Ti-MCM-41 Catalysts for the Ring Opening Reaction of Epoxy Compounds with Amines †

doi:10.7503/cjcu20190124

Abstract

Abstract:

The synthesis of β-aminoalcohols by conventional catalysts is limited by a variety of conditions. The mesostructure Ti-MCM-41 molecular sieve catalyst was synthesized from the template cetyltrimethyl ammonium bromide(CTAB) and the isopropyl titanate used as titanium source by hydrothermal synthesis method. All the catalysts were characterized by N₂ adsorption-desorption, XRD, SEM/TEM, DR UV-vis, FTIR and NH₃-TPD. The XRD and SEM/TEM results indicated that the Ti-MCM-41 catalyst was a mesoporous structure with average pores size of about 2.0—4.0 nm in the sample framework. The catalytic performance of Ti-MCM-41 catalysts for the ring opening reaction of ethylene oxide with dimethylamine was investigated in stainless steel batch reactor under solvent free condition. For the ring opening reaction of ethylene oxide(EO) with dimethylamine(DMA), the synthesized catalyst with the Si/Ti molar ratio of 5∶1 provided the most efficient catalyst performance and the selectivity in the products reaching up to 98.37% and at 86.68% conversion at 145 ℃ and 2.5 MPa. DR UV-Vis, FTIR and NH₃-TPD results indicated that the four coordinated Ti in the structure of catalyst makes the surface of molecule sieve catalyst possesses rich Lewis acid site. Moreover, increased the surface acidity is conducive to the improvement of catalytic activity. It revealed that acidic active sites on the catalyst surface might be responsible for promoting the ring opening reaction of epoxy compounds with amines. The mechanism of ring opening reaction of dimethylamine with ethylene oxide catalyzed by Ti-MCM-41 was also discussed.

Key words: Ring opening reaction, Epoxy compound, Dimethylamine, Mesoporous molecular sieve

CLC Number:

O643

TrendMD:

ZHAO Yun, WEI Jinjing, ZHOU Yu, ZHU Jixiu, WANG Houyong, CHEN Aimin. Ti-MCM-41 Catalysts for the Ring Opening Reaction of Epoxy Compounds with Amines ^†[J]. Chem. J. Chinese Universities, 2019, 40(9): 1937.

Figures/Tables 18

Fig.1 Low-angle(A) and wide-angle(B) XRD patterns of Ti-MCM-41(40)(a), Ti-MCM-41(20)(b), Ti-MCM-41(10)(c) and Ti-MCM-41(5)(d) calcined at 550 ℃ for 6 h

Fig.2 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of Ti-MCM-41(5)(a), Ti-MCM-41(10)(b), Ti-MCM-41(20)(c) and Ti-MCM-41(40)(d) calcined at 550 ℃

Entry	Catalyst	S_BET/(m²·g^-1)	V_t/(cm³·g^-1)	D/nm
1	MCM-41	790	0.75	3.8
2	Ti-MCM-41(5)	444	0.43	3.9
3	Ti-MCM-41(10)	682	0.56	3.3
4	Ti-MCM-41(20)	869	0.62	2.9
5	Ti-MCM-41(40)	811	0.63	3.1

Fig.3 SEM images of Ti-MCM-41(5)(A), Ti-MCM-41(10)(B), Ti-MCM-41(20)(C) and Ti-MCM-41(40)(D) calcined at 550 ℃

Fig.4 SEM images of Ti-MCM-41(5) samples at different calcination temperatures Calcination temperature/℃: (A) 450; (B) 500; (C) 550; (D) 600.

Fig.5 TEM images of Ti-MCM-41(5)(A) and Ti-MCM-41(40)(B)

Fig.6 FTIR spectra of MCM-41(a), Ti-MCM-41(40)(b), Ti-MCM-41(20)(c), Ti-MCM-41(10)(d) and Ti-MCM-41(5)(e)

Fig.7 UV-Vis diffuse re?ectance spectra of samples a. TiO2; b. Ti-MCM-41(5); c. Ti-MCM-41(10); d. Ti-MCM-41(20); e. Ti-MCM-41(40); f. MCM-41.

