Abstract
Triphenylmethane-based polyimides and copolyimides containing bulky t-butyl group (tBu) were obtained by one-step high temperature polycondensation of 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride with diamines of triphenylmethane (TPM) family. The polymers were obtained in quantitative yields with inherent viscosities of 0.45–0.80 dL/g. They exhibited high thermal stability with 5% weight loss above 500 °C and were cast in films with good mechanical properties capable of testing as gas separation membranes. All polyimides were readily soluble in polar aprotic solvents, and the solubility enhanced with the increase in tBu-group content. The amorphous, free-standing membranes were prepared from these polymers, and their permeabilities and selectivities to several gases were measured and discussed with respect to the structural differences in the polymers. It was shown that the presence of bulky tBu-units made the chain packing less efficient; free volume and d-spacing in the polyimides grew accordingly. As a consequence, the membranes with higher content of tBu-groups demonstrated improved permeabilities, showing 1.5–3.0 times higher permeability coefficients depending on the gas tested. The membranes’ separation performance was improved for CO2/CH4 gas pair in comparison with that of structurally similar polyimides, while it did not change for O2/N2 pair. Additionally, the mechanism of formation of triphenylmethane diamines in the reaction between aniline and benzaldehydes was investigated in order to optimize the monomer synthesis and to minimize possible side reactions. It was established that the secondary diamines, so-called aminals, were inevitable side products, particularly important in the condensation between aniline and tBu-benzaldehyde.
Similar content being viewed by others
References
Liaw DJ, Wang KL, Huang YC, Lee KR, Lai JY, Ha CS (2012) Advanced polyimides materials: synthesis, physical properties and applications. Prog Polym Sci 37:907–974
Mittal V (2011) High performance polymers and engineering plastics. Wiley, New Jersey
Ree M (2006) High performance polyimides for applications in microelectronics and flat panel displays. Macromol Res 14:1–33
Bernardo P, Drioli E, Golemme G (2009) Membrane gas separation: a review/state of the art. Ind Eng Chem Res 48:4638–4663
Baker RW (2002) Future directions of membrane gas separation technology. Ind Chem Eng Res 41:1393–1411
Baker RW, Lokhandwala K (2008) Natural gas processing with membranes: an overview. Ind Eng Chem Res 47:2109–2121
Xiao YC, Low BT, Hosseini SS, Chung TS, Paul DR (2009) The strategies of molecular architecture and modification of polyimide-based membranes for CO2 removal from natural gas—a review. Prog Polym Sci 34:561–580
Lin H, Freeman BD (2005) Materials selection guidelines for membranes that remove CO2 from gas mixtures. J Mol Struct 739:57–74
Yao P, Gu J, Lei X, Sun W, Chen Y, Zhang Q (2015) Highly soluble and thermally stable copolyimides modified with trifluoromethyl and siloxane. J Appl Polym Sci 132:41713
Wilks BR, Chung WJ, Ludovice PJ, Rezac ME, Meakin P, Hill AJ (2006) Structural and free-volume analysis for alkyl-substituted palladium-catalyzed poly(norbornene): a combined experimental and Monte Carlo investigation. J Polym Sci Part B Polym Phys 44:215–233
Zhuo L, Kou K, Wang Y, Yao P, Wu G (2014) Synthesis of soluble and thermally stable polyimides with phthalimide as pendent group from pyridine–containing triamine. J Mater Sci 49:5141–5150
