PUBLICATIONS
Separation and Purification Technology 2024: Recent progress in thermally rearranged (TR) polymer based membranes for sustainable gas separations
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- TR polymer based membranes for sustainable gas separations were summarized.
- TR polymer based mixed matrix membranes were discussed in detail.
- Future directions in this field are proposed for efficient gas separations.
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Chemical Engineering Journal 2024: Recent advances on porous organic polymers for sustainable gas separations
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- Summarizing recent advances in POPs in gas separation.
- Engineering strategies for improving the performance of various POPs.
- Discussing the current challenges and prospects in this field.
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Advanced and functional materials 2024: The magic of spiro-epoxy moiety: an easy way to improve CO2-separation performance of polymer membrane
• Preparation and gas-separation properties of novel vinyl-addition polynorbornenes containing oxirane-moieties at spiro centers, which combine high CO2-permeability with remarkable selectivities for separation of CO2 from its mixtures with nitrogen and methane are reported.
• Gas permeability data of the epoxidized polymer based on 5-ethylidene-2-norbornene exceed the Robeson upper bound of 2019 for the CO2/N2 system (CO2 permeability is 1000 Barrer, α(CO2/N2) = 67)).
• The data for CO2/CH4 separation are above or close to the upper bound of 2018 for mixed gases
• A simple synthesis of the epoxidized polymer from available 5-ethylidene-2-norbornene, combined with high CO2-permeability and selectivities, may open a window for industrial applications of this polymer in important membrane processes.
Learn more in Advanced and functional materials2024
• Preparation and gas-separation properties of novel vinyl-addition polynorbornenes containing oxirane-moieties at spiro centers, which combine high CO2-permeability with remarkable selectivities for separation of CO2 from its mixtures with nitrogen and methane are reported.
• Gas permeability data of the epoxidized polymer based on 5-ethylidene-2-norbornene exceed the Robeson upper bound of 2019 for the CO2/N2 system (CO2 permeability is 1000 Barrer, α(CO2/N2) = 67)).
• The data for CO2/CH4 separation are above or close to the upper bound of 2018 for mixed gases
• A simple synthesis of the epoxidized polymer from available 5-ethylidene-2-norbornene, combined with high CO2-permeability and selectivities, may open a window for industrial applications of this polymer in important membrane processes.
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Polymer 2024: Janus polytricyclononenes with trialkoxysilyl groups containing long alkyl tails for membrane separation of hydrocarbons
• Synthesis of Janus polytricyclononenes with bulky trialkoxysilyl groups.
• Structure-property study of polynorbornenes with Si–O–C moieties in side chains
• Solubility-controlled permeation of gaseous hydrocarbons.
• Long alkyl tails in the side chains are preferred for hydrocarbons separation.
• Janus polymers are weakly plasticized by butane in methane/butane mixtures.
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• Synthesis of Janus polytricyclononenes with bulky trialkoxysilyl groups.
• Structure-property study of polynorbornenes with Si–O–C moieties in side chains
• Solubility-controlled permeation of gaseous hydrocarbons.
• Long alkyl tails in the side chains are preferred for hydrocarbons separation.
• Janus polymers are weakly plasticized by butane in methane/butane mixtures.
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Journal of Membrane Science 2024: Polynorbornenes with carbocyclic substituents: a perspective approach to highly permeable gas separation membranes
• Structure-property study of polynorbornenes with carbocycles in side chains.
• Carbocyclic moieties improve both CO2 permeability and CO2/gas selectivity.
• Polymeric membranes for CO2/N2 and hydrocarbons separation.
• Framed carbocyclic structures are Si-free alternatives to SiMe3 substituents.
• The characteristics of AP-NBNBa for CO2/N2 are above 2008 Robeson upper bound
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• Structure-property study of polynorbornenes with carbocycles in side chains.
• Carbocyclic moieties improve both CO2 permeability and CO2/gas selectivity.
• Polymeric membranes for CO2/N2 and hydrocarbons separation.
• Framed carbocyclic structures are Si-free alternatives to SiMe3 substituents.
• The characteristics of AP-NBNBa for CO2/N2 are above 2008 Robeson upper bound
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Journal of Membrane Science 2024: CO2-separation performance of vinyl-addition polynorbornenes with ester functionalities
• Polynorbornenes with acetoxy and methoxycarbonyl groups displayed high efficiency of CO2/gas separation with stable properties over time.
• Polymer with acetoxy groups showed CO2 permeability of 270 Barrer and selectivity of CO2/N2 separation above 20.
• CO2 permeability and CO2/N2 selectivity of the polymer with methoxycarbonyl groups (McPNB) exceeded 350 Barrer and 50.
• The way ester groups are linked to backbones of polynorbornene has a significant impact on efficiency of CO2/gas separation.
• Mixed-gas study of McPNB for CO2/N2 and CO2/CH4 gas pairs confirmed its promising CO2/gas separation performance
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• Polynorbornenes with acetoxy and methoxycarbonyl groups displayed high efficiency of CO2/gas separation with stable properties over time.
• Polymer with acetoxy groups showed CO2 permeability of 270 Barrer and selectivity of CO2/N2 separation above 20.
