Bioplastics, monomers thereof, and processes for the preparation thereof from agricultural feedstocks

Abstract

The present invention relates generally to polymers and monomers derived from agricultural feedstocks, and more particularly to methods for the production of monomers from renewable agricultural resources such as feedstocks, for example canola, flax and tallow, and polymers, in particular polyurethanes produced from monomers derived from such feedstocks. The present invention also relates to novel processes for the production of short-chain alcohols, as well as hydroxyl wax esters, from renewable feedstocks. An improved apparatus for carrying out ozonolysis reactions is also disclosed.

1 .- 17 . (canceled) 
   
   
       18 . A method for producing a polyurethane polymer comprising:
 (i) preparing a polyol from a renewable feedstock comprising one or more unsaturated fatty acid triacylglycerols by a method that comprises the steps of:
 (a) ozonolysis of two or more double bonds in the unsaturated fatty acids of the one or more triacylglvcerols of the feedstock under conditions effective to afford two or more corresponding ozonide functionalities; 
 (b) subjecting the products of step (a) to reductive hydrogenation under conditions effective to product at least corresponding polyol. 
   wherein said at least one polyol comprise at least one triacylglycerol containing at least two primary hydroxyl groups and said method further comprises the production of one or more short chain alcohols as a by-product, and said one or more short chain alcohols is separated from the one or more polyols; and   (ii) reacting the polyol resulting from steps (a) and (b) with a suitable isocyanate to afford said polyurethane polymer, with the proviso that where said polyol is a flax-based polyol, said polyurethane polymer is not a foam.   
   
   
       19 . The method of  claim 18 , wherein the polyurethane polymer comprises an elastomer, a resin, a plastic, a flexible slab, or a foam. 
   
   
       20 . The method of  claim 19 , wherein said foam is rigid or flexible. 
   
   
       21 . The method of  claim 20 , wherein said foam is a flexible moulded foam. 
   
   
       22 . The method of  claim 19 , wherein said resin is a rigid set resin. 
   
   
       23 . The method of  claim 19 , wherein said plastic comprises a plastic sheet. 
   
   
       24 . A polyurethane polymer prepared by the method of  claim 18 . 
   
   
       25 .- 26 . (canceled) 
   
   
       27 . A method for the production of a hydroxyl wax ester from a renewable feedstock comprising one or more unsaturated fatty acid triacylglycerols, wherein the method comprises the steps of:
 a. ozonolysis of the double bonds in the unsaturated fatty acids of the one or more triacylglycerols of the feedstock;   b. subjecting the products of step (a) to reductive hydrogenation to produce at least one of a corresponding mono-ol, at least one of a corresponding polyol, or a mixture thereof, in the presence of a short chain alcohol;   wherein the at least one mono-ol, the at least one polyol, or the mixture thereof, comprises a triacylglycerol containing at least one terminal hydroxyl group, and wherein the reaction conditions are sufficient to afford transesterification between the triacylglycerol containing at least one terminal hydroxyl group and the short chain alcohol, thereby affording said hydroxyl wax ester.   
   
   
       28 . The method of  claim 27 , wherein said short chain alcohol contains 9 carbons. 
   
   
       29 . The method of  claim 27 , wherein said short chain alcohol is produced as a by-product in the preparation of said at least one mono-ol, said at least one polyol, or said mixture thereof, from said feedstock. 
   
   
       30 . The method of  claim 27 , wherein said short chain alcohol is used as a solvent in the hydrogenation reaction. 
   
   
       31 . An improved apparatus for carrying out ozonolysis reactions, said improvement comprising:
 a longitudinally disposed agitator operatively connected to a motor, said longitudinally disposed agitator comprising a plurality of pitched blades,   wherein said longitudinally disposed agitator extends downwardly into a reaction vessel having an upper and a lower end,   said reaction vessel comprising an ozone inlet channel disposed at the lower end and extending across the diameter of said reaction vessel,   said ozone inlet channel having two apertures for ozone input at opposing ends thereof   and a plurality of pores for release of ozone into said reaction vessel.   
   
   
       32 . The apparatus as claimed in  claim 31 , wherein said plurality of pitched blades are oriented such as to direct the contents of said reaction vessel downward toward said ozone inlet channel. 
   
   
       33 . The apparatus as claimed in  claim 32 , wherein the pitched blades extend from said longitudinally disposed agitator at an angle of from about 30 degrees to about 60 degrees relative to the longitudinal axis of the longitudinally disposed agitator. 
   
   
       34 . The apparatus as claimed in  claim 31 , wherein the pitched blades are trapezoidal in shape. 
   
   
       35 . The apparatus as claimed in  claim 31 , wherein the pitched blades contain a plurality of holes therein. 
   
   
       36 . A method for the production of a hydroxyl wax ester from a renewable feedstock comprising one or more unsaturated fatty acid triacylglycerols, wherein the method comprises the steps of:
 a. ozonolysis of the double bonds in the unsaturated fatty acids of the one or more triacylglycerols of the feedstock;   b. subjecting the products of step (a) to reductive hydrogenation to produce at least one corresponding mono-ol, at least one corresponding polyol, or a mixture thereof, wherein the at least one mono-ol, the at least one polyol, or the mixture thereof comprises a triacylglycerol containing at least one terminal hydroxyl group; and   c. subjecting the products of step (b) to transesterification with a short chain alcohol to produce said hydroxyl wax ester.   
   
   
       37 . The method as claimed in  claim 36 , wherein the renewable feedstock is canola oil, soybean oil, flax oil or palm oil. 
   
   
       38 . The method as claimed in  claim 36 , wherein the short chain alcohol is nonanol, hexanol, propanol, or 1,3-propanediol. 
   
   
       39 . The method as claimed in  claim 36 , wherein the short chain alcohol is nonanol and wherein the hydroxyl wax ester is nonyl-9-hydroxynonanoate. 
   
   
       40 . A compound having the formula: 
     
       
         
         
             
             
         
       
     
     wherein said compound is isolated in substantially pure form. 
   
   
       41 . The method of  claim 18 , wherein said separation of said one or more short chain alcohol by-products from the one or more polyols is carried out prior to isolating the one or more polyols from the reaction mixture of step (b). 
   
   
       42 . The method of  claim 18 , wherein said separation of said one or more short chain alcohol by-products from the one or more polyols comprises the use of wiped-blade molecular distillation.