Addition-Type Polynorbornenes with Si(CH<sub>3</sub>)<sub>3</sub> Side Groups:  Synthesis, Gas Permeability, and Free Volume

Финкельштейн, Е. Ш.; Makovetskii, K. L.; Gringolts, M. L.; Rogan, Yulia; Golenko, T. G.; Старанникова, Л. Э.; Yampolskii, Yu. P.; Shantarovich, V. P.; Suzuki, Takenori

doi:10.1021/ma061215h

Cited by 122 publications

(100 citation statements)

References 52 publications

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“…As was shown in the earlier studies, for PTMSP, P(O 2 ) decreases by an order of magnitude after heating at 100°C for 15 h [31] and by two orders of magnitude after heating at 120°C for 8 h [32]. At the same time, oxygen permeability of the addition Poly[5-(TriMethylSilyl)Norborn-7-ene] (PTMSN) decreases only from 980 to 900 Barrer after annealing in air at 80°C for 16 h [33].…”

Section: Thermal Resistancesupporting

confidence: 65%

Regeneration of Alkanolamine Solutions in Membrane Contactor Based on Novel Polynorbornene

Shutova

Trusov

Бермешев

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Re´sume´-Re´ge´ne´ration de solutions d'alcanolamine dans un contacteur a`membrane base´sur un nouveau polynorborne`ne -Un nouveau polyme`re vitreux a`haute perme´abilite´, le poly[bis (trime´thylsilyl)tricyclononene] (PBTMST), est propose´pour la premie`re fois pour une utilisation dans un contacteur gaz-liquide a`membrane pour la re´ge´ne´ration de liquides d'absorption riches en CO 2 (de´sorption de CO 2 ). Ce mate´riau membranaire posse`de une bonne stabilite´chimique et de bonnes proprie´te´s barrie`re pour de nombreuses alcanolamines (solutions de 30 % poids de MEA, DEA, MDEA, AMP, DEAE ou AEAE) dans des conditions typiques de re´ge´ne´ration (T = 100°C). Les e´tudes des proprie´te´s de transport des gaz du PBTMST (a`100°C et sous 1 a`40 bar) montrent que les coefficients de perme´abilite´al 'oxyge`ne, a`l'azote et au dioxyde de carbone tendent a`diminuer puis a`se stabiliser apre`s les 6 a`8 premie`res heures de mesure. Ce comportement peut eˆtre explique´par une relaxation partielle de la structure de volume libre du PBTMST. Aucune de´gradation a`haute tempe´rature du mate´riau polyme`re n'a pu eˆtre confirme´e par analyse IR. De plus, ce mate´riau membranaire conserve des coefficients de perme´abilite´aux gaz e´leve´s, supe´rieurs a`ceux des mate´riaux conventionnels utilise´s dans les contacteurs a`membrane. Un contacteur gaz-liquide a`membrane fabrique´a`partir d'une membrane dense de PBTMST pre´sente de performances bonnes et stables. En particulier, le taux de charge en CO 2 d'une solution de die´thanolamine (30 % poids) peut eˆtre re´duit de 0,05 a`0,34 mole/mole via un simple passage a`travers le re´ge´ne´rateur a`membrane a`100°C et a`pression e´leve´e. Il semble que le taux de de´sorption soit principalement controˆle´par la phase liquide, une diminution de l'e´paisseur membranaire de 50 % (de 31 a`21 lm) n'apportant qu'une ame´lioration de 1,5 a`8,5 % de la re´ge´ne´ration de la DEA. 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, CO 2 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 lm) leads to improvement of DEA regeneration only by 1.5-8.5%.

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Section: Thermal Resistancesupporting

confidence: 65%

Regeneration of Alkanolamine Solutions in Membrane Contactor Based on Novel Polynorbornene

Shutova

Trusov

Бермешев

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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“…It has been reported that the introduction of SiMe 3 group in poly(norbornene) results in a significant increase in a gas permeability, 12,18 and as a results of WAXD and PALS analysis, it was concluded that such behavior was ascribed to an increase in the free volume. Furthermore, the effect of the substituent on gas permeability was much stronger for addition-type poly(norbornene), compared to ROMP-type, relating to the rigidity of the backbone.…”

Section: Gas Permeation Properties Of Poly(norbornene) With Siloxane mentioning

confidence: 98%

“…[2][3][4][5][6][7][8][9][10][11][12][13] Heitz et al 2,3 investigated the addition-type copolymerizations of norbornene with norbornene carboxylic acid esters, and found that the solubility of the copolymers and the thermal properties, such as glasstransition and decomposition temperatures, were dependent on the content as well as structure of the substituents. Risse et al [4][5][6] came to the same conclusion by studying poly-(norbornene)s containing hydroxyl, carboxylic acid and ester.…”

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confidence: 99%

“…Goodall et al [7][8][9] and Grove et al 10 prepared alkyl-or alkoxysilyl-substituted poly(norbornene)s, which showed improved mechanical toughness and adhesion to common substrate materials. On the other hand, Dorkenoo et al 11 and Finkelshtein et al 12 investigated the homopolymers of norbornene derivatives bearing alkyl or alkylsilyl substituents, and demonstrated that the chain length and the bulkiness of the substituents played a decisive role in the transport properties, such as gas permeability and permselectivity, for the polymeric membranes. These results show that the nature of substituent and the content in the main chain are an important factor for the regulation of the material properties.…”

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Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

