple manner the importance of re-initiation. It is suggested that this treatment could be generally useful in the early stages of the study of a retarded polymerization.     

Rigid backbone polymers, XVII: Solution viscosity of polydisperse systems

When plotted against concentration V⁰₂, the viscosity η⁰ curve of isotropic solutions of lyotropic nematic mesomorphic polymers increases according to:

$\text{η}{}^0\text{=η}{}_0\text{[[η]V}{}^0{}_2\text{+(}\text{π}\text{4}\text{)[η]}{}^2\text{(V}{}^0{}_2\text{)}{}^2\text{+K}{}_2\text{(}\text{ln}\text{x}\text{)}{}^2\text{[η]}{}^3\text{(V}{}^0{}_2\text{)}{}^3\text{+…]}$

in which η₀ is the solvent viscosity, K₂ a numerical constant, x? is the average molecular axial ratio and [η] the intrinsic viscosity as defined by:

$\text{[η]=}\text{2}\text{x}{}^2\text{45}\text{1}\text{ln}\text{2}\text{x}\text{?1.84}\text{+}\text{3}\text{ln}\text{2}\text{x}\text{?0.61}\text{(+}\text{14}\text{15}\text{)}$

At the concentration $\text{v1}{}_2$ an anisotropic phase appears and the viscosity curve shows a decrease in slope followed by a change in direction at a peak viscosity η^p at v^p₂. Upon further increase in v⁰₂ the system undergoes a phase inversion and finally turns fully anisotropic at v^A₂. In the biphasic interval the viscosity is described by:

$\text{η}{}^0\text{=η}{}_{\mathrm{<mtext>mat</mtext>}}\text{1+}\text{(5λ+2)}\text{2(λ+1)}\text{V}{}_{\mathrm{<mtext>inc</mtext>}}$

where $\text{λ =}\text{η}{}_{\mathrm{<mtext>inc</mtext>}}\text{η}{}_{\mathrm{<mtext>mat</mtext>}}$, the ratio of the inclusions viscosity to the matrix viscosity, and v_inc the volume fraction of the inclusions in the system. It must be emphasized that the molecular weight of the polymer in both phases changes continuously with concentration, resulting in commensurate changes in η_ince, η_mat and their ratio λ. In the anisotropic region the viscosity first decreases moderately and then increases precipitously with v⁰₂, according to:

$\text{η}{}^0\text{=η}{}_0\text{[}\text{2}\text{x}{}^2\text{90S}\text{(}\text{5}\text{ln}\text{2}\text{x}\text{?1.8}\text{+}\text{6}\text{ln}\text{2}\text{x}\text{?0.61}\text{)+2]}\text{V}{}^0{}_2\text{1-}\text{V}{}_{\mathrm{25°}}\text{V}{}_{\mathrm{E}}$

in which S is an order parameter and V₂₅, V_E are volumes swept by the orbits of the flowing rodlike macromolecules. The equations give results in good qualitative and fair quantitative agreement with experimental data in the literature.     

Dielectric properties of oligomers: 4. Dielectric properties of vinyl acetate and methyl methacrylate oligomers

Dielectric properties of vinyl acetate and methyl methacrylate oligomers were studied in order to compare the dielectric properties of an oligomer with those of the corresponding high polymers. The two oligomers showed asymmetric dielectric relaxations at room temperatures. The complex dielectric constants vs. angular frequencies for these oligomers were well represented by the Havriliak-Negami equation:

$\text{?}{}^{\mathrm{ast;}}\text{??}{}_{\mathrm{\infty }}\text{=}\text{?}{}_0\text{??}{}_{\mathrm{\infty }}\text{[1+(jωτ}{}_0\text{)}{}^{\mathrm{1?\alpha }}\text{]}{}^{\mathrm{\beta }}$

The distribution parameters (1 - α) and β of vinyl acetate and methyl methacrylate oligomer are almost equal to those of poly(vinyl acetate) and poly(methyl methacrylate), respectively. It was concluded that the distribution of relaxation times was independent of the molecular weight of the polymers.     

