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Materials Chemistry a Accepted Manuscript Journal of Materials Chemistry A Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/materialsA Page 1 of 8 Journal Name Journal of Materials Chemistry A Dynamic Article Links ► Cite this: DOI: 10.1039/c0xx00000x www.rs c.org/xxxxxx ARTICLE TYPE Synthesis, Characterization, and Gas Transport Properties of Novel Poly(amine imide)s Containing Tetraphenylmethane Pendant Groups Hongchao Mao, a,b Suobo Zhang a* Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX 5 DOI: 10.1039/b000000x Manuscript Two bis(amine anhydride) monomers containing tetraphenylmethane pendant groups were synthesized from palladium-catalyzed amination reaction of N-methyl-4-chlorophthal-imide with arylamines, followed by alkaline hydrolysis of the intermediate bis(amine imide)s and subsequent dehydration of the resulting tetraacids. These monomers were polymerized with appreciate aromatic diamines to obtain a 10 series of novel poly(amine imide)s. The attained polymers exhibited good solubility in many aprotic solvents and had glass transition temperatures in the range of 310 to 395 oC. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 510 °C in nitrogen. The surface areas of these novel poly(amine imide)s ranged from 78 to 290 m 2/g. Films obtained by casting exhibited a combination of relatively high permeability and modest good permselectivity with values 15 close to the Robeson upper-bound for O 2/N 2 and CO 2/CH 4 gas pairs. Accepted Introduction therefore they were considered to be microporous materials A (PIMs). 13 The PIs containing spirobisindane moieties were first Aromatic polyimides (PIs) are widely studied for use in gas 14 50 prepared by Zhang et al. in 2007, and shortly thereafter PIM-PI separation owing to their good gas transport properties, membranes were reported that exhibited significantly higher exceptional chemical and thermal stability, as well as mechanical 15-17 1,2 permeability compared to conventional PI membranes. 20 robustness among the various classes of polymers. Their gas In our previous study, we reported the synthesis of a series separation properties could be easily tuned by numerous of poly(amine imide)s based on two kinds of N-linked combinations between diamines and dianhydrides. 3.4 In many 55 dianhydrides which were obtained from the Pd-catalyzed cases, PIs with stiff backbone chains are considered as organic amination reaction of 4-chlorophthalimide with aniline and p- molecular sieves among polymeric membrane materials for gas tert-butylaniline, respectively. 18 Because of the introduction of 25 separation due to their high selectivity. However, most of the PIs propeller-shaped tripenylamine groups in the dianhydride units, still fall below the Robeson upper-bound for important gas pairs Chemistry 5.6 the resulting PIs exhibited good solubility in many aprotic (e.g., O2/N 2, CO 2/N 2, and CO 2/CH 4), and there is need for the 60 solvents, good thermal resistance and exceptionally high glass polyimide materials that are both highly permeable and transition temperatures. 19,20 Moreover, the Pd-catalyzed selective. 7-9 To obtain better performing PIs, an effective strategy amination method provides a facile synthetic route to 30 is to introduce bulky and rigid groups into PIs, which tend to dianhydrides containing a variety of amines and diamines increase both polymer chain rigidity and free volume, what could moieties. 18,21 That is, many useful physical and chemical be translated into a combination of high permeability and good 65 properties in this kind of poly(amine imide)s could be tuned by selectivity. 10 Recently, J. de Abajo et al., prepared a series of using different dianhydrides from corresponding amines and copolyimides having adamantine ester pendant groups, and found diamines. Thus, from the perspective of obtaining the processable 35 that these copolyimides exhibited higher permeability and PIs possessing excellent gas separation properties and thermal diffusion coefficients than the starting copolyimide governed by Materials stability, amines with bulky and rigid groups should be adopted the internal free volume, which confirmed the positive effect of 70 to synthesize N-linked dianhydrides and corresponding adamantane groups on improving the gas separation properties. 