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Polynorbornenes are ideal materials for systematic structure–property investigations designed to correlate gas-transport properties to polymer structure. The modular nature of norbornene-based systems provides a facile route towards the synthesis of diverse polymeric materials. Though many valuable correlations between gas-permeability and polynorbornene structure have been summarized in a prior review (2017), many of these efforts focused heavily on the design of materials with high permeabilities. More recently, the design of next-generation polynorbornene membranes has shifted toward the development of materials that are highly selective for multiple targeted gas separations. Since 2017, tremendous progress has been realized in the preparation of stable and highly selective polynorbornenes for membrane-based gas separations. Examples include polynorbornene derivatives that exhibit very high selectivity for CO2/N2 and light hydrocarbon (e.g., C3+/C1) separations, some of which exhibit gas separation performances that approach or exceed the 2008 upper bound. Herein, we summarize prior findings, present recent developments in the field of advanced polynorbornene membrane materials for targeted gas separations, and provide an outlook for the future of this field of research.

Fluorinated polymers are attractive due to their special thermal, surface, gas separation, and other properties. In this study, new diblock, multiblock, and random copolymers of cyclooctene with two fluorinated norbornenes, 5-perfluorobutyl-2-norbornene and N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide, are synthesized by ring-opening metathesis copolymerization and macromolecular cross-metathesis in the presence of the first- to third-generation Grubbs’ Ru-catalysts. Their thermal, surface, bulk, and solution characteristics are investigated and compared using differential scanning calorimetry, water contact angle measurements, gas permeation, and light scattering, respectively. It is demonstrated that they are correlated with the chain structure of the copolymers. The properties of multiblock copolymers are generally closer to those of diblock copolymers than of random ones, which can be explained by the presence of long blocks capable of self-organization. In particular, diblock and multiblock fluorine-imide-containing copolymers show a tendency to form micelles in chloroform solutions well below the overlap concentration. The results obtained may be of interest to a wide range of researchers involved in the design of functional copolymers.

Commercial metathesis polynorbornene is used for the fabrication of high-damping coatings and bulk materials that dissipate vibration and impact energies. Functionalization of this non-polar polymer can improve its adhesive, gas barrier, and other properties, thereby potentially expanding its application area. With this aim, the post-modification of polynorbornene was carried out by inserting ethylene–vinyl acetate–vinyl alcohol blocks into its backbone via the cross-metathesis of polynorbornene with poly(5-acetoxy-1-octenylene) and subsequent deacetylation and hydrogenation of the obtained multiblock copolymers. For the first time, epoxy groups were introduced into the main chains of these copolymers, followed by the oxirane ring opening reaction. The influence of post-modification on the thermal, gas separation, and mechanical properties of the new copolymers was studied. It was shown that the gas permeability of the copolymer significantly depends on its composition, as well as on the amounts of hydroxyl and epoxy groups. The developed methods efficiently improve the barrier properties, reducing the oxygen permeability by 15–33 times in comparison with polynorbornene. The obtained results are promising for various applications and can be extended to a broader family of polydienes and other polymers containing backbone double bonds.

We investigate the structure–property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state.

The impact of double bond modification by gem-difluorocyclopropanation (gDFC) in poly(norbornenes) backbone on their gas transport properties was studied for the first time. With this aim the research of gDFC of polynorbornene (PNB) and poly(5-trimethylsilylnorbornene) (PNBSi) in the conditions of sodium chlorodifluoroacetate thermolyses at 180–190 °C in methyl benzoate solution were carried out. The starting poly(norbornenes) were synthesized via ring-opening metathesis polymerization of the corresponding monomers mediated by the first generation Grubbs’ catalyst. The degree of double bonds conversion into the gem-difluorocyclopropane and the molecular weight of modified polymers could be controlled by adjusting the reaction time, sodium chlorodifluoroacetate amount, and polymer concentration in reaction mixture, as well as by addition of inhibitor. The bulky Me3Si-substituent hindered the modification of double bonds in poly(norbornenes)’ backbone. The gDFC decreased the thermal stability of poly(norbornenes). However, the films of modified polymers demonstrated high stability during storage at the ambient conditions, especially in comparison with unmodified polynorbornene. The introduction of gem-difluorocyclopropane in poly(norbornenes) backbone increased their gas permeability coefficients P especially strongly for PNB. Simultaneously the values of ideal selectivity αij = Pi/Pj were not changed or slightly increased. The noted growth of P was caused by increases in the solubility coefficients S. To elucidate the role of the two types of modification fragment ( CF2 and O ) of double bonds a sample was prepared that included both types of the fragments. It was distinguished by increased P and αij values. So, a new and simple approach improving the gas permeation properties of metathesis polynorbornenes was developed. It may be extendable to broader families of polydienes and other polymers containing double bonds in the backbone.

