One-pot process using heterogeneous catalyst

Patent metadata

Field	Value
Publication number	US-9944571-B2
Application number	US-201515528338-A
Country	US
Kind code	B2
Filing date	Nov 16, 2015
Priority date	Nov 19, 2014
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

The present invention relates to a process for the one-pot hydrogenation and dehydration or isomerization of an organic compound, and to a catalyst composition for this process comprising transition metal particles having particle size below 50 nm supported on a material comprising at least one fluorinated polymer (P), wherein polymer (P) bears —SO 2 X functional groups, X being selected from X′ and OM, X′ being selected from the groups consisting of F, Cl, Br and I; and M being selected from the group consisting of H, and alkaline metal and NH 4 .

First claim

The invention claimed is:

1. A process for the one-pot hydrogenation and acid-catalysed isomerisation or dehydration of a substrate (I) containing at least a C═C, a C═O, an acetal, a 1,2-diol or a hemiacetal moiety to obtain a product (II), wherein said process comprises reacting the substrate (I) with hydrogen (H 2 ) in the presence of a catalyst (III), said catalyst comprising transition metal particles having particle size below 50 nm supported on a material comprising at least one fluorinated polymer (P), wherein polymer (P) bears —SO 2 X functional groups, X being selected from X′ and OM, X′ being selected from the group consisting of F, Cl, Br, and I; and M being selected from the group consisting of H, an alkaline metal and NH 4 .

2. The process according to claim 1 , wherein the transition metal particles in the catalyst consist of at least one transition metal, in non-charged or ionic form, selected from ruthenium, rhodium, platinum, palladium, copper, nickel, iridium, cobalt, osmium, rhenium, iron, and combinations thereof.

3. The process according to claim 1 , wherein the step of reacting the substrate (I) with catalyst (III) is carried out at a temperature from 50 to 150° C.

4. The process according to claim 1 , wherein levulinic acid (Ia) is converted into gamma-valerolactone (IIa), hemicellulose or cellulose (Ib) is converted into sorbitol (IIb), xylose (Ic) is converted into levulinic acid or an ester thereof (IIc), gamma-valerolactone (IIa) is converted into pentanoic acid (IId), glycerol (Ie) is converted into 1,2-propanediol (IIe), citronellal (If) is converted into menthol (IIf), acetone (Ig) is converted into methyl isobutyl ketone (IIg), or glucose (Ih) is converted into 1,6-hexanediol or 2,5-dimethylfuran (IIh).

5. The process according to claim 4 , wherein the substrate (I) is levulinic acid (Ia) and the product (II) is gamma-valerolactone (IIa).

6. The process according to claim 1 , wherein the a least one fluorinated polymer bearing —SO 2 X functional groups comprises recurring units derived from at least one ethylenically unsaturated fluorinated monomer containing at least one —SO 2 X′ functional group (monomer A) and recurring units derived from at least one ethylenically unsaturated fluorinated monomer (monomer B).

7. The process according to claim 6 , wherein the a least one fluorinated polymer (P) comprises:
recurring units derived from at least a monomer (A), wherein monomer (A) is selected from:
sulfonyl halide fluoroolefins of formula: CF 2 ═CF(CF 2 ) p SO 2 X′ wherein p is an integer between 0 and 10;
sulfonyl halide fluorovinylethers of formula: CF 2 ═CF—O—(CF 2 ) m SO 2 X′ wherein m is an integer between 1 and 10;
sulfonyl halide fluoroalkoxyvinyl ethers of formula: CF 2 ═CF—(OCF 2 CF(R F1 )) w —O—CF 2 (CF(R F2 )) y SO 2 X′ wherein w is an integer between 0 and 2, R F1 and R F2 , equal or different from each other, are independently F, Cl or a C 1 -C 10 fluoroalkyl group, optionally substituted with one or more ether oxygens, y is an integer between 0 and 6;
sulfonyl halide aromatic fluoroolefins of formula CF 2 ═CF—Ar—SO 2 X′ wherein Ar is a C 5 -C 15 aromatic or heteroaromatic substituent; and
recurring units derived from at least a monomer (B), wherein monomer (B) is selected from
C 2 -C 8 fluoroolefins;
C 2 -C 8 chloro- and/or bromo- and/or iodo-fluoroolefins;
fluoroalkylvinylethers of formula CF 2 ═CFOR f1 , wherein R f1 is a C 1 -C 6 fluoroalkyl;
fluoro-oxyalkylvinylethers of formula CF 2 ═CFOR O1 , wherein R O1 is a C 1 -C 12 fluoro-oxyalkyl having one or more ether groups; fluoroalkyl-methoxy-vinylethers of formula CF 2 ═CFOCF 2 OR f2 in which R f2 is a C 1 -C 6 fluoroalkyl or a C 1 -C 6 fluorooxyalkyl having one or more ether groups;
fluorodioxoles, of formula:

wherein each of R f3 , R f4 , R f5 , R f6 , equal or different each other, is independently a fluorine atom, a C 1 -C 6 fluoroalkyl, optionally comprising one or more oxygen atom.