• CO2 permeability and CO2/N2 selectivity of the polymer with methoxycarbonyl groups (McPNB) exceeded 350 Barrer and 50.
• The way ester groups are linked to backbones of polynorbornene has a significant impact on efficiency of CO2/gas separation.
• Mixed-gas study of McPNB for CO2/N2 and CO2/CH4 gas pairs confirmed its promising CO2/gas separation performance
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ChemCatChem 2023: Single-component catalysts for the vinyl-addition polymerization of norbornene and its derivatives
• A comprehensive review on the recent development of single-component catalytst for vinyl-addition polymerization of norbornene derivatives.
• Neutral, anionic and cationic catalysts based on Ni- and Pd-complexes are discussed in detail.
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• A comprehensive review on the recent development of single-component catalytst for vinyl-addition polymerization of norbornene derivatives.
• Neutral, anionic and cationic catalysts based on Ni- and Pd-complexes are discussed in detail.
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Polymer Chemistry 2023: Making accessible soluble silicon-containing polynorbornenes: hydrosilylation of vinyl-addition poly(5-ethylydene-2-norbornene)
• We report a facilitated and simple approach to synthesizing various silicon-containing vinyl-addition polynorbornenes via hydrosilylation of side chains in a parent polymer bearing vinyl groups.
• A series of Rh- and Pt-complexes were systematically studied as catalysts in model hydrosilylation reactions of 2-vinylnorbornane and poly(5-vinyl-2-norbornene) (PVNB) with pentamethyldisiloxane.
• Despite the traditional Rh- and Pt- (Karstedt's) catalysts exhibited high activity, they provided insoluble products in the case of the modification of high-molecular-weight PVNB. At the same time, (NHC)Pt-complexes (where NHC is N-heterocyclic carbene ligand) were less active, but gave soluble modified vinyl-addition polymers.
• Tuning the size of the NHC-ligand and the nature of the aryl-group in this ligand made it possible to find out the most efficient (NHC)Pt-catalyst among the studied complexes. This catalyst allowed us to reach high selectivities and conversions (>90%) of vinyl groups in PVNB.
Learn more in Polymer Chemistry 2023
• We report a facilitated and simple approach to synthesizing various silicon-containing vinyl-addition polynorbornenes via hydrosilylation of side chains in a parent polymer bearing vinyl groups.
• A series of Rh- and Pt-complexes were systematically studied as catalysts in model hydrosilylation reactions of 2-vinylnorbornane and poly(5-vinyl-2-norbornene) (PVNB) with pentamethyldisiloxane.
• Despite the traditional Rh- and Pt- (Karstedt's) catalysts exhibited high activity, they provided insoluble products in the case of the modification of high-molecular-weight PVNB. At the same time, (NHC)Pt-complexes (where NHC is N-heterocyclic carbene ligand) were less active, but gave soluble modified vinyl-addition polymers.
• Tuning the size of the NHC-ligand and the nature of the aryl-group in this ligand made it possible to find out the most efficient (NHC)Pt-catalyst among the studied complexes. This catalyst allowed us to reach high selectivities and conversions (>90%) of vinyl groups in PVNB.
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Journal of membrane science 2024: Vinyl-addition polynorbornenes with glycerol and diethylene glycol moieties: synthesis and structure-property study
• A set of new norbornene-type monomers containing linear and branched substituents with three C–O–C fragments was synthesized in good yields from commercially available glycerol and diethylene glycol monomethyl ether.
• As a result of optimizing the reaction conditions, a series of robust thin membranes was successfully prepared directly from the polymerization mixtures in the air.
• Gas separation performance for a wide range of gases was evaluated for the synthesized polymers, and new valuable structure-property relationships were found.
• Such membranes display the facilitated transport of CO2 and solubility-controlled hydrocarbon separation selectivity. The increase in the amount of C–O–C fragments in side chains enhances these effects, but only in the case of the linear structure of the substituents.
• The facilitated transport of CO2 is due to the specific dipole-quadrupole interaction between CO2 molecules and polymer matrix. For the studied polymers, the contribution of this specific interaction to the solubility of CO2 achieves 64 %.
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• A set of new norbornene-type monomers containing linear and branched substituents with three C–O–C fragments was synthesized in good yields from commercially available glycerol and diethylene glycol monomethyl ether.
• As a result of optimizing the reaction conditions, a series of robust thin membranes was successfully prepared directly from the polymerization mixtures in the air.
• Gas separation performance for a wide range of gases was evaluated for the synthesized polymers, and new valuable structure-property relationships were found.
• Such membranes display the facilitated transport of CO2 and solubility-controlled hydrocarbon separation selectivity. The increase in the amount of C–O–C fragments in side chains enhances these effects, but only in the case of the linear structure of the substituents.
• The facilitated transport of CO2 is due to the specific dipole-quadrupole interaction between CO2 molecules and polymer matrix. For the studied polymers, the contribution of this specific interaction to the solubility of CO2 achieves 64 %.
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Polymers 2023: Vinyl-addition homopolymerization of norbornenes with bromoalkyl groups
• Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare.
• In the present paper, the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups in the presence of Pd-NHC catalysts was performed.
• Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH2 groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers. The relative reactivity of such monomers in copolymerization was assessed.