Crystallinity of statistical multiblock copolymers of norbornene and cyclooctene with nearly equimolar composition and different degrees of blockiness is studied by differential scanning calorimetry including thermal fractionation by successive self-nucleation and annealing and by X-ray diffraction. The copolymers are synthesized via recently invented reaction of polymer cross-metathesis, as a result of interchain exchange between polynorbornene and polyoctenamer in the presence of Grubbs’ catalyst of the first generation. This catalyst raises the fraction of trans-octenylene units up to more than 80% promoting formation of triclinic crystals. The copolymer degree of crystallinity and melting peak temperature decrease with the cross-metathesis conversion. At the same time the equilibrium melting temperature predicted by the Flory theory of copolymer crystallization is not much affected by the interchange reaction. Compared with the pure polyoctenamer or its equimolar blend with polynorbornene, the norborene-cyclooctene copolymers form considerably smaller crystallites. Thermal fractionation makes it possible to find their size distribution, which correlates with the average length of trans-octenylene blocks. Short annealing the multiblock copolymers above their melting points gives rise to a small but persistent endotherm 5–10 degrees above the annealing temperature, which is absent in polyoctenamer and, therefore, may indicate mixing of segregated norbornene and cyclooctene blocks.

Heterochain polycarbosilanes are well-known materials possessed important properties. Some of their applications, such as gas separation membranes, require polymers with high molecular weight that provide good film-forming and mechanical properties. In this research, the synthesis of poly(1,1-dimethyl-1-silapentene) via the ring-opening metathesis polymerization (ROMP) of 1,1-dimethyl-1-silacyclopentene and the acyclic dienes metathesis (ADMET) of diallyldimethylsilane mediated by Ru-carbene Grubbs complexes 1st - 3rd generations as well as Hoveyda-Grubbs 2nd generation catalyst were studied for the first time. High molecular weight poly(1,1-dimethyl-1-silapentene) was synthesized by ROMP of 1,1-dimethyl-1-silacyclopentene. Varying the type and loading catalyst, temperature and monomer concentration, we obtained poly(1,1-dimethyl-1-silapentene) with Mw = 100–143 kDa, which is significantly higher (5–7 times) than that reached previously by olefin metathesis polymerization. The activities of 1,1-dimethyl-1-silacyclopentene and cyclopentene in ROMP were compared using 1H NMR monitoring the conversion of their double bonds. The ADMET polymerization of diallyldimethylsilane led to oligomers with the average polymerization degree not exceeded 4.4.

Copolymers of norbornene and cyclooctene were synthesized for the first time by the cross-metathesis of polynorbornene with polyoctenamer. This strategy made it possible to use the 1st generation Grubbs catalyst, which exhibits low activity toward copolymerization of those monomers. Statistical multiblock copolymers with average block lengths varying from 200 to 2 units were obtained.

Polymers of different classes are considered as membrane materials for separation of hydrocarbons C1–C4. It has been known for a long time that solubility controlled permeation is characteristic of rubbery polymers and in particular of the most permeable rubber polydimethylsiloxane. The transport properties of these polymers are considered. Discovery of poly(trimethylsilyl propyne) and other polyacetylenes showed that similar properties can be revealed in glassy polymers. As is discussed in this review, the most important properties are reduction of the permeability of light components (CH4) in the presence of more condensable penetrant (C4H10) and higher selectivity of mixture separation as compared with ideal separation factors measured in the experiments with pure gases. Recently, two other classes of glassy polymers with solubility controlled permeation were discovered: addition type Si-containing norbornene polymers and metathesis polynorbornenes with flexible Si–O bonds in side groups. The transport properties of these novel polymers are considered in detail. It was shown that for the former group of norbornene polymers the reasons for solubility controlled permeation is great and opened porosity just as is the case for polyacetylenes. For the latter group, the presence of flexible Si–O bonds in side groups is responsible for their transport properties.

The transport parameters (permeability coefficients, separation factors) were determined for the separation of mixtures of n-butane and methane. The content of butane in the feed was in the range 3.7–7.9% and simulated the composition of associated petroleum gas. The experiments were carried out at room temperature and feed pressure of 2–6 atm. Novel membrane materials – poly(trimethylsilylnorbornene) and poly(bis-(trimethylsilyl)tricyclononene) – were studied in the form of dense films. Both polymers reveal a distinct solubility controlled permeation: the permeate streams were strongly enriched (up to 58%) with the heavier component (C4H10), the permeability of methane was reduced by a factor 3–4 as compared to the permeability of pure methane, and high permeability of butane was observed. Novel Si-containing poly(cycloolefins) as membrane materials were compared with high permeability polyacetylenes.

