Synthesis of high-performance polymers via copper-catalyzed amination of dibromoarenes with primary aromatic ether diamines

Zhenfang Shang; Li Yang; Guanjun Chang

Macromolecular Research, Vol.23, No.10, 937-943, October, 2015

DOI10.1007/s13233-015-3125-y Export Citation

Synthesis of high-performance polymers via copper-catalyzed amination of dibromoarenes with primary aromatic ether diamines

Zhenfang Shang, Li Yang^†, and Guanjun Chang^†

State Key Laboratory Cultivation Base for Nonmetal Composite and Functional Materials & School of Material Science and Engineering, Southwest University of Science and Technology, Mianyang, 621010, China

E-mail:,

In this paper, we introduce three high-performance polymers with similar structures, poly(imino ether ketone) (PIEK)s, which are synthesized by the ligand free copper-catalyzed C-N cross coupling reaction of aryl halides and primary aromatic diamines at moderate temperature. The influence of the solvents, base, temperature, and catalyst ligands on the polycondensation reaction is investigated. The structures of the polymers are characterized by means of 1H NMR spectroscopy, FTIR spectrometer and elemental analyses, and the results show a good agreement with the proposed structure. They all exhibit high glass transition temperature (T g >170 °C), good thermal stability with high decomposition temperature (T d,5%>440 °C), and an excellent solubility in most organic solvents. In view of its good thermal stability and solubility, PIEK-1 foam with low density, 96 mg/cm3, is prepared via thermal induced phase separation and freeze-drying technology. The PIEK-1 foam possesses higher thermal stability than that of basal PIEK-1 (T d,5%>465 °C). Furthermore, due to intermolecular hydrogen bonds of the polymers, the achieved foam exhibits good mechanical property.

Keywords:poly(imino ether ketone)s;heat-resistant polymer;copper-catalysis;foam

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[2] Liu J, Zhang Q, Xia Q, Dong J, Xu Q, Polym. Degrad. Stabil., 97, 987 (2012)

[3] Chang G, Yang L, Liu S, Luo X, Lin R, Zhang L, RSC Adv., 4, 30630 (2014)

[4] Wang H, Wang G, Li W, Wang Q, Wei W, Jiang Z, Zhang S, J. Mater. Chem., 22, 21232 (2012)

[5] Zhang N, Zhao C, Ma W, Wang S, Wang B, Zhang G, Li X, Na H, J. Polym. Sci. A: Polym. Chem., 5, 4939 (2014)

[6] Shi Y, Yoonessi M, Weiss RA, Macromolecules, 46(10), 4160 (2013)

[7] Campagne B, David G, Ameduri B, Jones DJ, Roziere J, Roche I, Macromolecules, 46(8), 3046 (2013)

[8] Gebel G, Macromolecules, 46(15), 6057 (2013)

[9] Jung BJ, Lee JI, Chu HY, Do LM, Shim HK, Macromolecules, 35(6), 2282 (2002)

[10] Ayman S, Hussaini A, High Perform. Polym., 26, 166 (2014)

[11] Chang GJ, Yang L, Yang JX, Huang YW, Cao K, Zhang L, Lin RX, Polymer, 54(18), 5043 (2013)

[12] Chang GJ, Yang L, Yang JX, Huang YW, Cao K, Zhang L, Lin RX, J. Polym. Sci. A: Polym. Chem., 51(22), 4845 (2013)

[13] Chang GJ, Yang L, Yang JX, Lin RX, J. Mater. Sci., 49(20), 7213 (2014)

[14] Chang G, Yang L, Liu S, Lin R, You J, J. Polym. Sci. A: Polym. Chem., 6, 697 (2015)

[15] Jammi S, Sakthivel S, Rout L, Mukherjee T, Mandal S, Mitra R, Saha P, Punniyamurthy T, J. Org. Chem., 74, 1971 (2009)

[16] Wang J, Yin X, Wu J, Wu D, Pan Y, Tetrahedron, 69, 10463 (2013)

[17] Huang L, Yu R, Zhu X, Wan Y, Tetrahedron, 69, 8974 (2013)

[18] Khalilzadeh MA, Keipour H, Hosseini A, Zareyee D, New J. Chem., 38, 42 (2014)

[19] Trived M, Ujjain SK, Sharma RK, Singh G, Umar A, Rath NP, New J. Chem., 38, 4267 (2014)

[20] Rout L, Jammi S, Punniyamurthy T, Org. Lett., 17, 3397 (2007)

[21] Zhang H, Cai Q, Ma D, J. Org. Chem., 70, 5164 (2005)

[22] Li B, Liu T, Tang Z, Ji J, Zhong W, J. Mater. Chem., 21, 13546 (2011)

[23] Kumar R, Dhakate SR, Saini P, Mathur RB, RSC Adv., 3, 4145 (2013)

[24] Liu J, Zhang Q, Xia Q, Dong J, Xu Q, Polym. Degrad. Stabil., 97, 987 (2012)

[25] Singh H, Jain AK, J. Appl. Polym. Sci., 111, 1115 (2008)