Preparation method for alicyclic carbamate and use thereof

Patent metadata

Field	Value
Publication number	US-2025188021-A1
Application number	US-202218844333-A
Country	US
Kind code	A1
Filing date	Jul 26, 2022
Priority date	Mar 7, 2022
Publication date	Jun 12, 2025
Grant date	—

Abstract

Disclosed herein are a preparation method for an alicyclic carbamate and the use thereof. The preparation method comprises the following steps: mixing a carbamate containing an aromatic ring, a catalyst and a solvent, and then introducing hydrogen for reaction to obtain the alicyclic carbamate, wherein the catalyst comprises a carrier and an active component, which is loaded on the carrier, the active component comprising any one or a combination of at least two of Pt, Rh, Ru, Ir or Pd. The preparation method for the alicyclic carbamate provided in the present application has mild reaction conditions, easy operation, low potential safety hazard and a high yield of the alicyclic carbamate, is suitable for multiple reactors, is easy for large-scale continuous production, and has good industrial application prospects.

First claim

What is claimed is:

1 . A preparation method for an alicyclic carbamate, comprising the following steps: mixing an aromatic ring-containing carbamate, a catalyst and a solvent, and then performing a reaction with hydrogen introduced to obtain the alicyclic carbamate;
the catalyst comprises a carrier and an active component loaded on the carrier; the the active component comprises any one or a combination of at least two of Pt, Rh, Ru, Ir or Pd.

2 . The preparation method for an alicyclic carbamate according to claim 1 , wherein the active component is any one of a combination of Ru and Pd, a combination of Rh and Ru, a combination of Ru and Pt, a combination of Ru and Ir, a combination of Rh and Pt, a combination of Ir and Pt, a combination of Pd and Pt or a combination of Ir and Pd, preferably a combination of Ru and Pd.

3 . The preparation method for an alicyclic carbamate according to claim 1 , wherein the carrier comprises any one or a combination of at least two of SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , MgO, kaolin, bentonite, montmorillonite, ZSM-5, X-zeolite, Y-zeolite, B-zeolite, mordenite, spinel, magnesium-aluminum hydrotalcite, activated carbon, graphene, carbon nanotubes, g-C 3 N 4 , h-BN or a nitrogen-doped carbon composite.

4 . The preparation method for an alicyclic carbamate according to claim 1 , wherein the catalyst further comprises an auxiliary agent loaded on the carrier, and the auxiliary agent comprises an elemental metal and/or a metal oxide.

5 . The preparation method for an alicyclic carbamate according to claim 4 , wherein the elemental metal comprises any one or a combination of at least two of Ni, Fe, Co, La or Ce;
preferably, the auxiliary agent is any one or a combination of at least two of Ni, Fe, Co, La 2 O 3 , CeO 2 , NiO, Ni 2 O 3 , FeO, Fe 2 O 3 , Fe 3 O 4 , CoO, Co 2 O 3 or Co 3 O 4 , preferably a combination of Ni and Co.

6 . The preparation method for an alicyclic carbamate according to claim 1 , wherein a mass of the active component is 0.1-10% of the total mass of the catalyst;
preferably, a mass of the auxiliary agent is 0-10% of the total mass of the catalyst, and 0 means that the catalyst does not contain the auxiliary agent; preferably, a mass ratio of the aromatic ring-containing carbamate to the catalyst is (30-100):0.1.

7 . The preparation method for an alicyclic carbamate according to claim 1 , wherein the solvent comprises any one or a combination of at least two of methanol, water, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, 2-methyltetrahydrofuran, 1,4-dioxane, ethyl acetate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methylcyclohexane or cyclohexane, and preferably a combination of methanol and water, a combination of methanol and ethanol, a combination of ethanol and water, a combination of tetrahydrofuran and water, a combination of tetrahydrofuran and ethanol, and a combination of tetrahydrofuran and methanol, and further preferably a combination of ethanol and water.

8 . The preparation method for an alicyclic carbamate according to claim 1 , wherein the aromatic ring-containing carbamate has a general formula as follows:

wherein R 1 is selected from a substituted or unsubstituted C6-C30 aromatic ring-containing hydrocarbyl group, and a substitute or unsubstituted aryl group; substituted substituents are selected from any one of a nitro group, a hydroxyl group, an alkylmercapto group, an arylmercapto group, a sulfonyl group, a carbonyl group, a halogen atom, a cyano group, an amino group, a carboxyl group, an ester group, an alkoxy group or an aryloxy group, and the aryl group and aromatic ring are independently selected from a benzene ring, biphenyl, naphthalene or diphenylmethane;
n is an integer selected from 1 to 5; and
R 2 is selected from a linear or branched C1-C8 saturated hydrocarbyl group or a C5-C10 saturated cyclic hydrocarbyl group.

9 . The preparation method for an alicyclic carbamate according to claim 8 , wherein R 2 is selected from any one of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a cyclopentyl group or a cyclohexyl group.

10 . The preparation method for an alicyclic carbamate according to claim 1 , wherein a mass fraction of the aromatic ring-containing carbamate is 0.5-30% in the solvent.

11 . The preparation method for an alicyclic carbamate according to claim 1 , wherein the reaction is performed in a reactor, and the reactor is any one of a fixed bed, a fluidized bed or a tank reactor.

12 . The preparation method for an alicyclic carbamate according to claim 11 , wherein the reactor is a fixed bed or a fluidized bed, the reaction is performed at a temperature of 0-180° C., the reaction is performed at a pressure of 0.1-10 MPa, a molar ratio of the hydrogen to the aromatic ring-containing carbamate is (20-300):1, and a liquid hourly space velocity of the aromatic ring-containing carbamate is 0.1-10 h −1 .

13 . The preparation method for an alicyclic carbamate according to claim 11 , wherein the reactor is a tank reactor, the reaction is performed at a temperature of 0-180° C., and the reaction is performed at a pressure of 0.1-10 MPa.

14 . Use of the preparation method for an alicyclic carbamate according to claim 1 in the preparation of polyurethane.

Assignees

• Inst Process Eng Cas

Inventors

• Wang Liguo
• Xu Shuang
• Li Huiquan
• He Peng
• Cao Yan
• Zheng Zheng
• Chen Jiaqiang

Classifications

• C07C2601/14

  The ring being saturated · CPC title

• C07C269/06 Primary

  by reactions not involving the formation of carbamate groups · CPC title

• B01J21/04

  Alumina · CPC title

• B01J23/462

  Ruthenium · CPC title

• B01J23/892

  Nickel and noble metals · CPC title