Abstract:
Polymeric materials are recycled by transformation to useful chemicals by oxidization in the liquid phase using acetic acid as a solvent and a metal bromide catalyst.

Description:
This application is a 371 of PCT/US01/23320 filed Jul. 25, 2001 which claims benefit of application Ser. No. 60/221,156 filed Jul. 27, 2000. 
    
    
     FIELD OF INVENTION 
     The invention relates to a process for the production of useful chemicals from polymers, including salvage or waste polymeric material, comprising contacting the polymeric material with an oxidant in the presence of a metal bromide catalyst. The chemicals produced from the oxidation process can be utilized as monomers, solvents, and chemical intermediates. 
     BACKGROUND OF THE INVENTION 
     Every year over 140 billion pounds of polymeric materials are produced worldwide. When polymeric materials reach a post-consumer or post-industrial stage, disposal of the polymeric materials can become a political and social issue in terms of allocation of landfill space and sensitivities to incineration. Recycling polymeric materials is an alternative option to disposal of this material is becoming an increasing problem, with landfill space decreasing and incineration prohibited by environmental regulations. Recyclingdisposal. However, recycling of polymeric materials is difficult due to the commingling of polymers with other materials and the expense expense of chemical reactions such as depolymerization, necessary to produce useful materials from waste polymers. 
     In view of the foregoing, there is a need for efficient processes to convert polymeric materials without the need to cleanly separate the polymeric materials from other types of material, and that will produce good yields of easily separated, useful products. 
     Metal bromide catalysts have been used to oxidize many types of nonpolymeric compounds, especially substituted alkylbenzenes to various products including the oxidation of alkyl to aldehydes, alkyl to alcohols, alkyl to acids, alcohol to acid, and aldehydes to acids (W. Partenheimer,  Catalysis Today , 23(2), 69-158, (1995)). In U.S. Pat. No. 5,414,113 metal bromide catalysts were used as part of a processes to produce terephthalic acid from polyester, but only to oxidize impurities remaining after hydrolytic depolymerization. 
     SUMMARY OF THE INVENTION 
     The present invention is directed to a process for the oxidation of polymeric material comprising contacting the polymeric material with an oxidant in the presence of a homogenous metal-catalyst under conditions promoting oxidation of the polymeric material. 
     The present invention is also directed to a process for the oxidation of polymeric material comprising contacting the polymeric material with an oxidant in the presence of a metal bromide catalyst comprising a source of bromide and at least one metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Ag, Hf, Ru, Te, Mo, Zn and Ce. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The invention is directed to an oxidation process for the production of useful chemicals from polymeric material, including salvage or waste polymeric material, comprising contacting the polymeric material with an oxidant in the presence of a metal catalyst, preferably a metal bromide catalyst. The useful chemicals produced can be used in a wide variety of industrial processes; such as but not limited to use as monomers, solvents, and chemical intermediates. 
     The degree of oxidation in the process of the present invention can be easily controlled by many variables such as temperature, pressure, catalyst concentration, selection of catalyst, and selection of solvent. Control over degrees of oxidation in similar processes is described in the review article by W. Partenheimer,  Catalysis Today , vol. 23, no. 2, 69-158, (1995), which is incorporated by reference herein. Adjusting the degree of oxidation will allow the skilled person to select the useful chemicals that are produced. If a mild degree of oxidation is chosen, the polymer will become partially oxidized along the polymeric chain producing partially oxidized polymers, typically containing peroxide, alcohol, ketone or aldehyde functional groups which may improve polymer properties. Increasing the degree of oxidation will oxidize the polymeric chain into monomeric units containing carboxylic acids, alcohols, ketones or aldehydes and other compounds with oxygen containing functionalities. Further oxidation will result in monomer units containing largely carboxylic acids. A high degree of oxidation will produce carbon oxides (carbon monoxide and carbon dioxide). 
     The salvaged or waste polymeric material of the instant invention is herein defined as any polymer that contains a carbon backbone. This includes, but is not limited to, aminoresin, chloropolymer, epoxyresin, fluoropolymer, polyacetylene, polyacrylic, polyamic acid, polyamide, polyamine, polyanhydride, polyazomethine, polybenzimidazole, polybenzoxazole, polycarbodiimide, polycarbonate, polycyanurate, polyester, polyether, polyimide, polyisocyanurate, polyketone, polyolefin, polyphenyl, polyquinoxaline, polystyrene, polysulfonamide, polysulfone, polythioester, polythioether, polyurea, polyurethane, and polyvinyl polymers. Natural protein based and cellulose based polymers are generally not suitable to the processes of the instant invention as they tend to oxidize completely to carbon dioxide and water. 
     The polymeric materials can be addition or condensation polymers, thermoplastic or thermoset polymers, homopolymers, copolymer or terpolymers, or single polymers or blends thereof. The polymeric material may also be linear, branched or crosslinked. Surface modifications may also be present. 
     Preferably, the polymeric material is comprised of polyamide, polyester, polyolefin, polycarbonate, or copolymers or blends thereof. Most preferably, the polymeric material is polyester, polyolefin, polyvinylchloride, polycarbonate, or copolymers or blends thereof. 
     The salvaged or waste polymeric material of the instant invention may be from any source, such as but not limited to wastes from the production of plastics materials, commercial packaging wastes of plastics materials, residues, mixed and pure portions from the plastics-processing industry, waste manufactured or commercial articles, and materials generated from recycling programs. The waste polymeric materials can be in any suitable form including shaped parts, laminates, composite materials, foils or sheets, or synthetic fibers, but may be used in any suitable form. It is preferred that the material be in the form of particles such as pellets, granules, powder or flakes derived from comminution or other mechanical breakdown of manufactured articles or waste material. 
