Gas transport properties of new aromatic polyimides based on 3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride

doi:10.1016/j.memsci.2014.12.007

Journal of Membrane Science

Volume 476, 15 February 2015, Pages 442-448

https://doi.org/10.1016/j.memsci.2014.12.007 Get rights and content

Highlights

•
A planar and rigid dianhydride has been used to prepare gas separation polyimides.
•
PCO₂/PHe and PCH₄/PN₂ ratios are reversed compared to glassy polymers (as in PIMs).
•
Very high permeability has been attained by combining with ortho-substituted diamines.
•
Meta-substitution in diamine significantly improves permeability.
•
New polyimides show excellent combination of permeability and selectivity for CO₂/N₂.

Abstract

Three novel polyimides have been successfully synthesized from 3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride (DPPD), and three commercial diamines by solution polycondensation. All polymers exhibited high molecular weight, high thermal stability and high rigidity (no glass transition was detected up to 400 °C) and free volume. The new polymers have been tested as gas separation membranes, showing very good combination of permeability and selectivity, especially in the case of the polymer derived from trimethyl-m-phenylenediamine (TMPD), which overpassed the 1991 Robeson upper bound for the gas pairs O₂/N₂ and CO₂/CH₄ and was near the 2008 upper bound for CO₂/N₂.

Graphical abstract

Introduction

Polymeric membranes are an attractive option for gas separation because of the versatility of their chemistry, feasibility of synthesis and large scale production, processability and cost in comparison to other membranes, such as zeolites. The major requirements for polymeric membranes to efficiently separate gases are:

•
Enhancing membrane selectivity and permeability, thus overcoming the “trade-off” between membrane permeability and selectivity.
•
Addressing the limited chemical and thermal stability of membranes.
•
Enabling the design and fabrication of controlled membrane architectures.

Glassy aromatic polyimides are able to tackle these issues, and consequently they are among the most attractive and promising gas-separation polymers because of their high gas selectivity (separation efficiency), excellent thermal stability, high chemical resistance and good mechanical properties [1], [2].

Consequently, considerable research has been carried out on improved polyimide membrane materials, by rational molecular design of polymeric structures to create new membranes with superior gas separation properties. In many instances, the high degree of packing and low mobility of molecular chains greatly limits the diffusion of gas molecules through the polymer matrix, and consequently aromatic polyimide membranes commonly have low to moderate permeability. The introduction of packing-disrupting units into the backbone has been the most effective way of enhancing diffusivity through an increment of the fractional free volume (FFV).

In recent works, our approach to prepare polymer membranes with an improved selectivity/permeability balance has consisted of using monomers, diamines or dianhydrides, with bulky side groups conveniently placed to increase, in a synergistic way, chain rigidity and FFV [3], [4], [5], [6].

Rigid dianhydrides with bulky side groups have been used to obtain polyimides with excellent gas separation properties [7]. Also, the combination of ortho substituted diamines with rigid dianhydrides has been recently described by Pinnau et al. [8], who have used a bromo-substituted spirobifluorene diamine in combination with different dianhydrides to obtain polyimides with good gas separation. In that paper, it had been found that pyromellitic dianhydride gave better results than the significantly more expensive 6FDA, mainly when the bromo-substituted diamine was employed.

Therefore, in this work, we have studied a planar, very rigid, dianhydride that has been conveniently modified to bear pendant phenyl groups, which will hinder the tendency of the planar structure to stacking. This dianhydride has been combined with three commercial aromatic diamines, two of them having substituents ortho to the amino groups. It was expected that the combination of the dianhydride with the ortho substituted diamines would significantly difficult chain packing, thus giving a combination of very low chain mobility and high fractional free volume, which should produce membranes able to approach the Robeson upper bound [9].

