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

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 comprises the use of acetone cyanohydrin as a raw material, said 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 means of a reaction or series of reactions involving the biomass.

1 . A methyl methacrylate comprising from 0.2×10 −10 % to 1.2×10 −10 % by mass of  14 C relative to the total mass of carbon according to standard ASTM D6866. 
     
     
         2 . A monomer composition containing methyl methacrylate as defined in  claim 1 , and at least one polymerizable comonomer. 
     
     
         3 . The composition as claimed in  claim 2 , wherein the polymerizable comonomer(s) is (are) chosen from vinyl, vinylidene, diene and olefin monomers. 
     
     
         4 . A polymer composition comprising at least one polymer polymerized from the methyl methacrylate as defined in  claim 1 . 
     
     
         5 . The polymer composition of  claim 4 , wherein said polymer is a homopolymer or copolymer. 
     
     
         6 . The polymer composition of  claim 5 , wherein said polymer is a copolymer wherein said polymer composition has a random, block or alternating structure, or a core-shell structure. 
     
     
         7 . The polymer composition of  claim 6  wherein said copolymer is a block copolymer in which one of the blocks results from the polymerization of said methyl methacrylate. 
     
     
         8 . (canceled) 
     
     
         9 . The polymer composition as claimed in  claim 5 , comprising:
 as a matrix polymer comprising at least one said methyl methacrylate homopolymer and/or at least one said copolymer; and   a polymer additive chosen from block copolymers of said polymer composition selected from the group consisting of the block copolymers methyl (meth)acrylate-styrene, butyl (meth)acrylate-styrene, styrene-butadiene-methyl (meth)acrylate, and methyl (meth)acrylate-butyl acrylate-methyl (meth)acrylate, and polymers having a core-shell structure of said polymer composition.   
     
     
         10 . The polymer composition as claimed in  claim 9 , wherein it said composition further comprises at least one additive selected from the groups consisting of thermal stabilizers; lubricants; flame retardants; organic or inorganic pigments; anti-UV agents; antioxidants; antistatic agents; mattifying agents, inorganic fillers and organic fillers. 
     
     
         11 . The polymer composition as claimed in  claim 9 , wherein said composition is in the form of a powder, of granules or pellets. 
     
     
         12 . The polymer composition of  claim 4 , in the form of sheets, cast sheets, films, layers, fibers or tubes. 
     
     
         13 . The polymer composition of  claim 4  in the form of a multilayer structure, wherein said multilayer structure comprises at least one layer obtained from said polymer composition. 
     
     
         14 . The polymer composition of  claim 4  in the form of an extrudable resin, comprising:
 a polymer matrix comprising said polymer composition; and 
 highly crosslinked polymer particles. 
 
     
     
         15 . The polymer composition of  claim 4  in the form of a acrylic emulsion or resin. 
     
     
         16 . The polymer composition of  claim 4  comprising a manufactured article selected from the group consisting of articles for the car industry, household articles, office articles, signs and displays, transport articles, building articles, lighting articles, and bathroom articles. 
     
     
         17 . The polymer composition of  claim 16  wherein said article is obtained by extrusion, coextrusion, hot pressing or multi-injection molding. 
     
     
         18 . A method for the manufacture methyl methacrylate as defined in  claim 1 , comprising the steps of
 a) condensing of hydrocyanic acid with acetone to form acetone cyanohydrin, and,   b) introducing methanol to form methyl methacrylate,   characterized in that at least one from acetone, hydrocyanic acid and methanol was obtained by a reaction or a succession of reactions starting from biomass.   
     
     
         19 . The method as claimed in  claim 18 , 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, from which the acetone was separated by distillation or by membrane separation or by separation on silicalite, or other means of separation. 
     
     
         20 . The method as claimed in  claim 18 , wherein the acetone is obtained by hydrothermal liquefaction at 573 K of sewage treatment sludge so as to obtain black water containing hydrocarbons, followed by catalytic cracking of said black water in a steam atmosphere on a catalyst based on zirconia or zirconia/alumina supported on iron oxide, and then separation of the acetone, by distillation, or by membrane separation or separation on silicalite, or other means of separation. 
     
     
         21 . The method as claimed in  claim 18 , wherein the acetone is obtained by catalytic conversion of palm oil residues on a catalyst of zirconia or zirconia/alumina supported on iron oxide, and then separation of the acetone, by distillation, or by membrane separation or separation on silicalite, or other means of separation. 
     
     
         22 . The method as claimed in  claim 18 , wherein the hydrocyanic acid is obtained by ammoxidation of methane, the methane having been 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, the carbon dioxide having been 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. 
     
     
         23 . The method as claimed in  claim 18 , wherein the hydrocyanic acid is obtained by ammoxidation of methanol, the methanol having been obtained by pyrolysis of wood or by gasification of any materials of animal and/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. 
     
     
         24 . The method as claimed in  claim 18 , 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. 
     
     
         25 . The method as claimed in  claim 23 , wherein the syngas for preparing the methanol is obtained from the residual liquor from the manufacture and bleaching of cellulosic pulps. 
     
     
         26 . The method as claimed in  claim 18 , 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 cyanohydrins 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.   
     
     
         27 . The method as claimed in  claim 18 , 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.   
     
     
         28 . (canceled) 
     
     
         29 . The method as claimed in  claim 24 , wherein the syngas for preparing the methanol is obtained from the residual liquor from the manufacture and bleaching of cellulosic pulps.