Methods of making and using lignin derivatives

Patent metadata

Field	Value
Publication number	US-10533031-B2
Application number	US-201615552227-A
Country	US
Kind code	B2
Filing date	Feb 18, 2016
Priority date	Feb 18, 2015
Publication date	Jan 14, 2020
Grant date	Jan 14, 2020

Abstract

Materials and methods for preparing reactive lignin and for preparing a bio-based adhesive are described herein.

First claim

What is claimed is:

1. A process for preparing a lignin derivative, the process comprising:
contacting a lignin with a diazonium compound of Formula I:

wherein the contacting is performed in an aqueous solution having a pH of less than about 7; and wherein:
Ar 1 is a 6-10 membered aryl substituted by 1, 2, 3, or 4 independently selected R a groups;
L 1 is selected from the group consisting of —C 1-6 alkylene-, —Y—,—Y—C 1-6 alkylene-, —Y—C 1-6 alkylene-Y—, and —C 1-4 alkylene-Y—C 1-4 alkylene-;
R 1 is selected from the group consisting of —O—S(O) 2 OH and —O—S(O) 2 OR a
L 2 is selected from the group consisting of a bond, —C1-6 alkylene-, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups;
each Y is independently selected from the group consisting of O, S, S(O), S(O) 2 , C(O), C(O)NR c , NR c C(O), S(O) 2 NR c , NR c S(O) 2 , and NR c ;
each R a is independently selected from the group consisting of C 1-6 alkyl, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups;

each R b is independently selected from the group consisting of OH, NO 2 , CN, SH, halo, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-4 haloalkyl, and C 1-6 alkoxy;
each R c is independently selected from the group consisting of H and C 1-3 alkyl.

2. The process of claim 1 , wherein the diazonium compound of Formula I is a compound of formula Ia:

wherein:
L 1 is selected from the group consisting of —C 1-6 alkylene-, —Y—, —Y—C 1-6 alkylene-, —Y—C 1-6 alkylene-Y—, and —C 1-4 alkylene-Y—C 1-4 alkylene-;
R 1 is selected from the group consisting of —O—S(O) 2 OH and —O—S(O) 2 OR a
L 2 is selected from the group consisting of a bond, —C 1-6 alkylene-, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups;
each Y is independently selected from the group consisting of O, S, S(O), S(O) 2 , C(O), C(O)NR c , NR c C(O), S(O) 2 NR c , NR c S(O) 2 , and NR c ;
each R a is independently selected from the group consisting of C 1-6 alkyl, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups;

each R b is independently selected from the group consisting of OH, NO 2 , CN, SH, halo, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-4 haloalkyl, and C 1-6 alkoxy; and
each R c is independently selected from the group consisting of H and C 1-3 alkyl.

3. The process of claim 1 , wherein the diazonium compound of Formula I is a compound of formula Ib:

wherein:
L 1 is selected from the group consisting of —C 1-6 alkylene-, —Y—C 1-6 alkylene-,—Y—C 1-6 alkylene-Y—, and —C 1-4 alkylene-Y—C 1-4 alkylene-;
each Y is independently selected from the group consisting of O, S, S(O), S(O) 2 , C(O), C(O)NR c , NR c C(O), S(O) 2 NR c , NR c S(O) 2 , and NR c ;
each R c is independently selected from the group consisting of H and C 1-3 alkyl.

4. The process of claim 1 , wherein the diazonium compound of Formula I is a compound of formula Ic:

5. The process of claim 1 , wherein the aqueous solution has a pH of about 4 to about 5.

6. The process of claim 1 , further comprising forming the diazonium compound from the corresponding amine precursor prior to contacting the lignin with the diazonium compound.

7. The process of claim 6 , wherein forming the diazonium compound from the corresponding amine precursor comprises contacting the amine precursor with nitrous acid.

8. The process of claim 1 , further comprising contacting the lignin derivative with a basic aqueous solution to form an alkene lignin derivative of Formula II:

wherein:
Ar 1 is a 6-10 membered aryl substituted by 1, 2, 3, or 4 independently selected R a groups;

L 1 is selected from the group consisting of —C 1-6 alkylene-, —Y—, —Y—C 1-6 alkylene-, —Y—C 1-6 alkylene-Y—, and —C 1-4 alkylene-Y—C 1-4 alkylene-;
L 2 is selected from the group consisting of a bond, —C 1-6 alkylene-, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups;
each Y is independently selected from the group consisting of O, S, S(O), S(O) 2 , C(O), C(O)NR c , NR c C(O), S(O) 2 NR c , NR c S(O) 2 , and NR c ;
each R a is independently selected from the group consisting of C 1-6 alkyl, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups

each R b is independently selected from the group consisting of OH, NO 2 , CN, SH, halo, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-4 haloalkyl, and C 1-6 alkoxy; and
each R c is independently selected from the group consisting of H and C 1-3 alkyl; and
the wavy line indicates the point of attachment to a phenyl group of the lignin.

9. The process of claim 8 , wherein the alkene lignin derivative of Formula II is a compound of formula IIa:

wherein:
L 1 is selected from the group consisting of —C 1-6 alkylene-, —Y—, —Y—C 1-6 alkylene-, —Y—C 1-6 alkylene-Y—, and —C 1-4 alkylene-Y—C 1-4 alkylene-;
L 2 is selected from the group consisting of a bond, —C 1-6 alkylene-, 6-10 membered aryl, 5-10 membered heteroaryl, wherein the 6-10 membered aryl, 5-10 membered heteroaryl is optionally substituted by 1, 2, 3, or 4 independently selected R b groups;
each Y is independently selected from the group consisting of O, S, S(O), S(O) 2 , C(O), C(O)NR c , NR c (O), S(O) 2 NR c , NR c S(O) 2 , and NR c ;
each R b is independently selected from the group consisting of OH, NO 2 , CN, SH, halo, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-4 haloalkyl, and C 1-6 alkoxy; and

each R c is independently selected from the group consisting of H and C 1-3 alkyl; and
the wavy line indicates the point of attachment to a phenyl group of the lignin.

10. The process of claim 8 , wherein the alkene lignin derivative of Formula II is a compound of formula IIb):

wherein:
L 1 is selected from the group consisting of —C 1-6 alkylene -, —Y—, —Y—C 1-6 alkylene-,—Y—C 1-6 alkylene-Y—, and —C 1-4 alkylene-Y—C 1-4 alkylene-;
each Y is independently selected from the group consisting of O, S, S(O), S(O) 2 , C(O), C(O)NR c , NR c C(O), S(O) 2 NR c , NR c S(O) 2 , and NR c ;
each R c is independently selected from the group consisting of H and C 1-3 alkyl; and
the wavy line indicates the point of attachment to a phenyl group of th

Assignees

• Nutech Ventures

Inventors

• Helle Mark Alan
• Cheung Chin Li

Classifications

• C07C309/13

  containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton · CPC title

• C09K8/20

  Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives · CPC title

• C07G1/00 Primary

  Low-molecular-weight derivatives of lignin (high-molecular-weight derivatives of lignin {C08H6/00}) · CPC title

• C04B24/18

  Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye · CPC title

• C07C245/20

  Diazonium compounds · CPC title