• Variation of polymerization conditions allowed obtaining of high-molecular-weight homopolymers based on norbornenes with bromoalkyl groups (Mn up to 1.4 × 106).
• The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization.
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• Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare.
• In the present paper, the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups in the presence of Pd-NHC catalysts was performed.
• Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH2 groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers. The relative reactivity of such monomers in copolymerization was assessed.
• Variation of polymerization conditions allowed obtaining of high-molecular-weight homopolymers based on norbornenes with bromoalkyl groups (Mn up to 1.4 × 106).
• The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization.
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Journal of Membrane Science 2023: CO2-selective vinyl-addition polymers from nadimides: Synthesis and performance for membrane gas separation
• Polymers combining saturated rigid main chains and imide moieties were synthesized through vinyl-addition polymerization of substituted nadimides (VAP polymers) and assessed as potential membrane materials for gas separation for the first time
• Valuable structure-property relationships were established. VAP polynorbornene with fluoroaryl-groups in imides moieties exhibited the combination of high CO2 permeability with attractive CO2/N2 and CO2/CH4 selectivities.
• With CO2 permeability of >1300 Barrer and CO2/CH4 separation selectivity of 29, the performance of the polymer exceeded that of other VAP and metathesis nadimide polymers.
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• Polymers combining saturated rigid main chains and imide moieties were synthesized through vinyl-addition polymerization of substituted nadimides (VAP polymers) and assessed as potential membrane materials for gas separation for the first time
• Valuable structure-property relationships were established. VAP polynorbornene with fluoroaryl-groups in imides moieties exhibited the combination of high CO2 permeability with attractive CO2/N2 and CO2/CH4 selectivities.
• With CO2 permeability of >1300 Barrer and CO2/CH4 separation selectivity of 29, the performance of the polymer exceeded that of other VAP and metathesis nadimide polymers.
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Polymer 2023: Microporous polynorbornenes bearing carbocyclic substituents: Structure-property study
• Structure-property study of polynorbornenes with various carbocycles in side chains.
• Soluble and readily available microporous polymers with large surface area.
• The effect of main- and side-chains on the porosity was studied.
• Large values of surface area are for polymers with framed carbocyclic groups.
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• Structure-property study of polynorbornenes with various carbocycles in side chains.
• Soluble and readily available microporous polymers with large surface area.
• The effect of main- and side-chains on the porosity was studied.
• Large values of surface area are for polymers with framed carbocyclic groups.
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ACS Catalysis 2022: Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes
• Cationic Pd-complexes with N-heterocyclic carbene ligands (NHC ligands) and weak coordinating anion ligands were prepared and shown to be an effective catalysts for vinyl-addition polymerization of norbornenes.
• Air stable (solid and in solution) complexes are extremely efficient in polymerization of functionalized norbornenes containing reactive functional groups.
• Such single component catalysts remain effective even at concentrations as low as 2 ppm.
• Tuning the nature of NHC and allyl ligands in [(NHC)Pd(allyl)L]+A– complexes let perform living VAP, yielding block copolymers.
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• Cationic Pd-complexes with N-heterocyclic carbene ligands (NHC ligands) and weak coordinating anion ligands were prepared and shown to be an effective catalysts for vinyl-addition polymerization of norbornenes.
• Air stable (solid and in solution) complexes are extremely efficient in polymerization of functionalized norbornenes containing reactive functional groups.
• Such single component catalysts remain effective even at concentrations as low as 2 ppm.
• Tuning the nature of NHC and allyl ligands in [(NHC)Pd(allyl)L]+A– complexes let perform living VAP, yielding block copolymers.
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Polymers 2022: Chiral Polymers from Norbornenes Based on Renewable Chemical Feedstocks
• A set of new chiral monomers from cis-5-norbornene-2,3-dicarboxylic anhydride and chiral alcohols of various natures was prepared.
• High molecular weight metathesis polymers ( Mw in the range 1.9 × 105–5.8 × 105) were obtained.
• The polymers exhibited high thermal stability and good film-forming properties. Glass transition temperatures for the prepared polymers varied from −30 °C to +139 °C.
• The prepared polymers represent a new attractive platform of chiral polymeric materials for enantioselective membrane separation and chiral stationary phases for chromatography.•
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• A set of new chiral monomers from cis-5-norbornene-2,3-dicarboxylic anhydride and chiral alcohols of various natures was prepared.
• High molecular weight metathesis polymers ( Mw in the range 1.9 × 105–5.8 × 105) were obtained.
• The polymers exhibited high thermal stability and good film-forming properties. Glass transition temperatures for the prepared polymers varied from −30 °C to +139 °C.
• The prepared polymers represent a new attractive platform of chiral polymeric materials for enantioselective membrane separation and chiral stationary phases for chromatography.•
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Polymer 2022: Polymers from organosilicon derivatives of 5-norbornene-2-methanol for membrane gas separation
• A simple synthesis of norbornene monomers with Si–O–C motifs.
• Structure-property study of polynorbornenes with trialkylsiloxy groups.
• Opposite effects of substituent on permeability for glassy and rubbery polymers.
• Solubility-controlled dependence of permeability on the length of alkyl groups.
• Alk3SiO-groups are preferable for membranes rather than (AlkO)Alk2Si-groups.