Yi L, Li C, Huang W, Yan D (2014) Soluble aromatic polyimides with high glass transition temperature from benzidine containing tert-butyl groups. J Polym Res 21:572
Kin SD, Lee S, Heo J, Kim SY, Chung IS (2013) Soluble polyimides with trifluoromethyl pendent groups. Polymer 54:5648–5654
Chen G, Pei X, Liu J, Fang X (2013) Synthesis and properties of transparent polyimides derived from trans- and cis-1,4-bis(3,4-dicarboxyphenoxy)cyclohexane dianhydrides. J Polym Res 20:159
Kim YH, Ahn SK, Kim HS, Kwon SK (2002) Synthesis and characterization of new organosoluble and gas-permeable polyimides from bulky substituted pyromellitic dianhydrides. J Polym Sci Part B Polym Chem 40:4288–4296
Liaw DJ, Hsu PN, Chen WH, Lin SL (2002) High glass transitions of new polyamides, polyimides, and poly(amide-imide)s containing a triphenylamine group: synthesis and characterization. Macromolecules 35:4669–4676
Qiu Z, Chen G, Zhang Q, Zhang S (2007) Synthesis and gas transport property of polyimide from 2,2-disubstituted biphenyltetracarboxylic dianhydrides (BPDA). Eur Polymer J 43:194–204
Kim HS, Kim YH, Ahn SK, Kwon SK (2003) Synthesis and characterization of highly soluble and oxygen permeable new polyimides bearing a noncoplanar twisted biphenyl unit containing tert-butylphenyl or trimethylsilyl phenyl groups. Macromolecules 36:2327–2332
Robeson LM (1991) Correlation of separation factor versus permeability for polymeric membranes. J Membr Sci 62:165–185
Robeson LM (2008) The upper bound revisited. J Membr Sci 320:390–400
Freeman BD (1999) Basis of permeability/selectivity tradeoff relations in polymeric gas separation membranes. Macromolecules 32:375–380
Abetz V, Brinkmann T, Dijkstra M, Ebert K, Fritsch D, Ohlrogge K, Paul D, Peinemann KV, Pereira-Nunes S, Scharnagl N, Schossig M (2006) Developments in membrane research: from material via process design to industrial application. Adv Eng Mater 8:328–358
Nagel C, Gunther-Schade K, Fritsch D, Strunskus T, Faupel F (2002) Free volume and transport properties in highly selective polymer membranes. Macromolecules 35:2071–2077
Budd PM, McKeown NB, Fritsch D (2005) Free volume and intrinsic microporosity in polymers. J Mater Chem 15:1977–1986
Thran A, Kroll G, Faupel F (1999) Correlation between fractional free volume and diffusivity of gas molecules in glassy polymers. J Polym Sci Part B Polym Phys 37:3344–3358
Likhatchev D, Alexandrova L, Tlenkopatchev M, Vilar R, Vera-Graziano R (1995) Soluble aromatic polyimides and polyamides based on 4,4′-diaminotriphenylmethane. J Appl Polym Sci 57:37–44
Likhatchev D, Alexandrova L, Tlenkopatchev M, Martinez-Richa A, Vera-Graziano R (1996) One-step synthesis of aromatic polyimides based on 4,4′-diaminotriphenylmethane. J Appl Polym Sci 61:815–818
Aguilar-Lugo C, Perez-Martinez AL, Guzmán-Lucero D, Likhatchev D, Alexandrova L (2012) Polyimides based on 4,4′-diaminotriphenylmethane. In: Medard Abadie JM (ed) High performance polymers–polyimides based—from chemistry to applications, 1st edn. InTech, Rijeka, pp 3–14
Aguilar-Lugo C, Santiago-García JL, Loría-Bastarrachea MI, Guzmán-Lucero D, Alexandrova L, Aguilar-Vega M (2016) Synthesis, characterization, and structure-property relationships of aromatic polyimides containing 4,4′-diaminotriphenylmethane. J Polym Res 23:49