8. The process of claim 7 , wherein monomer (A) is selected from the group of the fluorovinylethers of formula CF 2 ═CF—O—(CF 2 ) m —SO 2 F, wherein m is an integer between 1 and 6, and/or monomer (B) is selected from:
C 3 -C 8 fluoroolefins;
chloro- and/or bromo- and/or iodo-C 2 -C 6 fluoroolefins;
fluoroalkylvinylethers of formula CF 2 ═CFOR f1 wherein R f1 is a C 1 -C 6 fluoroalkyl;
fluoro-oxyalkyl- vinylethers of formula CF 2 ═CFOR O1 , wherein R O1 is a C 1 -C 12 fluorooxyalkyl having one or more ether groups.

9. The process of claim 8 , wherein monomer (A) is CF 2 ═CFOCF 2 CF 2 —SO 2 F (perfluoro-5-sulfonylfluoride-3-oxa-1-pentene) and/or monomer (B) is tetrafluoroethylene.

10. The process of claim 1 , wherein the step of reacting the substrate (I) with hydrogen (H 2 ) in the presence of a catalyst (III) is carried out in a solvent system comprising water.

11. Use of a catalyst (III) comprising transition metal particles having particle size below 50 nm supported on a material comprising at least one fluorinated polymer (P), wherein polymer (P) bears —SO 2 X functional groups, X being selected from X′ and OM, X′ being selected from the group consisting of F, Cl, Br, and I; and M being selected from the group consisting of H, an alkaline metal and NH 4 , in the one-pot hydrogenation and acid-catalysed isomerisation or dehydration of a substrate (I) containing at least a C═C or C═O moiety to obtain a product (II), wherein said process comprises reacting the substrate with hydrogen (H 2 ) in the presence of catalyst (III).

12. A solid composition comprising transition metal particles having particle size below 50 nm supported on a material comprising at least one fluorinated polymer (P), wherein polymer (P) bears —SO 2 X functional groups, X being selected from X′ and OM, X′ being selected from the group consisting of F, Cl, Br, and I; and M being selected from the group consisting of H, an alkaline metal and NH 4 , and (P) comprises recurring units derived from tetrafluoroethylene (TFE) and a linear Sulfonyl Fluoride Vinyl Ether (SFVE).

13. The solid composition according to claim 12 , wherein the transition metal particles have a particle size below 10 nm.

14. The solid composition according to claim 12 , wherein the metal particles on the support (P) comprise at least one metal, in non-charged or ionic form, selected from ruthenium, rhodium, platinum, palladium, copper, nickel, iridium, cobalt, osmium, rhenium, iron, and combinations thereof.

15. The solid composition according to claim 12 , wherein the polymer (P) has an equivalent weight of 500 g/eq or higher in grams of fluorinated polymer per mole of —SO 3 H functional groups.

16. The solid composition according to claim 14 , wherein the metal particles on the support (P) consist of at least one metal, in non-charged or ionic form, selected from ruthenium, platinum, palladium and rhodium.

17. The solid composition according to claim 15 , wherein the polymer (P) has an equivalent weight of 380 g/eq or higher in grams of fluorinated polymer per mole of —SO 3 H functional groups.

18. The process according to claim 7 , wherein monomer (A) is selected from:
sulfonyl halide fluoroolefins of formula: CF 2 ═CF(CF 2 ) p SO 2 X′ wherein p is equal to 2 or 3 and X′ is F;
sulfonyl halide fluorovinylethers of formula: CF 2 ═CF—O—(CF 2 ) m SO 2 X′ wherein m equals 2 and X′ is F;
sulfonyl halide fluoroalkoxyvinyl ethers of formula: CF 2 ═CF—(OCF 2 CF(R F1 )) w —O—CF 2 (CF(R F2 )) y SO 2 X′ where

Assignees

• Solvay Specialty Polymers It

Inventors

• Oldani Claudio
• Merlo Luca
• Barbaro Pierluigi
• Moreno-Marrodan Carmen
• Liguori Francesca

Classifications

• B01J2231/643

  of R2C=O or R2C=NR (R= C, H) · CPC title

• C07C29/175 Primary

  with simultaneous reduction of an oxo group · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• B01J31/06

  containing polymers {(organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691)} · CPC title

• B01J31/28

  of the platinum group metals, iron group metals or copper · CPC title