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• A simple synthesis of norbornene monomers with Si–O–C motifs.
• Structure-property study of polynorbornenes with trialkylsiloxy groups.
• Opposite effects of substituent on permeability for glassy and rubbery polymers.
• Solubility-controlled dependence of permeability on the length of alkyl groups.
• Alk3SiO-groups are preferable for membranes rather than (AlkO)Alk2Si-groups.
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European Polymer Journal 2022: Olefin cross-metathesis of polynorbornene with polypentenamer: New norbornene–cyclopentene multiblock copolymers
• Multiblock PNB–PCP copolymers were synthesized by cross-metathesis.
• Inclusion of CP units into copolymer is hampered by PCP depolymerization.
• Polymer concentration during the reaction determines the copolymer chain structure.
• Other key factors are type of the catalyst and temperature.
• Copolymer hydrogenation allows to reveal the details of its structure.
Learn more in European Polymer Journal 2022
• Multiblock PNB–PCP copolymers were synthesized by cross-metathesis.
• Inclusion of CP units into copolymer is hampered by PCP depolymerization.
• Polymer concentration during the reaction determines the copolymer chain structure.
• Other key factors are type of the catalyst and temperature.
• Copolymer hydrogenation allows to reveal the details of its structure.
Learn more in European Polymer Journal 2022
Journal of Membrane Science and Research 2022: Molecular mobiluty of Polynorbornenes with Trimethylsiloxyxilyl side groups: Influence of the polymerization mechanism
• Dielectric and calorimetric studies on metathesis and addition-type polytricyclononenes, both based on the same monomer bearing three pendant -OSiMe3 groups, are reported.
• For the addition-type polymer, dielectric spectroscopy reveals a ß*-process related to the microporosity, whereas for its metathesis counterpart, the segmental dynamics (α-process) manifests.
• A significant conductivity contribution is detected for both samples which for the microporous addition-type polymer is three orders of magnitude greater than for the metathesis polymer.
• The calorimetric methods detected the glass transition for the metathesis polymer in agreement with the observed dielectric α-process.
• The discussed results reflect significant differences in molecular mobility of the two polymers affecting the appearance of microporosity which strongly determines the gas transport properties.
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• Dielectric and calorimetric studies on metathesis and addition-type polytricyclononenes, both based on the same monomer bearing three pendant -OSiMe3 groups, are reported.
• For the addition-type polymer, dielectric spectroscopy reveals a ß*-process related to the microporosity, whereas for its metathesis counterpart, the segmental dynamics (α-process) manifests.
• A significant conductivity contribution is detected for both samples which for the microporous addition-type polymer is three orders of magnitude greater than for the metathesis polymer.
• The calorimetric methods detected the glass transition for the metathesis polymer in agreement with the observed dielectric α-process.
• The discussed results reflect significant differences in molecular mobility of the two polymers affecting the appearance of microporosity which strongly determines the gas transport properties.
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Polymers 2022: Gas-Transport and the Dielectric Properties of Metathesis Polymer from the Ester of exo-5-Norbornenecarboxylic Acid and 1,1′-Bi-2-naphthol
• We synthesized a new metathesis polymer from exo-5-norbornenecarboxylic acid and 1,1′-bi-2-naphthol.
• The polymer is amorphous and glassy (Tg = 161 °C), and it shows good thermal stability. Unlike most, polyNBi is a classic low-permeable glassy polymer.
• Being less permeable than polyNB, polyNBi unexpectedly showed a lower value of dielectric permittivity (2.7 for polyNBi vs. 5.0 for polyNB).
• Molecular design of polynorbornenes has great potential to obtain polymers with desired properties in a wide range of required characteristics.
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• We synthesized a new metathesis polymer from exo-5-norbornenecarboxylic acid and 1,1′-bi-2-naphthol.
• The polymer is amorphous and glassy (Tg = 161 °C), and it shows good thermal stability. Unlike most, polyNBi is a classic low-permeable glassy polymer.
• Being less permeable than polyNB, polyNBi unexpectedly showed a lower value of dielectric permittivity (2.7 for polyNBi vs. 5.0 for polyNB).
• Molecular design of polynorbornenes has great potential to obtain polymers with desired properties in a wide range of required characteristics.
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Energy and Fuels 2022: High-Energy-Density Liquid Spiro-Norbornanes from Methylenenorbornane
• New spiro-hydrocarbons obtained from a versatile norbornane derivative.
• The effect of introducing a spiro-center is dependent on the nature of carbocycles at a spiro-carbon atom.
• Spirocycloalkenes with two norbornane motifs at a spiro-center have exhibited much higher values of densities and energy densities than the related hydrocarbons without a spiro-center and JP-10.
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• New spiro-hydrocarbons obtained from a versatile norbornane derivative.
• The effect of introducing a spiro-center is dependent on the nature of carbocycles at a spiro-carbon atom.
• Spirocycloalkenes with two norbornane motifs at a spiro-center have exhibited much higher values of densities and energy densities than the related hydrocarbons without a spiro-center and JP-10.
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Journal of Membrane Science 2022: Polynorbornenes bearing ether fragments in substituents: Promising membrane materials with enhanced CO2 permeability
• Norbornenes with cellosolve moieties are involved in vinyl-addition polymerization.