Studies of cyclic and linear poly(dimethyl siloxanes): 1. Limiting viscosity number-molecular weight relationships

The limiting viscosity numbers of ten cyclic and ten linear poly(dimethyl siloxane) fractions have been measured in a π-solvent (butanone at 293K) and in two ‘good’ solvents (toluene and cyclohexane at 298K). The dimethyl siloxane fractions studied were in the molecular weight range $\text{800 <}\text{M}\text{?}{}_{\mathrm{w}}\text{< 17 000}$. The data obtained are compared with related studies published in the literature. The ratio of the limiting viscosity numbers [η]_r and [η]_l of the cyclic and linear poly(dimethyl siloxanes) with $\text{M}\text{?}{}_{\mathrm{w}}\text{> 2500}$ was found to be 0.67 in butanone at 293K. This value is identical (within experimental error) to the theoretical ratio $\text{[η]}{}_{\mathrm{r}}\text{[η]}{}_{\mathrm{l}}\text{= 0.66}$ predicted by Bloomfield and Zimm and others for ring and chain polymers in π-solvents. The ratio $\text{[η]}{}_{\mathrm{r}}\text{[η]}{}_{\mathrm{l}}$ was found to be somewhat smaller for the higher molecular weight polymers in the ‘good’ solvents.     

Viscoelastic properties of poly(propylene glycols)

The relaxational and retardational properties of poly(propylene glycol) liquids, of nominal molecular weights 400 and 4000, are described. The viscoelastic behaviour of each liquid has been determined over a wide temperature range, using high frequency shear wave techniques operating at 30 and 454 MHz. It is found that the complex compliance $\text{J1(jω)}$ is described in terms of the viscosity ν, the limiting high frequency compliance J_∞, the retardational compliance J_r and a characteristic retardation time $\text{т}{}_{\mathrm{r}}$ by:

$\text{J}{}^1\text{(jω)=J}{}_{\mathrm{\infty }}\text{+}\text{1}\text{jωη}\text{+}\text{j}{}_{\mathrm{r}}\text{(1+jωτ}{}_{\mathrm{r}}\text{)}{}^{\mathrm{\beta }}$

where β is a parameter of the retardation time distribution.For the lower molecular weight liquid, $\text{J}{}_{\mathrm{r}}\text{J}{}_{\mathrm{\infty }}\text{= 17.4}$, β = 0.45 and $\text{т}{}_{\mathrm{r}}\text{т}{}_{\mathrm{m}}$ increases with decreasing temperature, reaching a limit of 170 near 0°C. This liquid shows no evidence of polymeric behaviour.For the other, $\text{J}{}_{\mathrm{r}}\text{J}{}_{\mathrm{\infty }}$, β = 0.76, $\text{т}{}_{\mathrm{r}}\text{т}{}_{\mathrm{m}}\text{= 15.4}$ and is constant over the temperature range investigated. The main difference between the two liquids appears as an additional retardational or relaxational process for the higher molecular weight material which occurs in the initial or low frequency part of the relaxation region. This process is characterized by a single time, but with relaxation time $\text{1}\text{7}$ and a stiffness 7 times the values calculated for the first Rouse mode of polymer chain motion.     

Activated diffusion of methane from coals at elevated pressures

Diffusion of methane from three coals ranging in rank from anthracite to HVA bituminous has been studied at initial methane pressures up to about 2.76 MPa (400 psi). Unsteady-state diffusion conditions existed, the methane pressure within the coal particle decreasing with time while the methane pressure outside the particles remained at atmospheric. The diffusion parameter $\text{D}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{r}{}_0$ increased with increasing methane concentration at high values of methane sorption. Diffusion was activated but the exact magnitude of the activation energy is uncertain owing to the suspected contribution of the heat of sorption to the temperature coefficient. $\text{D}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{r}{}_0$ increased with decreasing particle size of coal studied, but r₀ is clearly less than the particle radius.