Fig.8 NH3-TPD profiles of Ti-MCM-41(5)(a), Ti-MCM-41(10)(b), Ti-MCM-41(20)(c) and Ti-MCM-41(40)(d)

Fig.9 Effect of the reaction temperature on the conversion and selectivity Reaction condition: catalyst: Ti-MCM-41(5) calcined at 550 ℃; 2.2 MPa for 35 min; 5%(mass fraction) of catalyst with respect to EO, EO/DMA molar ratio: 1∶3.5.

Fig.10 Effect of the reaction pressure on the conversion and selectivity Reaction condition: catalyst: Ti-MCM-41(5) calcined at 550 ℃, 135 ℃ for 35 min, 5%(mass fraction) of catalyst with respect to EO, EO/DMA molar ratio: 1∶3.5.

Entry	Catalyst	EO conversion(%)	DMA selectivity(%)	DEMA yield(%)
1	TiO₂	97.37	81.21	79.07
2	MCM-41	97.44	83.53	81.40
3	Ti-MCM-41(5)	98.37	86.68	85.27
4	Ti-MCM-41(10)	97.56	73.84	75.60
5	Ti-MCM-41(20)	97.28	72.46	71.22
6	Ti-MCM-41(40)	97.23	76.52	74.40

Fig.11 Effect of the calcined temperatures of Ti-MCM-41(5) sample on the conversion and selectivity under 145 ℃ and 2.5 MPa for 40 min Ti-MCM-41(5) catalyst was added 5%(mass fraction) with respect to EO; the molar ratio EO to DMA is 1∶3.5.

Fig.12 Mechanism of epoxy compounds reacted with amines catalyzed by Ti-MCM-41 catalyst

Fig.13 Reuse performance of the Ti-MCM-41(5) catalyst

Fig.14 XRD patterns(A) and FTIR spectra(B) of the Ti-MCM-41(5) before(a) and after(b) repeated use