• Structure-property study of polynorbornenes with ether groups for CO2/N2 separation.
• Ether fragments improve permeability of gaseous hydrocarbons.
• Cellosolve moieties provide facilitated transport of CO2.
• Specific interactions between CO2 and cellosolve moieties are confirmed.
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• Norbornenes with cellosolve moieties are involved in vinyl-addition polymerization.
• Structure-property study of polynorbornenes with ether groups for CO2/N2 separation.
• Ether fragments improve permeability of gaseous hydrocarbons.
• Cellosolve moieties provide facilitated transport of CO2.
• Specific interactions between CO2 and cellosolve moieties are confirmed.
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Fuel Processing Technology 2022:
Design and preparation of liquid polycyclic norbornanes as potential high performance fuels for aerospace propulsion
• Four new liquid polycyclic norbornane-containing hydrocarbons were designed and prepared.
• Relationships between molecular structure and fuel properties were studied.
• The hydrocarbons exhibited density up to 1.0799 g/mL, kinematic viscosity up to 1.89 mm2·s−1 and low freezing points.
• Energy densities of the polycyclic norbornane-containing hydrocarbons were up to 45.38 MJ/L.
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Design and preparation of liquid polycyclic norbornanes as potential high performance fuels for aerospace propulsion
• Four new liquid polycyclic norbornane-containing hydrocarbons were designed and prepared.
• Relationships between molecular structure and fuel properties were studied.
• The hydrocarbons exhibited density up to 1.0799 g/mL, kinematic viscosity up to 1.89 mm2·s−1 and low freezing points.
• Energy densities of the polycyclic norbornane-containing hydrocarbons were up to 45.38 MJ/L.
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Polymer Chemistry 2021: Cocatalyst versus precatalyst impact on the vinyl-addition polymerization of norbornenes with polar groups: looking at the other side of the coin
• We report our examination of the precatalyst and cocatalyst influence on vinyl-addition polymerization of two types of norbornene monomers with bulky and polar groups (substituted nadimides and norbornenes with cellosolve motif)
• The key to successful vinyl addition polymerization of these monomers is the proper combination of a cocatalyst and a Pd precatalyst. Both components of a catalytic system seem to play equal roles.
• Impact of the cocatalyst depends on the monomer nature and can be different for norbornenes with nonpolar and polar groups.
• These results provide an insight and opportunity for further work expansion in order to obtain new high-performance polymers based on strained cycloalkenes with polar groups, which are not currently available
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• The key to successful vinyl addition polymerization of these monomers is the proper combination of a cocatalyst and a Pd precatalyst. Both components of a catalytic system seem to play equal roles.
• Impact of the cocatalyst depends on the monomer nature and can be different for norbornenes with nonpolar and polar groups.
• These results provide an insight and opportunity for further work expansion in order to obtain new high-performance polymers based on strained cycloalkenes with polar groups, which are not currently available
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Polymer Chemistry 2021: Substituted polynorbornene membranes: a modular template for targeted gas separations†
• The modular nature of norbornene-based systems provides a facile route towards the synthesis of diverse polymeric materials.
•Tremendous progress has been realized in the preparation of stable and highly selective polynorbornenes for membrane-based gas separations
• 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.
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Chemical Communications 2021: Activation of Pd-precatalysts by organic compounds for vinyl-addition polymerization of a norbornene derivative
• An approach to activating Pd-complexes without using organometallic additives has been developed for addition polymerization of norbornenes
• Aryl iodides and aryl diazonium salts were efficiently applied as cocatalysts to Pd(0)- and Pd(2+)-complexes.
• Novel approach is closely connected to Pd-catalyzed coupling reactions from organic chemistry. That can shed light on previously unknown processes in catalysis on vinyl-addition polymerization of norbornene derivatives.
• New systems catalyzed polymerization of norbornenes containing bulky and polar functional groups both in an inert atmosphere and air resulting in soluble and high-molecular-weight saturated polymers
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Fuel Processing Technology 2021: Design and preparation of liquid polycyclic norbornanes as potential high performance fuels for aerospace propulsio
• Four new liquid polycyclic norbornane-containing hydrocarbons were designed and prepared.
• Relationships between molecular structure and fuel properties were studied.
• The hydrocarbons exhibited density up to 1.0799 g/mL, kinematic viscosity up to 1.89 mm2·s−1 and low freezing points.
• Energy densities of the polycyclic norbornane-containing hydrocarbons were up to 45.38 MJ/L.
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• Relationships between molecular structure and fuel properties were studied.
• The hydrocarbons exhibited density up to 1.0799 g/mL, kinematic viscosity up to 1.89 mm2·s−1 and low freezing points.
• Energy densities of the polycyclic norbornane-containing hydrocarbons were up to 45.38 MJ/L.
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Journal of Membrane Science 2021: Microscopic dynamics of highly permeable super glassy polynorbornenes revealed by quasielastic neutron scattering
•The molecular mobility of highly permeable polynorbornenes is considered.
• Bulky side groups lead to an intrinsic microporosity.
• Qusielastic neutron scattering is chosen as experimental method.
