Thermal Stability of Polyimide Resins Containing Siloxane Structure and Their High Temperature Structural Evolution

doi:10.7503/cjcu20180342

Abstract

Abstract:

A series of phenylethynyl-terminated imide oligomers(PEPA-PIS) based on siloxane-containing aromatic diamine, i.e., bis(p-aminophenoxy)dimethyl silane(APDS), was synthesized. The effect of siloxane content on the thermal stability of cured polyimides resins was investigated. The influence of temperature on the evolution of siloxane structure was confirmed by the non-reactive phthalic-terminated model imide oligomers(PA-PIS). The thermal stability of polyimide resins after post-curing at elevated temperature and the correlation with the microstructure and surface morphology were discussed. The results indicated that the oxidative crosslinking reaction of siloxane was occurred at elevated temperature, and even resulting in the formation of inorganic silica on the resin surface. The significant enhancement in thermal stability of polyimide containing siloxane structure is attributed to their organic/inorganic hybrid characteristics.

Key words: Polyimide resin, Siloxane, Thermal stability, Microstructure, Organic/inorganic hybrid

CLC Number:

O631

TrendMD:

LIU Yi, XU Xiaozhou, MO Song, ZHAI Lei, HE Minhui, FAN Lin. Thermal Stability of Polyimide Resins Containing Siloxane Structure and Their High Temperature Structural Evolution[J]. Chem. J. Chinese Universities, 2019, 40(1): 187.

Figures/Tables 11

Fig.1 Chemical structures of PEPA-terminated and PA-terminated oligoimides

Table 1 Chemical composition of PEPA-terminated and PA-terminated oligoimides

Sample	n(TFDB):n(APDS)	Mass fraction of siloxane(%)	n	M_n(Theoretical)
PEPA-PIS-0	10:0	0	1.23	1500
PEPA-PIS-1	9:1	1.29	1.25	1500
PEPA-PIS-2	8:2	2.59	1.26	1500
PEPA-PIS-3	7:3	3.92	1.28	1500
PA-PIS-1	9:1	1.47	1.60	1500
PA-PIS-10	0:10	15.81	1.76	1500

Fig.2 Effect of siloxane content on the thermal stability of cured polyimide resins

Fig.3 DMA curves of polyimide resins after curing at 370 ℃(A) and post-curing at 450 ℃(B)

Fig.4 Isothermal melt viscosities of PA-PIS-1 at different temperatures for 2 h

Fig.5 29Si NMR spectra of PA-PIS-10 exposed at 370 ℃(a) and 500 ℃(b) for 1 h

Fig.6 Si2p XPS spectra of PEPA-PIS-1 cured at 370 ℃(A), as well as after post-curing at 420 ℃(B) and 450 ℃(C), respectively

Table 2 Curve fitting results of Si2p XPS spectra for cured and postcured PEPA-PIS-1

Structure	370 ℃		420 ℃		450 ℃
Structure	E_b/eV	Molar fraction of Si(%)	E_b/eV	Molar fraction of Si(%)	E_b/eV	Molar fraction of Si(%)
D[(CH₃)₂SiO_2/2]	102.01	90.19	102.06	14.76	101.96	6.90
T[CH₃SiO_3/2]	102.97	9.81	102.90	48.34	102.93	23.61
Q[SiO_4/2]	——	——	103.53	36.90	103.51	69.49

Fig.7 Si2p XPS spectra measured for different depths of PEPA-PIS-1 after post-curing at 450 ℃Depth/mm: (A) 0.02; (B) 0.10; (C) 0.15; (D) 0.20; (E) 0.40; (F) 0.80.

