Methods of making and using lignin derivatives

Patent metadata

Field	Value
Publication number	US-2018037598-A1
Application number	US-201615552227-A
Country	US
Kind code	A1
Filing date	Feb 18, 2016
Priority date	Feb 18, 2015
Publication date	Feb 8, 2018
Grant date	—

Abstract

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

First claim

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

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 contacting is performed in an aqueous solution.

6 . The process of claim 5 , wherein the aqueous solution has a pH of less than about 7.

7 . The process of claim 6 , wherein the aqueous solution has a pH of about 4 to about 5.

8 . 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.

9 . The process of claim 8 , wherein forming the diazonium compound from the corresponding amine precursor comprises contacting the amine precursor with nitrous acid.

10 . 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.

11 . The process of claim 10 , 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 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.

12 . The process of claim 10 , 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

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

• C04B24/18

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

• C07G1/00 Primary

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

• C07C245/20

  Diazonium compounds · CPC title