Section snippets

Materials

Naphthalene (99%, Alfa Aesar), benzoyl chloride (99%, Sigma-Aldrich), aluminum chloride (AlCl₃, 99.5%, Sigma-Aldrich), diethylene glicol (99%, Alfa Aesar), hydrazine monohydrate (64–65%, Sigma-Aldrich), sodium hydroxide (NaOH, Panreac), maleic anhydride (99%, Acros Organics), iodine (99.8%, Sigma-Aldrich), nitrobenzene (99%, Alfa Aesar), N-methylpyrrolidinone, NMP, (99%, Sigma-Aldrich), N,N-dimethylformamide, DMF, (99,8%, Sigma-Aldrich), pyridine (anhydrous, 99.8%, Sigma-Aldrich) and benzoic

Results and discussion

Pyrene-1,2,6,7-tetracarboxylic dianhydride is a planar, very rigid dianhydride constituted of six fused rings, four from pyrene and two from the cyclic anhydrides. Because of its planar structure, it is expected that this dianhydride will have a strong tendency to stack and consequently it would not be suitable to prepare gas separation membranes, where a high internal free volume is needed. Therefore, in this work, two phenyl rings have been introduced in ortho positions to the anhydride rings

Conclusions

By combining a flat, rigid dianhydride, with bulky groups, and commercial diamines, new polyimides with excellent gas separation properties have been obtained. The permeability order is: PCO₂>PHe>PO₂>PCH₄>PN₂, as occurs in PIMs and other microporous polymers. The presence of ortho substituents in the diamine increases the rotational barrier around the imide bond and increases rigidity, thus increasing the membrane performance. Moreover, the combination of ortho substituents with

Acknowledgments

The financial support provided by Projects MAT2013-45071-R and Consolider-Ingenio 2010-CSD-0050-MULTICAT of the Spanish Secretaría de Estado de Investigación, Desarrollo e Innovación is gratefully acknowledged. J. L. Santiago-García gratefully acknowledges a CONACYT postdoctoral fellowship (186332).

References (24)

D. Ayala et al.
Gas separation properties of aromatic polyimides
J. Membr. Sci.
(2003)
Y. Xiao et al.
The strategies of molecular architecture and modification of polyimide-based membranes for CO₂ removal fromnatural gas—a review
Progr.Polym. Sci.
(2009)
M. Calle et al.
Design of gas separation membranes derived of rigid aromatic polyimides. 1. Polymers from diamines containing di-tert-butyl side groups
J. Membr. Sci.
(2010)
M. Calle et al.
Local chain mobility dependence on molecular structure in polyimides with bulky side groups: correlation with gas separation properties
J. Membr. Sci.
(2013)
L.M. Robeson
Correlation of separation factor versus permeability for polymeric membranes
J. Membr. Sci.
(1991)
E. Clar et al.
New benzenogenic diene syntheses
Tetrahedron
(1974)
J.Y. Park et al.
Correlation and prediction of gas permeability in glassy polymer membrane materials via a modified free volume based group contribution method
J. Membr. Sci.
(1997)
W. Qiu et al.
Gas separation performance of 6FDA-based polyimides with different chemical structures
Polymer
(2013)
J. de Abajo et al.
Microstructural parameters controlling gas permeability and permselectivity in polyimide membranes
Macromol. Symp.
(2003)
M. Calle et al.
Novel aromatic polyimides derived from 5′-t-butyl-2′-pivaloylimino-3,4,3ʺ,4ʺ-m-terphenyltetracarboxylic dianhydride with potential application on gas separation processes
Macromolecules
(2010)

Y-H. Kim et al.

Synthesis and characterization of new organosoluble and gas-permeable polyimides from bulky substituted pyromellitic dianhydrides

J. Polym. Sci. Part A: Polym. Chem.

(2002)

X. Ma et al.

Novel spirobifluorene- and dibromospirobifluorene-based polyimides of intrinsic microporosity for gas separation applications

Macromolecules

(2013)

Cited by (39)