Addition polymerization and copolymerization of bis(Me3Si)-substituted norbornene-type monomers such as 5,5-bis(trimethylsilyl)norbornene-2, 2,3-bis(trimethylsilyl)norbornadiene-2,5 and 3,4-bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7, in the presence of Ni(II) naphtenate/MAO catalyst were studied. Disubstituted norbornene and norbornadiene were found to be practically inactive in homopolymerization. On the other hand, their copolymerization with norbornene proceeded with moderate yields of copolymers containing predominantly norbornene units. Under studied reaction conditions 2,3-bis(trimethylsilyl)norbornadiene-2,5 was transformed into the only exo-trans-exo-dimer as a result of the [2+2]-cyclodimerization reaction. Moving Me3Si-substituents one carbon atom away from norbornene double bond made 3,4-bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7 active in homopolymerization and allowed to obtain addition homo-polymer with two Me3Si-substituents in each elementary unit. The reaction mechanism and steric effect of Me3Si-substituents are also discussed.

Polymerization of norbornene bearing Si(CH 3 ) 3 groups in the five position with the opening of double bonds was performed. By accurate selection of the ratios catalyst/co-catalyst and monomer/catalyst the samples with increased molecular mass (about 400,000) were obtained. Transport parameters of this, addition type poly(trimethylsilyl norbornene) (PTMSN) were measured using the gas chromatographic and mass spectrometric methods for different gases (H 2 , He, O 2 , N 2 , CO 2 , CH 4 , C 2 H 6 , C 3 H 8 and n -C 4 H 10 ). Temperature dependence of the permeability coefficients ( P ) indicated that low activation energies of permeation ( E P ) and diffusion ( E D ) are characteristic for PTMSN. In some cases (CO 2 , C 2 H 6 ) negative E P values were observed. Thermodynamics of vapor sorption in this polymer was studied using the inverse gas chromatography method. It was shown that PTMSN is characterized by very large solubility coefficients S similar to those of poly(trimethylsilyl propyne) (PTMSP). The comparison of the P , D , and S values of these highly permeable polymers showed that the greater permeability of PTMSP is determined by the larger D values. Application of different approaches for the determination of the size of microcavities in PTMSN indicated that this polymer is characterized by large size of microcavity (800–1200 Ǻ 3 ).

Addition polymerization of 5-trimethylsilyl- and endo -, exo -5,6-bis(trimethylsilyl)-norbornenes was studied in the presence of Ni-based catalytic systems: [π-C 5 H 9 NiCl) 2 ]-Et 3 Al 2 Cl 3 , Ni(II) naphtenate-methylaluminoxane (MAO) and (π-C 5 H 9 NiCl) 2 -MAO. Completely saturated and soluble in aromatic solvents poly(5-trimethylsilyl-2-norbornene) was obtained with the yields up to 80%. In the course of the reaction exo -conformer was consumed much faster than endo -form independently of the type of catalytic system employed. Exo -, endo -5,6-bis(trimethylsilyl)-2-norbornene was practically inactive in the presence of the studied Ni-catalysts. At the same time its addition copolymerization with norbornene and 5- n -hexyl-2-norbornene could be readily realized.

International audience; For the first time, a novel highly permeable glassy polymer, addition poly[bis(trimethylsilyl)tricyclononene] (PBTMST), was proposed for its use in a gas-liquid membrane contactor for the regeneration of CO2 absorption liquids (desorption of CO2). This membrane material possesses a good chemical stability and high barrier properties for a number of alkanolmines (30 wt% solutions of MEA, DEA, MDEA, AMP, DEAE or AEAE) under typical regeneration conditions (T = 100°C). Studies on gas transport properties of PBTMST (100°C and 1-40 bar) show that permeability coefficients of oxygen, nitrogen and carbon dioxide initially tend to decrease, and then level off after first 6-8 hours of operation. This behavior can be explained by partial relaxation of the free-volume structure of PBTMST, no chemical degradation of polymer material at high temperature was confirmed by IR analysis. At the same time, this membrane material preserves high gas permeability coefficients which are higher than those of conventional materials used in the membrane contactors. Gas-liquid membrane contactor based on dense PBTMST membrane shows a good, stable performance; particularly, CO2 loading in diethanolamine solution (30 wt%) can be reduced for 0.05-0.34 mole/mole by single pass through the membrane desorber at 100°C and elevated pressure. It seems that desorption rate here is mainly controlled by liquid phase because decreasing of membrane thickness by 50% (from 31 to 21 μm) leads to improvement of DEA regeneration only by 1.5-8.5%.