• The observed mobility is assigned to the rotation of methyl groups
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• Bulky side groups lead to an intrinsic microporosity.
• Qusielastic neutron scattering is chosen as experimental method.
• The observed mobility is assigned to the rotation of methyl groups
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Journal of Membrane Science 2021: Switching on/switching off solubility controlled permeation of hydrocarbons through glassy polynorbornenes by the length of side alkyl groups
• Structure-property study of vinyl-addition poly(5-alkyl-2-norbornenes) was performed.
• Permeability of permanent gases changed non-linearly with the size of alkyl groups.
• The highest gas permeability was achieved for the polymers with short side-alkyl groups.
• No traditional trade-off between gas permeability and selectivity was for these polymers.
• Truly solubility-controlled permeability of hydrocarbons appeared for the polymers with butyl or larger side-groups.
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• Permeability of permanent gases changed non-linearly with the size of alkyl groups.
• The highest gas permeability was achieved for the polymers with short side-alkyl groups.
• No traditional trade-off between gas permeability and selectivity was for these polymers.
• Truly solubility-controlled permeability of hydrocarbons appeared for the polymers with butyl or larger side-groups.
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Fuel 2021: Metal chlorides supported on silica as efficient catalysts for selective isomerization of endo-tetrahydrodicyclopentadiene to exo-tetrahydrodicyclopentadiene for JP-10 producing
• Metal chlorides on SiO2 were prepared as catalysts for synthesis of JP-10 fuel.
• Properties of the catalysts were studied by SEM, low temperature N2 adsorption, NH3-TPD.
• Activity of the catalysts was evaluated in endo-/exo-THDCPD isomerization.
• AlCl3 on SiO2 exhibited the highest catalytic activity, selectivity was higher 99%.
• Thermodynamic and kinetic parameters for the isomerization reaction were evaluated.
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Journal of Membrane Science 2021: Polymers based on exo-substituted norbornenes for membrane gas separation
• A simple and selective approach to Si-substituted poly(exo-norbornenes) was developed.
• Structure-property study of poly(siloxanylnorbornenes) for C4H10/CH4 separation.
• Si–O–Si-moieties improved light hydrocarbons permeability.
• Effect of exo-/endo-orientation of substituent on gas permeability was studied.
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• Structure-property study of poly(siloxanylnorbornenes) for C4H10/CH4 separation.
• Si–O–Si-moieties improved light hydrocarbons permeability.
• Effect of exo-/endo-orientation of substituent on gas permeability was studied.
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Polymer reviews 2021: Design and Synthesis of Porous Organic Polymeric Materials from Norbornene Derivatives
This comprehensive review surveys recent research trends in the development of porous polynorbornenes.
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- A rational design was achieved in metathesis, addition, and CANAL polymers as an extension of the modular strategy using norbornene motifs as building blocks.
- Tuning the structure of norbornene-containing monomer units allowed obtaining high-free-volume polymers with apparent Brunauer–Emmett–Teller (BET) surface areas up to 1000 m2/g that made these materials promising for various engineering applications such as membrane gas separation, gas sorbents, CO2 capture, scaffolds to support catalysts, or reagents for catalysis.
- The synthesis and porous characteristics of polynorbornenes are presented along with the discussion of correlations between the chemical structure of these materials and their porous structures.
- Possible important applications of porous polynorbornenes are also emphasized
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Fuel 2021: Synthesis and properties of high-energy-density hydrocarbons based on 5-vinyl-2-norbornene
A norbornane derivative, exo-tetrahydrodicyclopentadiene, is the main component of the high-density liquid fuel called JP-10. In the current communication, we describe the preparation of some related norbornane-containing hydrocarbons and their energetic properties.
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- An approach to high-energy-density hydrocarbons based on 5-vinyl-2-norbornene was developed.
- Structure-property study of norbornane hydrocarbons for high-energy-density liquid fuels was performed.
- High densities (0.856–0.977 g/cm3) and low freezing points (below −60 °C) were disclosed for the studied hydrocarbons.
- A high energy density (up to 41.24 MJ/L) was achieved, which is noticeably higher than that of JP-10
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Polymers 2020: Synthesis and Gas Transport Properties of Addition Polynorbornene with Perfluorophenyl Side Groups
Addition polynorbornene with fluoroorganic substituents was synthesized for the first time. A study on the gas transport properties of the polymer was executed.
Therefore, this investigation opens the door to fluorinated addition polynorbornenes as new potential polymeric materials for membrane gas separation.
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- A norbornene-type monomer with a pentafluorophenyl group was involved in addition polymerization. The products are soluble, high-molecular-weight polymers obtained in good or high yields.
- The molecular structure was confirmed by NMR and FTIR analysis.
- The hydrophobic nature of the synthesized polymer was revealed by the study of contact angle with distilled water was studied.
- A study of the permeability of various gases (He, H2, O2, N2, CO2, and CH4) through the prepared polymer was studied. Addition poly(3-pentafluorophenyl-exo-tricyclononene-7) was more permeable than its metathesis analogue by a factor of 7–21.
- The effect achieved is due to the presence of both bulky perfluorinated side groups and rigid saturated main chains.
Therefore, this investigation opens the door to fluorinated addition polynorbornenes as new potential polymeric materials for membrane gas separation.
