Biomass-derived methyl methacrylate and corresponding manufacturing method, uses and polymers

Patent metadata

Field	Value
Publication number	US-9938225-B2
Application number	US-201414175291-A
Country	US
Kind code	B2
Filing date	Feb 7, 2014
Priority date	May 30, 2008
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

The invention relates to methyl methacrylate characterized in that at least one portion of the carbons thereof is biologically sourced and, more specifically, in that it contains between 0.2×10 −10 and 1.2×10 −10 wt.-% of 14 C in relation to total carbon weight according to the ASTM D6866 standard. The preparation method uses acetone cyanohydrin as a raw material, the acetone cyanohydrin being obtained by condensing cyanohydric acid on acetone, and the methyl methacrylate is prepared using a process involving the addition of methanol. According to the invention, at least one from among the acetone, cyanohydric acid and methanol is obtained by a reaction or series of reactions involving the biomass.

First claim

What is claimed:

1. A method for the manufacture methyl methacrylate, comprising:
a) condensing hydrocyanic acid with acetone to form acetone cyanohydrin, and
b) introducing methanol to form methyl methacrylate,
wherein the acetone, hydrocyanic acid and methanol are obtained by a reaction or a succession of reactions starting from biomass, and wherein the methyl methacrylate comprises 1.2×10 −10 % by mass of 14 C relative to the total mass of carbon according to standard ASTM D6866,
wherein the acetone is obtained by acetobutylic fermentation of C 6 and C 5 sugars, resulting in an acetone-butanol mixture, where appropriate with ethanol, and separating the acetone by distillation or by membrane separation or by separation on silicalite, or other means of separation,
wherein the hydrocyanic acid is obtained by ammoxidation of methane, wherein the methane is obtained by fermentation, in the absence of oxygen, of animal and/or plant organic materials, resulting in a biogas mainly composed of methane and carbon dioxide, wherein the carbon dioxide is removed by washing the biogas with a basic aqueous solution of sodium hydroxide, potassium hydroxide or amine, or else with water under pressure, or by absorption in a solvent, and
wherein the methanol is obtained by pyrolysis of wood or by gasification of any materials of animal or plant origin, resulting in a syngas mainly composed of carbon monoxide and hydrogen which is reacted with water, or by fermentation starting from plant crops giving fermentable products and therefore alcohol.

2. The method as claimed in claim 1 , wherein:
in a first step, hydrocyanic acid is condensed with acetone via a basic catalysis in order to obtain acetone cyanohydrin;
in a second step; the acetone cyanohydrin is reacted in a concentrated sulfuric medium in order to obtain α-oxyisobutyramide monosulfate, which is converted to sulfuric methacrylamide under the action of the heat of the reaction which is highly exothermic;
in a third step, the methacrylamide is hydrolyzed and esterified with methanol so as to form methyl methacrylate and ammonium hydrogen sulfate, and the desired starting material is recovered.

3. The method as claimed in claim 1 , wherein:
in a first step, hydrocyanic acid is condensed with acetone via a basic catalysis in order to obtain acetone cyanohydrin;
in a second step, the acetone cyanohydrin is reacted with methanol in order to obtain methyl hydroxymethacrylate;
in a third step, the methyl hydroxymethacrylate is dehydrated so as to recover the desired starting material.

4. The method as claimed in claim 1 , wherein the syngas for preparing the methanol is obtained from the residual liquor from the manufacture and bleaching of cellulosic pulps.

Assignees

• Arkema France

Inventors

• Dubois Jean-Luc
• Croizy Jean Francois

Classifications

• Y10T428/139

  Open-ended, self-supporting conduit, cylinder, or tube-type article · CPC title

• B32B27/08

  of synthetic resin · CPC title

• B32B2605/08

  Cars · CPC title

• C07C67/22 Primary

  from nitriles · CPC title

• Y10T428/2998

  including synthetic resin or polymer · CPC title