     Although it is preferred that major impurities such as metal be separated from the salvaged or waste material before use, it may contain impurities such as pigments, glass fibers, fillers such as titanium oxide or zinc oxide, flame-proofing agents, pigment-containing printing inks, adhesives, and paper or other cellulose material. The polymeric material does not have to be cleansed of dirt, food waste, or other contamination present. A particular advantage of the instant invention is that the oxidation will effectively incinerate impurities such as food waste, paper, adhesives, and other organic contaminates often found on waste polymeric products. Inorganic contaminants and solid impurities remaining after oxidation can be easily separated from the final product, usually by filtration. 
     Any soluble, homogenous metal autoxidation catalyst can be used for the process of the invention. In general, these metal catalysts are chosen from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Ag, Hf, Ru, Te, Mo, Zn and Ce. 
     Each of the metal catalyst components can be provided in any of their known ionic or combined forms. Preferably the metal or metals are in a form that is soluble in the reaction solvent. Examples of suitable metal catalyst forms include, but are not limited to, metal carbonate, metal acetate, metal acetate tetrahydrate, and metal bromide. Preferably metal acetate tetrahydrates are used. Other substances can be added to the metal catalyst such as bromide and NHPI (N-hydroxyphthalimide). 
     A preferred catalyst for the process of the instant invention is comprised of a source of bromine and at least one metal selected from the group consisting of Co, Mn, Ce, V and Ni, and optionally containing Zr, Hf, Ce, and Ni. More preferably the metal bromide catalyst contains Co or V. The addition of bromide generally increases the activity and selectivity of the catalyst used. 
     Metal bromide catalysts employed in the process of this invention comprise a soluble transition metal compound and soluble bromine-containing compound, as described in Partenheimer, supra. One metal or a combination of two or more metals may be present. Many such combinations are known and may be used in the processes of the instant invention. These metal bromide catalysts and their preparation are described further in Partenheimer, supra, in particular 9 pages 89-95. Preferably the metal is cobalt and/or manganese, optionally containing zirconium. More preferably, the catalyst is comprised of Co/Mn/Zr/Br in the molar ratios of 1.0/1.0/0.1/2.0. The amount of catalyst in the reaction mixture can be 59/55/203/4 ppm to 5900/5500/20000/390 ppm Co/Mn/Br/Zr, preferably 150/140/510/10 ppm to 2400/2200/8100/160 ppm (g of metal/g of solvent). As used herein, the molar ratio is the ratio of moles of the metals alone, not the metals as in their compound forms. 
     The source of bromide can be any compound that produces bromide ions in the reaction mixture. These compounds include, but are not limited to, hydrogen bromide, hydrobromic acid, sodium bromide, elemental bromine, benzyl bromide, and tetrabromoethane. Preferred is sodium bromide or hydrobromic acid. As used herein, the amount of bromine means the amount measured as Br. Thus, the molar ratio of bromine to total of the metals used in the catalyst is the moles of Br divided by the sum of the moles of the metal. 
     An unexpected advantage of the instant invention is the fact that the polymeric material does not have to dissolve in the solvent in order for the process to proceed. As described in Partenheimer, supra, pages 86-88, suitable solvents for use in the processes of the present invention, described above, generally have at least one component that contains a monocarboxylic acid functional group. The processes may be run in a solvent or solvent mixture that does not contain an acid group, provided that one of the reagents does contain such a group. Suitable solvents can also be aromatic acids such as benzoic acid and derivatives thereof. A preferred solvent is an aliphatic C 2 -C 6  monocarboxylic acid, such as but not limited to acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, and caproic acid and mixtures thereof. Components of said mixtures can include benzene, acetonitrile, heptane, acetic anhydride, chlorobenzene, o-dichlorobenzene, and water. Most preferred as solvent is acetic acid. Another preferred solvent is water. Acetic acid is the usual solvent for the Co/Mn/Zr/Br catalyst. 
     The oxidant in the processes of the present invention is preferably an oxygen containing gas or gas mixture, such as, but not limited to air. Oxygen by itself is also a preferred oxidant. Other oxidants such as peroxides are also suitable. 
     A vanadium or vanadium/bromide catalyst can be used with water as a solvent. The amount of vanadium in the reaction mixture can be 100 ppm to 20,000 ppm V, preferably 200 ppm to 14,000 ppm (g of metal/g of solvent). For a vanadium/bromide catalyst the vanadium/bromide in the reaction mixture can be 100/200 to 3000/30,000 ppm, preferably 200/300 to 4000/25,000 ppm. 
     The processes of the instant invention described above can be conducted in the batch, semi-continuous or continuous mode. Reactors may be a continuously stirred reactor (CSTR) or plug flow reactor. As stated above, the polymeric material does not have to be completely dissolved in the solvent, but can be slurried or agitated. Preferred temperatures are about 50° C. to about 250° C.; more preferred is about 100° C. to about 220° C. In general, increasing reaction time should increase yield. Pressure must be sufficiently high to keep the majority of the liquid in the reactor. If more than one polymeric material is present, they can be separated before the process is conducted, or the products can be separated after the reaction is complete. Separation can be performed by any means known in the art. 
     The following abbreviations are used herein: 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 BPA 
                 Bisphenol A 
               
