Yuri Yampolskii

Polymeric Gas Separation Membranes

This short Perspective conveys to the general reader of Macromolecules basic approaches of materials science of polymeric membranes for gas and vapor separation. The relations between the polymer structure and transport properties of rubbery and glassy membrane materials are considered. On the basis of acquired information, several methods for quantitative prediction of permeability were developed, and their comparative analysis is given in the Perspective. The past decade was marked by the appearance of a number of novel interesting membrane materials, which will be briefly described in the text. In conclusion, novel approaches for achieving highly permeable and permselective materials (e.g., mixed matrix membranes) will be considered as well as several relevant but not solved so far problems of membrane gas separation.

Materials Science of Membranes for Gas and Vapor Separation: Freeman/Materials Science of Membranes for Gas and Vapor Separation

Contributors. Preface. 1. Transport of Gases and Vapors in Glassy and Rubbery Polymers (Scott Matteucci, Yuri Yampolskii, Benny D. Freeman and Ingo Pinnau). 2. Principles of Molecular Simulation of Gas Transport in Polymers (Doros N. Theodorou). 3. Molecular Simulation of Gas and Vapor Transport in Highly Permeable Polymers (Joel R. Fried). 4. Predicting Gas Solubility in Membranes through Non-Equilibrium Thermodynamics for Glassy Polymers (Ferruccio Doghieri, Massimiliano Quinzi, David G. Rethwisch and Giulio C. Sarti). 5. The Solution-Diffusion Model: A Unified Approach to Membrane Permeation (Johannes G. (Hans) Wijmans and Richard W. Baker ). 6. Positron Annihilation Lifetime Spectroscopy and Other Methods for Free Volume Evaluation in Polymers (Yuri Yampolskii and Victor Shantarovich). 7. Prediction of Gas Permeation Parameters of Polymers (Alexander Alentiev and Yuri Yampolskii ). 8. Synthesis and Permeation Properties of Substituted Polyacetylenes for Gas Separation and Pervaporation (Toshio Masuda and Kazukiyo Nagai). 9. Gas and Vapor Transport Properties of Perfluoropolymers (Tim C. Merkel, Ingo Pinnau, Rajeev Prabhakar and Benny D. Freeman). 10. Structure and Transport Properties of Polyimides as Materials for Gas and Vapor Membrane Separation (Kazuhiro Tanaka and Ken-Ichi Okamoto). 11. The Impact of Physical Aging of Amorphous Glassy Polymers on Gas Separation Membranes (Peter H. Pfromm). 12. Zeolite Membranes for Gas and Liquid Separations (George R. Gavalas). 13. Gas and Vapor Separation Membranes Based on Carbon Membranes (Hidetoshi Kita). 14. Polymer Membranes for Separation of Organic Liquid Mixtures (Tadashi Uragami ). 15. Zeolite Membranes for Pervaporation and Vapor Permeation (Hidetoshi Kita). 16. Solid-State Facilitated Transport Membranes for Separation of Olefins/Paraffins and Oxygen/Nitrogen ( Yong Soo Kang, Jong Hak Kim, Jongok Won and Hoon Sik Kim ). 17. Review of Facilitated Transport Membranes (Richard D. Noble and Carl A. Koval ). Index.

Synthesis and gas permeation properties of novel spirobisindane-based polyimides of intrinsic microporosity

Three novel polyimides (PIM-PIs) with characteristics similar to a polymer of intrinsic microporosity (PIM) were prepared by the reactions of a novel spirobisindane-based dianhydride with appropriate aromatic diamines. A polymerisation procedure via in situ ester precursor formation provided PIM-PIs with very high molar masses. The gas permeation parameters (permeability (P), diffusion (D) and solubility (S) coefficients) were determined for these polymers. These PIM-PIs exhibit both high apparent surface areas and high gas permeability coefficients, greater than those of most polyimides studied so far and only slightly smaller than the permeability coefficients of the archetypal polymer of intrinsic microporosity, PIM-1. Treatment of the films with alcohols results in significant increases the P values, just as has been noted for PIM-1. This enhancement is caused by an increase of the diffusion coefficients, while the solubility coefficients are much less sensitive to this treatment. However, PIM-PIs are distinguished by extremely high gas solubility coefficients a property, which is characteristic to all PIMs.

