Biomass-derived polymers and copolymers incorporating monolignols and their derivatives

Patent metadata

Field	Value
Publication number	US-10941104-B2
Application number	US-201615767309-A
Country	US
Kind code	B2
Filing date	Oct 14, 2016
Priority date	Oct 16, 2015
Publication date	Mar 9, 2021
Grant date	Mar 9, 2021

Abstract

The invention includes methods and materials for forming and manipulating aromatic-based polymers and copolymers using biomass compounds as starting materials. Embodiments of the invention can be used in processes designed to replace those used in the petro-chemical industry. Typical embodiments of the invention include methods and materials for forming and/or modifying compounds including dicarboxylic acid ester dimers, benzoxazines and dicarboxylic acid ether dimers. Embodiments of the invention further provide methods and materials for utilizing these compounds to form commercially desirable polymers having structures and physical properties akin to those found in polymers formed from petroleum products.

First claim

The invention claimed is:

1. A method of forming a poly(ester-amide) comprising the steps of:
(a) disposing an aromatic aldehyde selected from vanillin, 4-hydroxybenzaldehyde and 4-hydroxy-3,5-dimethoxybenzaldehyde in a reaction vessel;
(b) disposing a t-butyl malonate in the reaction vessel;
(c) reacting the aromatic aldehyde with the t-butyl malonate in a Doebner modification of a Knoevenagel condensation reaction so as to generate an ester compound;
(d) reacting the ester compound of (c) with a deprotonating agent in situ so as to generate a salt of the ester compound;
(e) reacting the salt of the ester compound of (d) with a diacid chloride or bromide in a salt metathesis reaction so as to generate an ester of a monolignol dimer; and
(f) converting the ester of a monolignol dimer of (e) into a carboxylic acid via a reaction with trifluoroacetic acid (TFA);
a so that a dicarboxylic acid ester dimer is formed;
converting the dicarboxylic acid ester dimer to a diacid chloride via a reaction with thionyl chloride;
removing excess thionyl chloride under vacuum;
dissolving the diacid chloride ester dimer in a halogenated organic solvent; and
combining the halogenated organic solvent solution with an aqueous basic solution comprising a diamine in a condensation polymerization reaction so as to form a poly(ester-amide).

2. The method of claim 1 , wherein the diamine is:

wherein n=1, 2, 3, 4 or 5.

3. The method of claim 1 , wherein the poly(ester-amide) is formed via an interfacial polymerization reaction.

4. The method of claim 1 , further comprising reacting the poly(ester-amide) in:
an atom-transfer radical-polymerization (ATRP) reaction; or
a reversible addition-fragment chain transfer (RAFT) reaction.

5. The method of claim 1 , further comprising concentrating the poly(ester-amide) via a precipitation process.

6. The method of claim 5 , further comprising:
dissolving the poly(ester-amide) precipitate in a solution comprising toluene combined with itaconic acid or Tulipalin A;
adding azobisisobutyronitrile (AIBN) to the solution;
degassing the solution;
heating the solution; and
purifying the resulting copolymer via precipitation.

7. The method of claim 1 , wherein the poly(ester-amide) exhibits:
an onset of thermal decomposition (T d5 ) between 220° C. and 260° C.; and/or
a glass transition temperature (T g ) between 64.7 and 138.2° C.

8. A method of forming a poly(ester-amide) comprising the steps of:
(a) reacting an aromatic aldehyde with a malonic ester in a Doebner modification of a Knoevenagel condensation reaction so as to generate an ester compound;
(b) reacting the ester compound of (a) with a deprotonating agent in situ so as to generate a salt of the ester compound;
(c) reacting the salt of the ester compound of (b) with a diacid chloride or bromide in a salt metathesis reaction so as to generate an ester of a monolignol dimer; and
(d) converting the ester of a monolignol dimer of (c) into a carboxylic acid via a reaction with trifluoroacetic acid (TFA);
so that a dicarboxylic acid ester dimer is formed;
converting the dicarboxylic acid ester dimer to a diacid chloride via a reaction with thionyl chloride;
removing excess thionyl chloride under vacuum;
dissolving the diacid chloride ester dimer in a halogenated organic solvent; and
combining the halogenated organic solvent solution with an aqueous basic solution comprising a diamine in a condensation polymerization reaction so as to form a poly(ester-amide).

Assignees

• Univ California

Inventors

• Upton Brianna Marie
• Kasko Andrea

Classifications

• C08G69/40 Primary

  Polyamides containing oxygen in the form of ether groups (C08G69/12, C08G69/32 take precedence) · CPC title

• C07C67/28

  by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group · CPC title

• C07C67/31

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C67/343

  by increase in the number of carbon atoms · CPC title

• C07C67/14

  from carboxylic acid halides · CPC title