Fig.8 TEM image of PEPA-PIS-1 after post-curing at 450 ℃

Scheme 1 Schematic diagram of microstructural changes at elevated temperature for polyimide containing siloxane structure

References 25

[1]	Meador M. A., Annu. Rev. Mater. Sci., 1998, 28, 599—630
[2]	Liaw D. J., Wang K. L., Huang Y. C., Lee K. R., Lai J. Y., Ha C. S., Prog. Polym. Sci.,2012, 37, 907—974
[3]	Hergenrother P. M., High. Perform. Polym., 2003, 15, 3—45
[4]	Miyauchi M., Ishida Y., Ogasawara T., Yokota R., Polym. J.s,2012, 44, 959—965
[5]	Yu X. H., Zhao X. G., Liu C. W., Dang G. D., Wang Y. L., Zhou H. W., Chem. J. Chinese Universities,2009, 30(11), 2297—2300
	(于晓慧, 赵晓刚, 刘长威, 党国栋, 王运良, 周宏伟. 高等学校化学学报, 2009, 30(11), 2297—2300)
[6]	Rao X. H., Dang G. D., Zhou H. W., Deng Y. Q., Lu Y. B., Chen C. H., Wu Z. W., Chem. J. Chinese Universities,2006, 27(9), 1775—1778
	(饶先化, 党国栋, 周宏伟, 邓勇强, 路迎宾, 陈春海, 吴忠文. 高等学校化学学报, 2006, 27(9), 1775—1778)
[7]	Hergenrother P. M., Connell J. W., Smith J. G., Polymer,2000, 41, 5073—5081
[8]	Su C. N., Ji M., Fan L., Yang S. Y., High Perform. Polym.,2011, 23, 352—361
[9]	Vij V., Haddad T. S., Yandek G. R., Ramirez S. M., Mabry J. M., Silicon,2012, 4, 267—280
[10]	Seurer B., Vij V., Haddad T., Marby J. M., Lee A., Macromolecules,2010, 43, 9337—9347
[11]	Yue J., Li Y. T., Li H., Zhao Y., Zhao C. X., Wang X. Y., RSC. Adv.,2015, 5, 98010—98019
[12]	Yue J., Li Y. T., Zhao Y., Xiang D., Dai Y. X., Polym. Degrad. Stab.,2016, 129, 286—295
[13]	Lincoln J. E., Hout S., Flaherty K., Curliss D. B., Morgan R. J., J. Appl. Polym. Sci.,2008, 107, 3557—3567
[14]	Lincoln J. E., Morgan R. J., Curliss D. B., Polym. Compos.,2008, 29, 585—596
[15]	Liu Y., Mo S., He M.H., Zhai L., Xu C. H., Fan L.,High Perform. Polym., 2018, DOI: 10.1177/0954008 318780211
[16]	Tiptipakorn S., Damrongsakkul S., Ando S., Hemvichian K., Rimdusit S., Polym. Degrad.Stab.,2007, 92, 1265—1278
[17]	Lee Y. B., Park H. B., Shim J. K., Lee Y. M., J. Appl. Polym. Sci.,1999, 74, 965—973
[18]	Coburn J. C., Soper P. D., Auman B. C., Macromolecules,1995, 28, 3253—3260
[19]	Hergenrother P. M., Smith J. G., Polymer,1994, 35, 4857—4864
[20]	Fang X. M., Xie X. Q., Simone C. D., Stevens M. P., Scola D. A., Macromolecules,2000, 33, 1671—1681
[21]	Camino G., Lomakin S. M., Lazzari M., Polymer,2001, 42, 2395—2404
[22]	Chang T. C., Wu K. H., Polym. Degrad. Stab.,1998, 60, 161—168
[23]	Ahmad Z., Sagheer F. A., Arbash A. A., Ali A. A. M., J. Non-Cryst. Solids,2009, 355, 507—517
[24]	O’Hare L. A., Parbhoo B., Leadley S. R., Surf. Interface. Anal.,2004, 36, 1427—1434
[25]	Brookes P. N., Fraser S., Short R. D., Hanley L., Fuoco E., Roberts A., Hutton S., J. Electron. Spectrosc. Relat. Phenom.,2001, 121, 281—297