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ACS Catalysis 2020: Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships
We studied the addition polymerization of readily available bifunctional norbornene derivatives, 5-alkylidene-2-norbornenes, in the presence of modified Pd complexes with N-heterocyclic carbene ligands activated by borates. The structure–catalytic activity relationships were established for Pd–N-heterocyclic carbene complexes.
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- New catalytic systems (Pd–N-heterocyclic carbene complex/phosphine/borate) selectively catalyze the addition polymerization of 5-methylene-2-norbornene and 5-ethylidene-2-norbornene.
- Only endocyclic norbornene double bond took part in polymerization. The exocyclic double bond remained intact.
- The catalysts exhibited extremely high activity and durability: the activity was higher than 100 million g polymer/(molPd·h) and some catalysts were active at a very high monomer/Pd molar ratio of 20 millions.
- Pd complexes bearing five-membered heterocyclic rings and/or less sterically hindered aryl groups at nitrogen atoms in carbene ligands exhibited the highest activity.
- The polymerization can be performed in an atmosphere of air and in wet solvents.
- The resulting polymers are amorphous and high-molecular-weight products consisting of rigid saturated main chains and reactive side groups. They can be considered as promising intermediates in the production of polymeric materials with high glass-transition temperatures and desired properties by targeted modifications.
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Polymer 2020: Dielectric properties of addition and metathesis polynorbornenes with bulky side-substituents
- Structure-property study of polynorbornenes for low dielectric constant materials.
- Dielectric properties of two groups of polymers derived from Si-, F- and alkenyl-substituted norbornenes were studied.
- Incorporation of Me3Si- and perfluoroalkyl-groups as side groups in polynorbornenes results in a lower dielectric constant.
- The lowest dielectric constants among polynorbornenes were achieved, and they were observed on PTCNSi2g and MPF16 films.
- Polynorbornenes studied possess a promising combination of properties: dielectric constant, water uptake, stability, etc.
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Reactive and functional polymers 2020: Modifications of addition poly(5-vinyl-2-norbornene) and gas-transport properties of the obtained polymers
We prepared four modified polymers derived from readily available addition poly(5-vinyl-2-norbornene) (PVNB). Properties of the modified polymers were studied.
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- Hydrogenation, epoxidation, cyclopropanation and thiol-en reactions of addition poly(5-vinyl-2-norbornene) were performed.
- The modifications were carried out in high yields without the destruction of main chains.
- Structure-property study of polynorbornenes for membrane gas separations.
- Cyclopropanation and hydrogenation increase permeability with a minimal decrease in selectivity.
- Epoxidation or thioacetylation gave a substantial increase in CO2/N2 selectivity with a decrease in permeability.
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Macromolecular Rapid Communications 2020: Addition Polyalkylnorbornenes: A Promising New Class of Si-Free Membrane Materials for Hydrocarbons Separation
Nanoporous glassy polymers are perspective materials for the fabrication of gas separation membranes, especially for the application of gaseous hydrocarbon separation. However, the drawback of such materials is the pronounced physical aging resulting in the dramatic drop of gas transport properties due to relaxation of high‐free‐volume fraction in time. Herein, a novel and readily available group of such glassy polymers is reported based on 5‐alkylnorbornenes.
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- These polymers are easily synthesized from dicyclopentadiene and α‐olefins by Diels‐Alder reaction and vinyl (addition) polymerization of the formed cycloadducts.
- The obtained polymers display low‐fraction free volume, stable gas permeability over time.
- Polyalkylnorbornenes possess a unique feature for the glassy polymers—solubility controlled permeation of hydrocarbons and enhanced C4H10/CH4 selectivity.
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Polymer Engineering and Science 2019: Crosslinking of addition copolymers from tricyclononenes bearing (CH3)3Si- and (C2H5O)3Si-groups as a modification of membrane gas separation materials
We report the synthesis and the study of gas‐transport properties of crosslinked highly permeable addition copolymers derived from Si‐containing norbornenes
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- The obtained copolymers included up to 10 mol% of units bearing reactive Si–O–C‐containing substituents.
- The crosslinking was readily realized by using simple sol–gel chemistry in the presence of Sn‐catalyst.
- Only a small reduction of gas‐permeability was observed when TNCSiOEt units were incorporated into the main chains, and the copolymers were crosslinked.
- Selectivity for C4H10/CH4 pair was increased.
- The suggested approach has allowed obtaining crosslinked polymers from Si‐containing monomers without a loss of the main membrane characteristics.
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RSC Advances 2019: The selective hydrosilylation of norbornadiene-2,5 by monohydrosiloxanes
A simple one-step approach for the selective synthesis of exo-norbornenes with organosilicon substituents is suggested through the direct hydrosilylation of norbornadiene-2,5 with chlorine-free silanes.
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- The possibility of obtaining exo-isomers of Si-containing norbornenes with 100 exo-/endo-selectivity is shown
- The investigation of Pt-, Rh-, and Pd-complexes in combination with various ligands as catalysts was performed.
- The hydrosilylation of norbornadiene-2,5 in the presence of Pt- or Rh-catalysts was not selective and led to a mixture consisting of three isomers
- The selectivity of exo-norbornene/nortricyclane formation strongly depended on the nature of the ligand in the Pd-catalyst.
