Gas separation properties of polymer films based on semicrystalline poly(4-methyl-1-pentene) (PMP) with T_g = 30°C for permanent gases and some lower hydrocarbons have been experimentally studied in the temperature range of −20 to 80°C. Experiments have been performed using the differential permeability technique involving the determination of the diffusion coefficient by the characteristic time and functional scaling-up methods. It has been shown that PMP as a biphasic system may be characterized by one diffusion coefficient that includes the contributions of diffusion in the amorphous and crystalline phases. It has also been shown that despite the glass transition (phase transition) at 30°C, the permeability coefficients of the test gases exponentially increase with gas temperature and the temperature dependence curves do not exhibit an inflection in the glass transition region. On the other hand, the Arrhenius plots of the diffusion coefficients show a bend over the entire glass transition range in PMP, with the activation energy of diffusion decreasing with an increase in temperature. This fact demonstrates the unusual, earlier unknown effect of increasing activation energy of diffusion E_D for gases below T_g.

Designing hollow fiber (HF) membrane modules occupies one of the key positions in the development of efficient membrane processes for various purposes. In developing HF membrane modules, it is very important to have a uniform HF distribution and flow mixing in the shell side to significantly improve mass transfer and efficiency. This work suggests the application of different textile 3D HF structures (braided hoses and woven tape fabrics). The 3D structures consist of melt-spun, dense HFs based on poly(4-methyl-1-pentene) (PMP). Since the textile processing of HFs can damage the wall of the fiber or close the fiber bore, the membrane properties of the obtained structures are tested with a CO₂/CH₄ mixture in the temperature range of 0 to 40 °C. It is shown that HFs within the textile structure keep the same transport and separation characteristics compared to initial HFs. The mechanical properties of the PMP-based HFs allow their use in typical textile processes for the production of various membrane structures, even at a larger scale. PMP-based membranes can find application in separation processes, where other polymeric membranes are not stable. For example, they can be used for the separation of hydrocarbons or gas mixtures with volatile organic compounds.

The features of the butane transfer through homogeneous membranes 40–50 μm thick based on poly(4-methyl-1-pentene) (PMP) of various crystallinity degrees have been investigated in the temperature range from 10 to 80°C. It has been shown that in this temperature range, including T_g of the polymer, for continuous PMP membranes obtained by the melt technology there is a significant influence of butane activity, which was previously described in the literature for composite membranes based on PMP with thin selective layers formed from solutions. It has been noted that the degree of crystallinity of PMP has a significant effect on the permeability. Based on the experimental data, the temperature parameters have been calculated taking into account the exponential form of the dependence of permeability on the butane activity. Temperature dependences have been obtained in the absence of the influence of butane on the polymer, which have a nearly linear form in the Arrhenius coordinates, while practically coinciding for samples with different degrees of crystallinity.

New hollow fiber gas separation membranes with a non-porous selective layer based on poly(4-methyl-1-pentene) (PMP) granules have been obtained using the solution-free melt spinning process. The influence of the preparation conditions on the geometry of the obtained samples was studied. It was found that a spin head temperature of 280 °C and a specific mass throughput of 103 g mm⁻² h⁻¹ are optimal to obtain defect-free, thin-walled hollow fibers in a stable melt spinning process, using the given spinneret geometry and a winding speed of 25 m/min. The gas permeability and separation properties of new fibers were studied using CO₂/N₂ and CO₂/CH₄ mixtures, and it was found that the level of gas selectivity characteristic of homogeneous polymer films can be achieved. The features of the gas mixture components permeability below and above the PMP glass transition temperature have been experimentally studied in the range of CO₂ concentrations from 10 to 90% vol. The temperature dependences of the permeability of the CO₂/CH₄/N₂ mixture through the obtained HF based on PMP have been investigated, and the values of the apparent activation energies of the permeability have been calculated, which make it possible to predict the properties of membrane modules based on the obtained membranes in a wide temperature range.

Poly (4-methyl-2-pentyne) (PMPentyne) and poly (4-methyl-1-pentene) (PMPentene) as membrane gas-separating media were studied with a combination of experimental and theoretical approaches. Experimental approaches included the permeability measurements for C₁–C₄ alkanes in linear heating mode (for PMPentyne) and under isothermal conditions (for PMPentene), and diffusivity evaluation by a differential method for PMPentene. Theoretical approaches included the ‘hard-spheres’ theory for calculation of gas solubility in PMPentyne and gas transport theory for two-phase systems for the estimation of the amorphous and crystalline phases contribution in PMPentene. Correlation analysis was used for any type of gas transfer parameter calculation where experimental data were lacking. These combinations of methods allowed obtaining the whole set of parameters for any gas–polymer pairing and explained the butane-selective properties revealed in PMPentyne (C₁ < C₂ < C₃ < C₄) and methane-selective properties of PMPentene (C₁ > C₂ > C₃ > C₄).