Water vapor sorption and transport in carbon molecular sieve membranes
2024, Journal of Membrane Science
Carbon Molecular Sieve (CMS) membranes have been extensively studied for gas separations. Many gas separation applications involve humidified streams, but reports on water vapor transport in CMS membranes are limited. In this study, water permeability, diffusivity, and solubility were determined as a function of water activity for CMS membranes. Water transport properties of membranes synthesized at different pyrolysis temperatures (550 °C and 800 °C) and with different polyimide precursors were examined. Water sorption followed Type V isotherms as previously observed for the adsorption of water in microporous carbons. Water permeability was much higher at all water activity values for CMS samples prepared at lower pyrolysis temperature. Water permeabilities as a function of water activity of the three different polyimides pyrolyzed at 800 °C were very similar. Water permeability of CMS membranes was high compared to many other polymeric materials, showing potential for dehydration applications. Finally, the steady-state water vapor diffusivity (D_ss), estimated from steady state permeability and equilibrium sorption measurements, was compared to the experimental transient diffusivity (D), matching reasonably well.
Metal-free redox-active diphenylpyrenediimides: A comparison between the photocatalytic performance of molecular and polymeric catalysts
2023, Journal of Catalysis
Herein we described a donor–acceptor porous conjugated polydiphenylpyreneimide (DPPy-PI) with high thermal stability (530 °C) and surface area of 710 m².g⁻¹ prepared by condensation of 3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride (DPPyDA) and tris(4-aminophenyl)benzene and a series of pyrenediimides (DPPy-DIs) as molecular references for comparative purposes. To evaluate the effect of the photoactive pyrene unit the polydiphenylperyleneimide (DPP-PI) having perylene units was also prepared.
DPPy-PI has shown to see an efficient metal-free heterogeneous photocatalyst in the selective oxidation of aromatic sulfides and for Diels-Alder cycloadditions reaching almost full conversions with low reaction times and high selectivity that can be reused for at least fifteen cycles without significant loss of catalytic activity. Characterization data reveals that imide radicals are the important active intermediates during the redox processes of these PIs.
CMS membranes from rigid diphenyl pyrene polyimides: Effect of precursor structure in the final gas permeability and separation properties
2023, Journal of Membrane Science
Carbon molecular sieve membranes CMSM were prepared by pyrolysis at 600 °C final temperature under Ar from 4 high temperature resistant polyimides, DP-TMPD, DP-MBDAM, DPt-TMPD and DPt-MBDAM, based in 3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride (DP) and tert-butyl lateral group modified 3,8-di(4-tert-butylphenyl)pyrene-1,2,6,7-tetracarboxylic dianhydride (DPt) reacted each with two different diamines 2,4,6-trimethyl-m-phenylenediamine (TMPD) and 4,4′-methylenebis(2,6-dimethyl-aniline) (MBDAM). As obtained CMSM show between 3 and 7 times higher selectivity compared to polyimide precursor. In these CMSM CO₂/CH₄ surpasses 2019 Robeson's upper bond selectivity, for H₂/N₂ and O₂/N₂ it also lies above 2015 Robeson's upper bond. There is also an increase in gas permeability coefficients, P, between 1.5 and 3 times those of the polyimide precursors. CMSM Ageing for 8040 h show only a slight decrease and P with a slight increase on gas selectivity. CMSM membranes characterization by wide angle X-ray diffraction (WADX) indicate that the presence, in the polyimide precursor, of tert-butyl lateral groups in the diphenyl pyrene structure (DPt) gives rise to a third intermediate d-space value, around 8 Å, between those presented by DP. As a result, DPt based CMSM's increase P while selectivity decreases slightly compared to DP based CMSMs. Diffusion coefficients, D, for pyrolyzed DP-TMPD-P, DPt-TMPD-P, DP-MBDAM-P and DPt-MBDAM-P are lower than those of the precursor membranes. In all cases reduction in, D, particularly for the large d_k gases, CH₄ up to 10 time lower, is the main reason for selectivity increases in CMSM. In general DP and DPt based CMS membranes studied in this work present an important increase in selectivity reaching or surpassing Robeson's latest upper bond limit with an increase or minimum loss in P. This increase in selectivity is comparable and in some instances it surpasses that of other high rigidity precursor polyimide or CMS membranes reported in the literature.
Polymer materials derived from the SEAr reaction for gas separation applications