- The best selectivity was revealed when R-MOP was the ligand
- The highest catalytic activity was reached with a dioxalane-containing ligand.
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Polymer 2018: Metathesis-type poly-exo-tricyclononenes with fluoroorganic side substituents: Synthesis and gas-transport properties
We executed a detailed study of the synthesis and properties of metathesis polytricyclononenes. New correlations between the structure of the side chain and polymer's membrane performance were revealed.
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- Novel highly reactive fluoro-containing exo-tricyclononenes were synthesized via [2 + 2+2]-cycloaddition reaction.
- A group of new metathesis polytricyclononenes bearing side fluoroorganic-substituents was prepared.
- The obtained polymers possessed both chemical and thermal stability.
- The synthesized metathesis polytricyclononenes with fluorooganic-substituents exhibited improved gas permeability and selectivity towards H2/CH4.
- Polymer bearing four rigid CF3-groups turned out to be the most permeable among the described fluorinated polynorbonenes known to date.
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Progress in Polymer Science 2018: Addition polymerization of functionalized norbornenes as a powerful tool for assembling molecular moieties of new polymers with versatile properties
This comprehensive review surveys recent research trends in the addition polymerization of functionalized norbornenes for the macromolecular design of high-performance materials in terms of catalyst activity, monomer reactivity, modifications, and potential applications of addition polynorbornenes bearing functional groups.
The structure of addition polynorbornene backbones is responsible for their high thermal resistance and chemical stability. In order to impart desired properties to the polymers, various functional side groups can be incorporated into the monomer units by the Ti-, Ni-, or Pd-catalyzed polymerization of norbornenes, which are available via cycloaddition reactions or norbornadiene-2,5 modifications.
Based on the use of different substituents in the norbornene monomer units and different polymer compositions, the addition polynorbornenes have been successfully developed for the preparation of pervaporation, gas separation, and proton-conducting membranes, sensors, catalyst supports, and for applications as photoresist, electrooptical, and dielectric materials, etc.
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The structure of addition polynorbornene backbones is responsible for their high thermal resistance and chemical stability. In order to impart desired properties to the polymers, various functional side groups can be incorporated into the monomer units by the Ti-, Ni-, or Pd-catalyzed polymerization of norbornenes, which are available via cycloaddition reactions or norbornadiene-2,5 modifications.
Based on the use of different substituents in the norbornene monomer units and different polymer compositions, the addition polynorbornenes have been successfully developed for the preparation of pervaporation, gas separation, and proton-conducting membranes, sensors, catalyst supports, and for applications as photoresist, electrooptical, and dielectric materials, etc.
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Polymers 2018: Metathesis-type poly-exo-tricyclononenes with fluoroorganic side substituents: Synthesis and gas-transport properties
New microporous homopolymers were readily prepared from norbornadiene-2,5, its dimer and trimer by addition (vinyl) polymerization of the corresponding monomers.
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- The synthesized polynorbornenes are cross-linked and insoluble.
- They are glassy and amorphous polymers. Depending on the nature of the catalyst applied, BET surface areas were in the range of 420–970 m2/g.
- The polymers with the highest surface area were obtained in the presence of Pd-catalysts from the trimer of norbornadiene-2,5.
- The total pore volume of the polymers varies from 0.39 to 0.79 cm3/g, while the true volume of micropores was 0.14–0.16 cm3/g according to t-plot.
- These polymers gave CO2 uptake from 1.2 to 1.9 mmol/g at 273 K and 1 atm.
- The porous structure of new polymers was studied.
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Journal of Materials Chemistry A 2018: Janus tricyclononene polymers bearing tri(n-alkoxy)silyl side groups for membrane gas separation
A new type of polymers containing 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.
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- High-molecular weight metathesis and addition polynorbornenes were obtained with good yields.
- 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.
- Change of the polymer main chain structure and the length of tri(n-alkoxy)silyl side groups led to the dramatic tuning of polymer gas-transport properties.
- For the first time we obtained metathesis polynorbornenes being more permeable than their addition isomers.
- 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).
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Macromolecular Chemistry and Physics 2018: Addition Homo- and Copolymerizations of Dicyclopentadiene and 5-n -Hexylnorbornene in the Presence of Pd-N-Heterocyclic Carbene Complexes
For the first time addition homopolymerization of dicyclopentadiene (DCPD) and its copolymerization with 5‐n‐hexylnorbornene in the presence of different Pd‐N‐heterocyclic carbene complexes activated by a borate (NaBARF) or methylaluminoxane (MAO) are investigated.
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- Systems based on Pd‐N‐heterocyclic carbene complex in combination with NaBARF or MAO are an effective catalyst
- Polymerization can proceed in the air.
- The influence of the N‐heterocyclic carbene structure, the nature of cocatalyst, and solvent on the catalyst activity of a system based on Pd‐N‐heterocyclic carbene complex is determined.
- Thermal stability, solid‐state structure, and porosity of the obtained addition polydicyclopentadiene are studied. The material possessed a high surface area.
- The addition polymerization of DCPD can be considered as a single‐step and convenient way to synthesize porous polymers from a norbornene derivative.
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