Enhanced gas separation factors of microporous polymer constrained in the channels of anodic alumina membranes.

New composite membranes based on porous anodic alumina films and polymer of intrinsic microporosity (PIM-1) have been prepared using a spin-coating technique. According to scanning electron microscopy, partial penetration of polymer into the pores of alumina supports takes place giving rise to selective polymeric layers with fiber-like microstructure. Geometric confinement of rigid PIM-1 in the channels of anodic alumina causes reduction of small-scale mobility in polymeric chains. As a result, transport of permanent gases, such as CH4, becomes significantly hindered across composite membranes. Contrary, the transport of condensable gases (CO2, С4H10), did not significantly suffer from the confinement due to high solubility in the polymer matrix. This strategy enables enhancement of selectivity towards CO2 and C4H10 without significant loss of the membrane performance and seems to be prospective for drain and sweetening of natural gas.

A Current Position of Polyacetylenes Among Other Highly Permeable Membrane Materials

ABSTRACT Synthesis of polyacetyelenes and investigation of their gas permeation properties strongly influenced membrane material science. Many other highly permeable glassy polymers that belong to different chemical classes have been created and investigated. In many case their design was similar to that of disubstituted polyacetyelenes. Structure and properties of various polymers with SiMe3 side groups are considered in this review. Many of them are characterized by solubility controlled permeation of hydrocarbons like polyacetylenes. An important factor that determines high permeability of all these polymers is large free volume caused by bulky substituents and rigid backbone chains.

Janus tricyclononene polymers bearing tri(n-alkoxy)silyl side groups for membrane gas separation

A series of polymers of a new type, which contain rigid polymer main chains (glassy nature) and long flexible side substituents (rubbery nature), were prepared from norbornene derivatives with (AlkO)3Si-groups of a different length (Alk = Me, Et, n-Pr, n-Bu) as promising materials for membrane separation of gaseous hydrocarbons. The 1st generation Grubbs complex and Pd–N-heterocyclic carbene complex in combination with Na+[(3,5-(CF3)2C6H3)4B]− and PCy3 were used as catalysts of metathesis and addition polymerization in the synthesis of high-molecular weight polymers (Mw ≤ 1.1 × 106) with good or high yields (up to 99%). The prepared addition polymers were glassy, while the glass transition temperature of metathesis polymers depended on the length of the alkyl-group in (AlkO)3Si-substituents and it varied in the range of −44 to 61 °C. The dramatic tuning of polymer gas-transport properties was demonstrated by the change of the polymer main chain structure and the length of tri(n-alkoxy)silyl side groups. For example, we have succeeded for the first time in obtaining metathesis polynorbornenes, which turned out to be more permeable than their addition isomers. Not being large free volume polymers, all studied metathesis and addition polytricyclononenes exhibited solubility controlled permeation of hydrocarbons (P(n-C4H10) up to 8100 barrer) and high C4/C1 selectivity (22–49).

Synthesis and properties of polynorbornenes containing trialkoxysilyl groups

In this work we report the synthesis and polymerization of new norbornenes containing trialkoxysilyl groups. These monomers were reactive both in ROMP and in addition polymerization. Obtained polymers possessed interesting properties. So despite of low surface area they were good permeable, and some of them exhibited a low tendency to aging. The solubility controlled selectivity for hydrocarbons was observed. These properties would allow finding industrial application of obtained polymers for the membrane gas separation of hydrocarbon mixtures.In this work we report the synthesis and polymerization of new norbornenes containing trialkoxysilyl groups. These monomers were reactive both in ROMP and in addition polymerization. Obtained polymers possessed interesting properties. So despite of low surface area they were good permeable, and some of them exhibited a low tendency to aging. The solubility controlled selectivity for hydrocarbons was observed. These properties would allow finding industrial application of obtained polymers for the membrane gas separation of hydrocarbon mixtures.