2009

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Vinyl addition copolymerization of norbornene with norbornene derivatives bearing siloxane substituent, three arm-, cyclicand phenyl-siloxane groups, was realized in the presence of the binary Ni(acac) 2 /B(C 6 F 5 ) 3 system. The resulting copolymers show good solubility in common organic solvents and possess a very high grass transition temperature between 265 and 360 C, depending on the content and structure of the siloxane groups. The incorporation of siloxane groups linked to the polymer chain results in a significant increase in the mechanical flexibility of the corresponding films. Furthermore, the gas permeability is also dependent on the content and structure of the siloxane groups, and the films obtained for the polymers with three arm-siloxane group (-Si(OSiMe 3 ) 3 ) display high oxygen permeability in the range of 39 to 239 Barrer.KEY WORDS: Polynorbornene / Siloxane Substituent / Copolymerization / Nickel Catalyst / Norbornene can be polymerized by three different methods: ring opening metathesis polymerization (ROMP), cationic or radical polymerization, and vinyl addition polymerization. 1Among these polymers, addition-type poly(norbornene), presenting the rigid bicyclic structure, is recently attracting strong interest in optical and opto-electronic device applications because of high optical transparency, low birefringence, very high glass transition temperature and low dielectric constant. However, poor solubility in common organic solvents and mechanical brittleness are serious disadvantages for the processing of the polymer materials. These problems can be improved markedly by copolymerizing a small amount of functional norbornene derivatives.So far, many types of poly(norbornene)s with functional groups have been prepared. [2][3][4][5][6][7][8][9][10][11][12][13] Heitz et al. 2,3 investigated the addition-type copolymerizations of norbornene with norbornene carboxylic acid esters, and found that the solubility of the copolymers and the thermal properties, such as glasstransition and decomposition temperatures, were dependent on the content as well as structure of the substituents. Risse et al. [4][5][6] came to the same conclusion by studying poly-(norbornene)s containing hydroxyl, carboxylic acid and ester. Goodall et al.7-9 and Grove et al. 10 prepared alkyl-or alkoxysilyl-substituted poly(norbornene)s, which showed improved mechanical toughness and adhesion to common substrate materials. On the other hand, Dorkenoo et al. 11and Finkelshtein et al.12 investigated the homopolymers of norbornene derivatives bearing alkyl or alkylsilyl substituents, and demonstrated that the chain length and the bulkiness of the substituents played a decisive role in the transport properties, such as gas permeability and permselectivity, for the polymeric membranes. These results show that the nature of substituent and the content in the main chain are an important factor for the regulation of the material properties.Poly(siloxane) is a class of polymers that has practical importance in the consumer and indus...

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“…Another example of very stiff and highly permeable material is the recently discovered addition type polynorbornene with Si(CH3)3 substituents 15) . This glassy polymer (Tg > 350 ℃)…”

Section: Yampolskii： Some Trends In Materials Science Of Membranes Fomentioning

confidence: 99%

Some Trends in Materials Science of Membranes for Gas Separation

Yampolskii

2006

membrane

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be characterized as rather attractive, industrial membrane gas separation 1) is based today on mainly〝old〟membrane materials: polysulfone, cellulose acetate, silicon rubber, polyphenylene oxide, polyimides. It is difficult to answer if this is a result of conservatism of industrial companies, high cost of manufacture of novel membranes or saturation of membrane market.Due to the theoretical works performed in 1990s, our knowledge on regularities and transport mechanism of small molecules in polymers increased substantially (extended discussion of these results can be found in 2) ). We know now how polymer structure affects permeability (P) and permselectivity (α), we are aware on the role of diffusion and solubility factors in determining permeability and selectivity.Different types of increments allow more or less accurate prediction of the P and α values for different gases 3, 4) , however, this approach is more suitable to interpolations than extrapolations. Orientation of the〝clouds〟of the data points on Robeson diagram and position of upper bound lines can be interpreted on the basis of free volume model and activation diffusion theory, respectively 5,6) . Free volume nano-structure is understood today based on the data of positron annihilation and other probe methods 7 ～ 9) . Computer simulation using molecular dynamics method enables a visualization of free volume (its size distribution and connectivity) and the prediction of solubility coefficients (with accuracy of tens percents) and diffusion coefficients (within factors of 2-3) 10,11) .All this also is (or must be) helpful in search for better membrane materials.Studies of gas permeation properties of polymers started in the middle of XX century, however, only the last decades were marked by enhanced attention to potentially improved membrane materials. Initially, the objects of investigations were mainly semi-crystalline polyolefins and rubbers. Then the interest shifted gradually to glassy polymers, which had been earlier considered as only low permeable materials hardly suitable as candidates for membrane materials.The dynamics of accumulation of our knowledge on gas permeation parameters of glassy polymers can be illustrated

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Addition-Type Polynorbornenes with Si(CH₃)₃ Side Groups: Synthesis, Gas Permeability, and Free Volume

Cited by 122 publications

References 52 publications

Regeneration of Alkanolamine Solutions in Membrane Contactor Based on Novel Polynorbornene

Regeneration of Alkanolamine Solutions in Membrane Contactor Based on Novel Polynorbornene

Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

Some Trends in Materials Science of Membranes for Gas Separation

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Addition-Type Polynorbornenes with Si(CH3)3 Side Groups: Synthesis, Gas Permeability, and Free Volume

Cited by 122 publications

References 52 publications

Regeneration of Alkanolamine Solutions in Membrane Contactor Based on Novel Polynorbornene

Regeneration of Alkanolamine Solutions in Membrane Contactor Based on Novel Polynorbornene

Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

Some Trends in Materials Science of Membranes for Gas Separation

Contact Info

Product

Resources

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Addition-Type Polynorbornenes with Si(CH₃)₃ Side Groups: Synthesis, Gas Permeability, and Free Volume