Guzmán-Lucero D, Palomeque-Santiago JF, Camacho-Zúñiga C, Ruiz-Treviño FA, Guzmán J, Galicia-Aguilar A, Aguilar-Lugo C (2015) Gas permeation properties of soluble aromatic polyimides based on 4-Fluoro-4,4′-diaminotriphenylmethane. Materials 8:1951–1965
Guzmán-Lucero D, Guzmán J, Likhatchev D, Martínez-Palou R (2005) Microwave-assisted synthesis of 4,4′-diaminotriphenylmethanes. Tetrahedron Lett 46:1119–1122
Saya I, Damaceanu MD, Constantin CP, Asandulesa M, Wolinska-Grabczyk A, Jankowski A (2018) Structure–promoted high performance properties of triphenylmethane-containing polyimides and copolyimides. Eur Polym J 108:554–569
Huang X, Pei X, Wang L, Mei M, Liu C, Wei C (2016) Design and synthesis of organosoluble and transparent polyimides containing bulky substituents and noncoplanar structures. J Appl Polym Sci 133(14):43266
Serberzeanu D, Carja ID, Bruma M, Ronova IA (2016) Correlation between physical properties and conformational rigidity of some aromatic polyimides having pendant phenolic groups. Struct Chem 27:973–981
Cheng SW, Huang TT, Tsai CL, Liou GS (2017) Highly transparent polyhydroxyimide/TiO2 and ZrO2 hybrid films with high glass transition temperature (Tg) and low coefficient of thermal expansion (CTE) for optoelectronic application. J Mater Chem C 5(33):8444–8453
Campbell KN, Sommers AH, Cambell BK (1944) The preparation of unsymmetrical secondary aliphatic amines. J Am Chem Soc 66(1):82–84
Ohashi S, Cassidy F, Huang S, Chiou K, Ishida H (2016) Synthesis and ring-opening polymerization of 2-substituted 1,3-benzoxazine: the first observation of the polymerization of oxazine ring-substituted benzoxazines. Polym Chem 7:7177–7184
Loría-Bastarrachea MI, Aguilar-Vega M (2013) Membranes from rigid block hexafluoro copolyaramides: effect of the block lengths on gas permeation and ideal separation factors. J Membr Sci 443:36–44
Ahmadi SJ, Hosseinpour M, Sadjadi S (2012) Non-catalytic condensation of aromatic aldehydes with aniline in high temperature water. Green Chem Lett Rev 5(3):403–407
Alinezhad H, Ardestani E, Noroozi S (2009) Synthesis of 4,4′-diaminotriphenylmethane derivatives using H3PW12O40 and HZSM5 zeolite under solvent-free conditions. J Iran Chem Soc 6(4):816–822
Cho BP, Yang T, Blankenship RL, Moody JD, Churchwell M, Beland FA, Culp SJ (2003) Synthesis and characterization of N-demethylated metabolites of malachite green and leucomalachite green. Chem Res Toxicol 16:285–294
Le Goff T, Wood S (2008) Production of malachite green oxalate and leucomalachite green reference materials certified for purity. Anal Bioanal Chem 391:2035–2045
Cui Y, Ni Y (2001) Preparation of N,N-diphenyl toluene. Synth Commun 31(2):257–261
Rowland GB, Zhang H, Rowland EB, Chennamadhavuni S, Wang Y, Antilla JC (2005) Brønsted acid-catalyzed imine amidation. J Am Chem Soc 127(45):15696–15697
Godoy-Alcántar C, Yatsimirsky AK, Lehn JM (2005) Structure-stability correlations for imine formation in aqueous solution. J Phys Org Chem 18:979–985
Saggiomo V, Lüning U (2009) On the formation of imines in water—a comparison. Tetrahedron Lett 50:4663–4665
Ishida H, Wellinghoff ST, Baer E, Koenig JL (1980) Spectroscopic studies of poly(N,N′-bis(phenoxyphenyl)pyromellitimide). 1. Structures of the polyimide and three model compounds. Macromolecules 13:826–834
Sulub-Sulub R, Loría-Bastarrachea MI, Vázquez-Torres H, Santiago-García JL, Aguilar-Vega M (2018) Highly permeable polyimide membranes with a structural pyrene containing tert-butyl groups: synthesis, characterization and gas transport. J Membr Sci 563:134–141
