Isomerization of methylenedianilines using shape-selective zeolites

doi:10.1016/S1872-2067(24)60071-9

Abstract

Abstract:

Methylenedianilines (MDA) are widely used as intermediates in the production of polyurethanes and polyisocyanurates. The current routes for the production of MDA offer only limited control of the isomer ratio (4,4’/(2,4’+2,2’)), with 4,4’-MDA being the most valuable isomer. While 2,4’-MDA is also marketed, significant added value could be unlocked upon further steering the production towards 4,4’-MDA. We here show that zeolites such as Beta can selectively isomerize 2,4’-MDA towards the desired 4,4’-MDA via a bimolecular mechanism, in an aniline background. While several acid zeolites were found to be active isomerization catalysts, MCM-68 (MSE topology) in particular combines high isomerization activity with efficient shape-selective suppression of the formation of unwanted 2,2’-MDA and oligomers. The origin of this shape-selectivity was studied, highlighting the crucial role of the acid site location in the pore confinement of MSE zeolites.

Key words: Aluminum distribution, Heterogeneous catalysis, Isomerization, Methylenedianiline, Polyurethane, Shape-selectivity

Sam Van Minnebruggen, Ka Yan Cheung, Trees De Baerdemaeker, Niels Van Velthoven, Matthias Degelin, Galahad O’Rourke, Hiroto Toyoda, Andree Iemhoff, Imke Muller, Andrei-Nicolae Parvulescu, Torsten Mattke, Jens Ferbitz, Qinming Wu, Feng-Shou Xiao, Toshiyuki Yokoi, Nils Bottke, Dirk De Vos. Isomerization of methylenedianilines using shape-selective zeolites[J]. Chinese Journal of Catalysis, 2024, 62: 124-130.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60071-9

https://www.cjcatal.com/EN/Y2024/V62/I7/124

Figures/Tables 8

Scheme 1. Reaction network for the isomerization of 2,4’-MDA.

Fig. 1. Product distribution obtained in the solventless MDA isomerization for *BEA topology zeolites with different Si/Al mass ratio. Conditions: 50 mg zeolite, 250 mg 2,4’-MDA at 170 °C for 6 h.

Fig. 2. Product distribution obtained in the MDA isomerization for *BEA topology with varying aniline quantity. Mass ratio of Beta (Si/Al = 12.5):MDA:aniline = 0.2:1:x, with x = 0?8 at 170 °C for 24 h.

Fig. 3. Role of aniline in the isomerization of 2,4’-MDA using zeolite Beta. Conditions: 100 mg Beta (Si/Al = 12.5), 500 mg 2,4’-MDA and x mol L?1 aniline at 170 °C. The kinetic values represent respectively the following: kiso,1 (2,4’→ 4,4’), kiso,2 (2,4’→ 2,2’) and koligo (MDA → oligomer).

Fig. 4. Temperature dependence of the rate constant for isomerization of 2,4’- to 4,4’-MDA and derived apparent activation energies. Conditions: 100 mg zeolite Beta (Si/Al = 12.5), 500 mg 2,4’-MDA and 200 μL aniline at 140?200 °C.

Table 1 Kinetic parameters for different acid catalysts. Conditions: 100 mg zeolite, 500 mg 2,4’-MDA and 1.2 mL aniline at 170 °C.

Catalyst	Topology	Si/Al	k_iso,1 (10^‒6 s^‒1)^a	k_iso,-1 (10^‒6 s^‒1)	k_iso,2 (10^‒6 s^‒1)	k_iso,-2 (10^‒6 s^‒1)	k_oligo (10^‒7 s^‒1)
CF₃SO₃H^b	—	—	2.7	19.7^c	1.0	0.5	4.2
ZSM-5	MFI	15	0.4	0.6	0.2	0.5	0.4
Mordenite	MOR	10	0.6	0.6	0.3	0.5	0.4
Beta	*BEA	12.5	5.3	0.5	0.3	1.0	2.3
Faujasite	FAU	40	1.9	0.1	0.3	0.2	0.1
MCM-68	MSE	10.8	4.7	0.6	0.2	0.5	0.2
UZM-35	MSE	7.8	1.0	0.1	0.3	1.0	0.5
YNU-5	YFI	9.8	4.8	15.0	0.6	0.1	0.2
MCM-22	MWW	14	0.5	5.3	19.9	215	2.0

Fig. 5. Shape-selectivity in MDA isomerization, comparing zeolite Beta and MCM-68. Conditions: 100 mg zeolite, 500 mg MDA and 0.2 mL aniline at 170 °C. Beta (Si/Al = 12.5) in the isomerization of (a) 2,4’- and (b) 4,4’-MDA. MCM-68 in the isomerization of (c) 2,4’- and (d) 4,4’-MDA.

Fig. 6. Proposed origin of shape-selectivity in MCM-68. (a) Concept of 10-MR docked aniline reacting with a 4-NH2-benzylium cation at the intersection with 12-MR. (b,d) optimized structures for the reactants at the intersection, leading to resp. 4,4’- and 2,4’-MDA. (c,e) Optimized structures of the carbo-cationic intermediates at the intersection, leading to resp. 4,4’- and 2,4’-MDA.

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