11 poly(amine imide)s. of Park et al., reported a new platform of high performance In the present paper, we describe the successful synthesis of 40 polyimide based on 2,6-diaminotriptycene, which had internal novel poly(amine imide)s derived from two new N-linked free volume elements and thus led to the formation of high dianhydrides containing bulky and rigid tetraphenylmethane fractional free volume with proper cavity size to separate small 75 moieties as pendant groups, which could stiff the polymer gas molecules with high selectivity as high permeability. 12 backbone by restricting the segmental mobility and give rise to Especially, the spirobisindane unit was also incorporated into the high free volume through increasing inter-chain separation that 45 PIs, which inhabited the space-efficient packing of the polymer are essential requirements for good gas separation property. 10,22-23 chains and led to a large amount of free volume. The free volume Additionally, the poly(amine imide) based on the diamine and Journal was accessible to probe molecules as for instance nitrogen and 80 dianhydride both containing tetraphenylmethane groups as This journal is © The Royal Society of Chemistry [year] [journal] , [year], [vol] , 00–00 | 1 CREATED USING THE RSC ARTICLEJournal TEMPLATE of (VER. Materials 3.0) - SEE WWW.RSC.ORG/ELECTRONICFILESChemistry A FOR DETAILS Page 2 of 8 ARTICLE TYPE www.rsc.org/xxxxxx | XXXXXXXX pendant group was also prepared for further comparison. from methanol and DMAc (2:1,v/v) in a yield of 81% (21.2 g). IR Physical, thermal, and gas separation properties of these novel (KBr): 1767 and 1715 (C=O of imide), 1380 (C-N stretching), -1 1 poly(amine imide)s were studied. We expect that these 742 cm (C=O bending). H (DMSO-d6): 7.78-7.81 (d, 2H), 7.28- poly(amine imide)s could be equipped with good gas separation 7.39 (m, 10H), 7.14-7.26 (m, 13H), 3.00 (s, 6H). Anal. Calcd for 5 properties, solubility and thermal stability. 60 C43 H31 N3O4 (653.72): C, 79.00; H, 4.78; N, 6.43. Found: C, 78.85; H, 4.91; N 6.29. Experimental Part N′-Methyl-N,N-bis(3,4-phthalimide)-4-(tris(4-(tert- butyl)phenyl)methyl)aniline (2II) Materials This compound was prepared from 1 and 4-(tris(4-(tert- 4-Chlorophthalic anhydride (99.2%) was purified by distillation. 65 butyl)phenyl)methyl)aniline using the same procedure as THF and bis(2-methoxy ethyl)ether were dried by refluxing over described above. The yield of 2II was 86% (28.3g). IR (KBr): 1769 and 1716 (C=O of imide), 1376 (C-N stretching), 742 cm -1 10 sodium distilled prior to use. Dimethyl sulfoxide (DMSO; 1 ACROS) were dried over calcium hydride overnight, distilled (C=O bending). H (DMSO-d6): 7.70-7.73 (d, 2H), 7.49-7.52 (d, under reduced pressure. Cesium carbonate (Cs CO ) and cesium 2H), 7.25-7.34 (m, 8H), 7.24-7.19 (d, 2H), 7.06-7.11 (d, 6H), 2 3 Manuscript fluoride (CsF) was dried in vacuum at 150 oC for 24h prior to use. 70 6.95-7.03 (d, 2H), 2.99 (s, 6H), 1.31(s, 27H). Anal. Calcd for C H N O (822.04): C, 80.34; H, 6.74; N, 5.11. Found: C, m-Cresol was dried over CaCl 2, then over molecular sieves, 55 55 3 4 80.11; H, 6.85; N 5.03. 15 distilled under reduced pressure and stored under nitrogen in the N,N′-bis(3,4-dicarboxyphenyl)-4-tritylaniline dianhydride (I) dark. Pd 2(dba) 3 (Aldrich), 9,9-dimethyl-4,5- bis(diphenylphosphino)xanthene (Xantphos, Acoros), To a solution of 15% NaOH aqeous solution (60 mL) was added isoquinoline (Acoros), 4,4′-(hexafluor-oisopropylidene)dianiline 75 13.1 g of compound 2I (20 mmol ). The mixture was refluxed for (6FpDA, Aldrich), 2,4,6-trimethylbenzene-1,3-diamine ( m- 48 h under nitrogen atmosphere after the solid was completely dissolved. After cooling to room temperature, the solution was 20 TMDA, Acros), Mg (Acros), 10% Pd/C (Aldrich), 4- adjusted to pH=1.0 with 6N HCl. The yellow precipitate was fluoronitrobezene (Aldrich) were used as received. Other collected by filtration and dried in vacuum at 100 oC. The commercially available reagent grade chemicals were used Accepted without further purification. N-methyl-4-chlorophthalimide ( 1) 80 resulting tetracarboxylic acid was dissolved in acetic acid (25 were prepared as previously described.18 4-Tritylaniline, and 4- mL) and acetic anhydride (25 mL).
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