References 41

[1]	Corey E.J., Zhang F. Y.,Angew. Chem. Int. Ed. Engl., 1999, 38, 1931—1934
[2]	Johannes C. W., Visser M. S., Weatherhead G. S., Hoveyda A. H., ,J. Am. Chem. Soc., 1998, 120, 8340— 8347
[3]	Ager D. J., Prakash I., Schaad D. R., ,Chem. Rev., 1996, 96, 835— 875
[4]	Brien P. O ., Angew. Chem. Int. Ed. Engl. 1999, 38, 326— 329
[5]	Tu Y. Q., Xia W. J., ,Chem. J. Chinese Universities, 1999,20( 4), 587— 589
	(涂永强,夏吾炯. 高等学校化学学报, 1999, 20(4), 587— 589)
[6]	Clarkson C., Musonda C. C., Chibale K., Campbell W. E., Smith P., ,Bioorg. Med. Chem., 2003, 11, 4417— 4422
[7]	Palomo C., Oiarbide M., Laso A., ,Angew. Chem. Int. Ed., 2005, 44, 3881— 3884
[8]	Pujala B., Rana S., Chakraborti A. K., ,J. Org. Chem., 2011, 76( 21), 8768— 8780
[9]	Cai P. Y., Zhang E. S., Wu Y. S., Fang T. B., Li Q. Q., Yang C., Wang J., Shang Y. J., ,ACS Omega., 2018, 3( 11), 14575— 14584
[10]	He W., Wang L., Sun C., Wu K., He S., Chen J., Wu P., Yu Z., ,. Chem. Eur. J. 2011, 17, 13308— 13317
[11]	Cui X. J., Dai X. C., Deng Y. Q., Shi F., ,. Chem. Eur. J. 2013, 19, 3665— 3675
[12]	Jumde V. R., Petricci E., Petrucci C., Santillo N., Taddei M., Vaccaro L., ,Org. Lett., 2015, 17( 16), 3990— 3993
[13]	Kamal A., Prasad R. B., Reddy A. M., Naseer M., Khan A., ,Catal. Commun., 2007, 8, 1876— 1880
[14]	Brahmam P., Shivani R., Asit K. C., ,J. Org. Chem., 2011, 76, 8768— 8780
[15]	Wu X. Y., Shu F. C., ,Chem. J. Chinese Universities, 1999,20( 12), 1892— 1896
	(伍新燕, 舒福昌. 高等学校化学学报, 1999, 20(12), 1892— 1896)
[16]	Narsaiah A. V., Sreenu D., Nagaiah K., ,Syn. Commun., 2006, 36, 3183— 3189
[17]	Loukrakpam D. C., Phukan P., ,. Tetrahedron Lett. 2017, 58( 52), 4855— 4858
[18]	An D. L., Song W. K., Peng Z. H., Zhang Y. J., Dong W. R ., Chemistryselect 2018, 3( 45), 12946— 12950
[19]	Struble T. J., Lankswert H. M., Pink M., Johnston J. N., ,ACS. Catal., 2018, 8( 12), 11926— 11931
[20]	Kamal A., Ramu R., Azhar M. A., Khanna G. B. R., ,Tetrahedron. Lett., 2005, 46, 2675— 2677
[21]	Feher C., Tomasek S., Hancsok J., Skoda-Foldes R., ,. Appl. Catal. B 2018, 239, 52— 60
[22]	Tamboli A. H., Bandal H. A., Kim H., ,Chem. Eng. J., 2016, 306, 826— 831
[23]	Medamoni V., Kishore P., Narender P., Satyanarayana B., ,. J. Mol. Catal. A 2007, 266, 290— 293
[24]	Mathew W. C., Robinson D. A., Timms S M., Williams A. E. G., ,Tetrahedron. Lett., 2007, 48, 6249— 6251
[25]	Fraile J. M., García N., Mayoral J. A., Santomauro F. G., Guidotti M., ,ACS Catal., 2015, 5, 3552— 3561
[26]	Martinez E. G., Balmori A., Ponton I., Sanchez G. D ., Catal. 2018, 8(12), 617-1—62
[27]	Nadeem S., Mumtaz A., Mumtaz M., Mutaib M. I., Shaharun M. S., Abdullah B., ,J. Mol. Liq., 2018, 272, 656— 667
[28]	Chen A., Wang H. Y., Liu R., Bo Y. Y., Hu J., ,Catal. Lett., 2016, 146( 7), 1182— 1193
[29]	Selvaraj M., Lee K., Yoo K. S., Lee T. G., ,Micropor. Mesopor. Mater., 2005, 81, 343— 355
[30]	Jeﬀrey K., Jacek J., Sharon M., Javier P. R ., Langmuir 2015, 31, 1242— 1247
[31]	Peter B. W., Wang X. L., Wolfgang Z., Klaus R. L., Hui T. C., ,. Acta Phys. Chim. Sinica 2014, 118, 8350— 8358
[32]	Chao C., Hua W., Jin Y. H., ,Appl. Surf. Sci., 2011, 257, 9802— 9808
[33]	Qin X. Y., Zhao W. B., Han B., Liu B. A., Lian P. C., Wu S. S., ,Korean J. Chem. Eng., 2015, 32( 6), 1064— 1068
[34]	Maria S. B., Joana M. F. M., Dulce M. A., Joana M. F., Braga R. M., Marcus A. F., Fontes V. A., ,J. Therm. Anal. Calorim., 2015, 119, 197— 204
[35]	Eimer G. A., Chanquia C. M., Sapag K., Herrero E. R., ,Micropor. Mesopor. Mater., 2008, 116, 670— 676
[36]	Chao M. C., Lin H. P., Mou C. Y., Cheng B. W., Cheng C. F., ,Catal. Today., 2004, 97, 81— 87
[37]	Thomas R., Antje P., Jurgen R., ,Synthetic. Commun., 2002, 32( 3), 457— 465
[38]	Parker R. E., ,Chem. Rev., 1959, 2, 737— 799
[39]	Satyarthi J. K., ,Appl. Catal. A:Gen., 2007, 330, 145— 151
[40]	Ahmed. K., Rajendra. P. A., MallaR. M., Malla R. M., Naseer A. K., ,Catal. Commun., 2007, 8, 1876— 1880
[41]	Boningari T., Rapelli S., Avvari N., Prasad J. K., Prashanth K., Benjaram M., ,Org. Process. Res. Dev., 2010, 14, 1457— 1463