2023, Polymer
A set of linear polymers were synthesized utilizing an electrophilic aromatic substitution reaction (SEAr) between biphenyl and ketone containing electron-withdrawing groups (isatin, IS; N-methylisatin, MeIS; and 4,5-diazafluoren-9-one, DF). Optimization of the polycondensation reaction was made to obtain high molecular weight products when using DF, which has not previously been used for linear polymer synthesis. Due to the absence of chemically labile units, these polymers exhibited excellent chemical and thermal stability. Linear SEAr polymers were blended with porous polymer networks derived from IS and MeIS, and both neat/mixed materials were tested as membranes for gas separation. The gas separation properties of both pristine polymers and mixed matrix membranes were good, showing some polymer membrane CO₂ permeability values higher than 200 barrer.
Advances, challenges, and perspectives of biogas cleaning, upgrading, and utilisation
2022, Fuel
Biogas as a renewable energy resource can be broadly recognised as a carbon–neutral fuel which reduces anthropogenic greenhouse gas emissions, mitigates global warming, and diversifies energy supply. However, the biogas share in the global renewable energy supply chain and technology deployment and maturity are not commensurate with the potential. The first half of this study critically reviews state of the art developments in biogas cleaning and upgrading technologies by considering their present status, current challenges, and barriers associated with their future development. The second part of this paper aims to address critical gaps in converting biogas to biomethane, proposing required pre-treatment steps for different technologies. The third part focuses on current policies concerning the strict regulations implemented for flaring consent applications. In this section, biogas upgrading technologies were compared by estimating the global warming potential (GWP) resulting from waste gases (WG). It was observed that due to high methane losses, WGs from membrane technologies have the highest GWP, but with flaring have the lowest GWP. In the last part of this review, the recent applications of biogas in cogeneration (CHP), tri-generation (CCHP), quad-generation systems, heat, and vehicles are discussed. The use of biogas by different technologies, and their resulting efficiencies were analysed in CHP applications, including microturbines, micro humid air turbine (mHAT), solid oxide fuel cells (SOFC) and hybrid systems of SOFC-microturbines.
Thin film composite membranes for postcombustion carbon capture: Polymers and beyond
2022, Progress in Polymer Science
The escalating level of atmospheric carbon dioxide (CO₂) due to the combustion of fossil fuels has been identified as a major contributor to climate change. CO₂ capture using membrane-based gas separation provides a promising route to offset anthropogenic emissions. Thin film composite (TFC) membranes offer the capability to handle large gas flux demands and represent one of the most energy-efficient, industrially viable candidates for CO₂ capture. In this review, we provide an overview of trends in materials science of TFC membranes for CO₂ capture from flue gas. We explore the range of synthetic approaches and diverse materials (polymers, inorganics, and carbon materials) used in TFC assemblies, and critically examine the structural and chemical properties of prospective membrane materials that can help to meet the challenges of industrial CO₂ capture. A comparison of the CO₂/N₂ separation performance and current technical limitations of the latest TFC membranes is also provided. We conclude by sharing outstanding challenges and opportunities for future research directions in the field.

View all citing articles on Scopus

View full text

Gas transport properties of new aromatic polyimides based on 3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Results and discussion

Conclusions

Acknowledgments

J. Membr. Sci.

Progr.Polym. Sci.

J. Membr. Sci.

J. Membr. Sci.

J. Membr. Sci.

Tetrahedron

J. Membr. Sci.

Polymer

Microstructural parameters controlling gas permeability and permselectivity in polyimide membranes

Macromol. Symp.

Novel aromatic polyimides derived from 5′-t-butyl-2′-pivaloylimino-3,4,3ʺ,4ʺ-m-terphenyltetracarboxylic dianhydride with potential application on gas separation processes

Macromolecules

Synthesis and characterization of new organosoluble and gas-permeable polyimides from bulky substituted pyromellitic dianhydrides

J. Polym. Sci. Part A: Polym. Chem.

Novel spirobifluorene- and dibromospirobifluorene-based polyimides of intrinsic microporosity for gas separation applications

Macromolecules