               
                   
                 DMSO 
                 Dimethylsulfoxide 
               
               
                   
                 GC 
                 Gas chromatography 
               
               
                   
                 GC/MS 
                 Gas chromatography/mass spectroscopy 
               
               
                   
                 LC 
                 Liquid chromatography 
               
               
                   
                 NDC 
                 2,6-Naphthalenedicarboxylic acid 
               
               
                   
                 NHPI 
                 N-hydroxyphthalimide 
               
               
                   
                 NMR 
                 Nuclear magnetic resonance 
               
               
                   
                 PABA 
                 4-Acetoxybenzoic Acid 
               
               
                   
                 PBT 
                 Poly(butylene)terephthalate 
               
               
                   
                 PC 
                 Poly(bisphenol A)carbonate 
               
               
                   
                 PE 
                 Polyethylene 
               
               
                   
                 PEN 
                 Poly(ethylene)naphthenate 
               
               
                   
                 PET 
                 Poly(ethylene) terephthalate 
               
               
                   
                 PHBA 
                 p-Hydroxybenzoic Acid 
               
               
                   
                 PP 
                 Polypropylene 
               
               
                   
                 PS 
                 Polystyrene 
               
               
                   
                 PVC 
                 Polyvinylchloride 
               
               
                   
                 PVP 
                 Polyvinylpyridine 
               
               
                   
                 TA 
                 Terephthalic acid 
               
               
                   
                 THF 
                 Tetrahydrofuran 
               
               
                   
                   
               
             
          
         
       
