Ti-MCM-41催化环氧化合物与胺的开环反应

doi:10.7503/cjcu20190124

摘要/Abstract

摘要：

以十六烷基三甲基溴化铵(CTAB)为模板剂, 钛酸异丙酯为钛源, 通过水热法合成了Ti-MCM-41分子筛催化剂并对其进行了表征, 结果表明, Ti-MCM-41催化剂具有介孔结构, 其孔径约2.0~4.0 nm. 考察了无溶剂条件下Ti-MCM-41对环氧化合物与胺的开环反应的催化性能. 结果表明, 当反应温度和压力分别为145 ℃和2.5 MPa时, Ti-MCM-41(5)对环氧乙烷(EO)与二甲胺(DMA)的反应具有良好的催化性能, 环氧乙烷的转化率和N,N-二甲基乙醇胺的选择性分别为98.37%和86.68%. 表征结果表明, 催化剂骨架中四配位结构的Ti使其表面具有丰富的路易斯酸性位, 该酸性位对环氧化合物与胺的开环反应具有重要促进作用. 此外, 还对Ti-MCM-41催化环氧乙烷与二甲胺开环反应的机理进行了初步探讨.

关键词: 开环反应, 环氧化合物, 二甲胺, 介孔分子筛

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

中图分类号:

O643

TrendMD:

赵韵, 魏金晶, 周煜, 朱继秀, 王后勇, 陈爱民. Ti-MCM-41催化环氧化合物与胺的开环反应. 高等学校化学学报, 2019, 40(9): 1937.

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 ^†. Chem. J. Chinese Universities, 2019, 40(9): 1937.

图/表 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 ℃

Table 1 Textural properties of Ti-MCM-41 samples with different Si/Ti molar ratios*

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)

Scheme 1 Reaction of EO and DMA catalyzed by Ti-MCM-41(x)

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.

Table 2 Reaction results of EO with DMA over various catalysts*

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

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