Schmaljohann D, Häussler L, Pötschke P, Voit BI, Loontjens TJ (2000) Modification with alkyl chains and the influence on thermal and mechanical properties of aromatic hyperbranched polyesters. Macromol Chem Phys 201:49–57
Ragosta G, Abbate M, Musto P, Scarinzi G (2012) Effect of the chemical structure of aromatic polyimides on their thermal aging, relaxation behavior and mechanical properties. J Mater Sci 47:2637–2647
Liu SL, Wang R, Liu Y, Chng ML, Chung TS (2001) The physical and gas permeation properties of 6FDA-durene/2,6-diaminotoluene copolyimides. Polymer 42:8847–8855
Kothawade SS, Kulkarni MP, Kharul UK, Patil AS, Vernekar SP (2008) Synthesis, characterization, and gas permeability of aromatic polyimides containing pendant phenoxy group. J Appl Polym Sci 108:3881–3889
Zhang J, Kang H, Martin J, Zhang S, Thomas S, Merkel TC, Jin J (2016) The enhancement of chain rigidity and gas transport performance of polymers of intrinsic microporosity via intramolecular locking of the spiro-carbon. Chem Commun 52:6553–6556
Pixton MR, Paul DR (1994) Relationships between structure and transport properties for polymers with aromatic backbones. In: Paul DR, Yampolskii YP (eds) polymeric gas separation membranes, 1st edn. CRC Press, Boca Raton, pp 83–154
Ordonez MJC, Balkus KJ, Ferraris JP, Musselman IH (2010) Molecular sieving realized with ZIF-8/Matrimid® mixed-matrix membranes. J Membr Sci 361:28–37
Soleymanipour SF, Saeedi-Dehaghani AH, Pirouzfar V, Alihosseini V (2016) The morphology and gas-separation performance of membranes comprising multiwalled carbon nanotubes/polysulfone–Kapton. J Appl Polym Sci 133:43839–43847
Kim TH, Koros WJ, Husk GR, O’Brien KC (1988) Relationship between gas separation properties and chemical structure in a series of aromatic polyimides. J Membr Sci 37:45–62
Okamoto K, Tanaka K, Kita H, Ishida M, Kakimoto M, Imai Y (1992) Gas permeability and permselectivity of polyimides prepared from 4,4′-diaminotriphenylamine. Polym J 24:451–457
Zhang CL, Cao B, Li P (2018) Thermal oxidative crosslinking of phenolphthalein-based cardo polyimides with enhanced gas permeability and selectivity. J Membr Sci 546:90–99
Zhang C (2019) Synthesis and characterization of bis(phenyl)fluorine based cardo polyimide membranes for H2/CH4 separation. J Mater Sci 54:10560–10569
Zou L, Cao X, Zhang Q, Dodds M, Guo R, Gao H (2018) Friedel–Crafts A2 + B4 polycondensation toward regioselective linear polymer with rigid triphenylmethane backbone and its property as gas separation membrane. Macromolecules 51:6580–6586
Acknowledgements
This work was supported by grants from DGAPA # IN107117 and by Spain’s MINECO (Projects MAT2016-76413-C2-R2, and MAT2016-76413-C2-R1). The authors thank G. Cedillo Valverde, M.A. Canseco Martinez, E. Hernandez Mecinas, E. R-Morales and A. Tejeda Cruz (all from IIM-UNAM) for different kinds of analyses and also would like to acknowledge Sara Rodriguez for the gas separation measurements. R.A.C.B. is grateful to CONACyT for the financial support.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Castro-Blanco, R.A., Rojas-Rodríguez, M., Hernández, A. et al. Aromatic polyimides and copolyimides containing bulky t-butyltriphenylmethane units. Polym. Bull. 77, 5103–5125 (2020). https://doi.org/10.1007/s00289-019-03003-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-019-03003-7