     
     The following non-limiting Examples are meant to illustrate the invention but are not intended to limit it in any way. 
     Materials and Methods 
     About 0.2-0.5 g of polymer feedstock was placed in 5.2 g of a solution containing cobalt(II) acetate tetrahydrate, manganese(U) acetate tetrahydrate, optionally zirconium(IV) acetate, and sodium bromide in proportions shown, and 0 to 10% water in acetic acid. This was placed in an agitated glass reactor. The reactor was heated to the specified temperature under 1000 psia given pressure of air for the specified amount of time. The reactor was then cooled and its contents prepared for analysis. If solids were present, the solution was filtered before analysis. The solids were air-dried analyzed by NMR and standard elemental analysis methods. The filtrates were analyzed by GC/MS and LC. Yields, unless otherwise specified, were calculated as follows: (100×moles product)/(moles polymer repeat unit). 
     Terephthalic acid is virtually insoluble in acetic acid/water solutions at room temperature. The terephthalic acid yields from the reactions of PET and PBT, which are insoluble in the solvent used, were based on the amount of isolated solids at room temperature. The yields are estimates only since typically only 0.20 g of polymers was used initially. When co-oxidation of p-xylene with PET was performed, the solids were based on both the terephthalic acid content of the PET as well as the terephthalic acid formed from the p-xylene. The yield of the 2,6-naphthalenedicarboxylic acid formed in the reaction of PEN was determined using the same method as it is also very insoluble in acetic acid/water mixtures. 
     An estimation of the oligomer present in the solids during polyester oxidation (PET, PBT, PEN) was obtained by dissolving the isolated solids, obtained at the end of the experiment, in deuterated dimethylsulfoxide and obtaining its carbon and hydrocarbon NMR spectrum. The presence of oligomer was evidenced by the peaks at 4.5 tau units. The relative amount of oligomer in the solids was obtained from the integrated area at 4.5 tau units and that of terephthalic acid by the integrated area at 8.0 tau units. The percent oligomer in the solids was thus calculated. PET is virtually insoluble in dimethylsulfoxide. If the sample was only partially soluble in DMSO the percent oligomer is given the ‘greater than’ sign (&gt;). 
     EXAMPLES 1-12 
     
       
                 
         
             
             
         
      
     
     The results from the oxidation of three different sources of polystyrene are given in Table 1. The yields, as high as 73%, vary as a function of time and temperature. At the termination of most of the reactions there are a small amount of solids which are believed to be unreacted PS. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Oxidation of Polystyrene (PS) 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                 Initial 
                   
               
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Conc. 
                 Product Yields 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 Hr 
                 Psi 
                 Wgt % 
                 Mol % 
               
               
                   
               
             
          
           
               
                 1 
                 (1) 
                 407/379/1103/20 
                 8.0 
                 150 
                 2 
                 1000 
                 3.8 
                  benzoic acid, 7.1 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 0.0 
               
               
                 2 
                 (1) 
                 407/379/1103/20 
                 8.0 
                 180 
                 2 
                 1000 
                 3.8 
                 benzoic acid, 36 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                  benzil, 0.49 
               
               
                 3 
                 (1) 
                 407/379/1103/20 
                 8.0 
                 220 
                 2 
                 1000 
                 3.8 
                 benzoic acid, 73 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 0.1 
               
               
                 4 
                 (1) 
                 407/379/1103/20 
                 8.0 
                 220 
                 5 
                 1000 
                 3.8 
                 benzoic acid, 73 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 0.0 
               
               
                 5 
                 (2) 
                 407/379/1103/0  
                 8.0 
                 205 
                 0.5 
                 1000 
                 3.8 
                 benzoic acid, 13 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 0.6 
               
               
                 6 
                 (2) 
                 407/379/1103/0  
                 8.0 
                 205 
                 1.0 
                 1000 
                 3.8 
                 benzoic acid, 27 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 1.5 
               
               
                 7 
                 (2) 
                 407/379/1103/0  
                 8.0 
                 205 
                 2.0 
                 1000 
                 3.8 
                 benzoic acid, 52 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 3.0 
               
               
                 8 
                 (2) 
                 407/379/1103/0  
                 8.0 
                 205 
                 3.0 
                 1000 
                 3.8 
                 benzoic acid, 38 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 2.3 
               
               
                 9 
                 (3) 
                 407/379/1103/0  
                 8.0 
                 205 
                 3.0 
                 1000 
                 3.8 
                 benzoic acid, 59 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 3.2 
               
               
                 10 
                 (3) 
                 407/379/1103/0  
                 8.0 
                 205 
                 3.0 
                 1000 
                 3.8 
                 benzoic acid, 60 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 2.5 
               
               
                 11 
                 (3) 
                 407/379/1103/0  
                 8.0 
                 205 
                 3.0 
                 1000 
                 3.8 
                 benzoic acid, 62 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 1.6 
               
               
                 12 
                 (3) 
                 407/379/1103/0  
                 8.0 
                 205 
                 3.0 
                 1000 
                 3.8 
                 benzoic acid, 57 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 benzil, 2.6 
               
               
                   
               
               
                 Polymer sources:  
               
               
                 (1) Polystyrene pellets (Aldrich, cat. no. 18,242-7)  
               
               
                 (2) Black, rigid polystyrene plate, washed (Boston Market ®, Golden, CO)  
               
               
                 (3) Clear, rigid polystyrene cup (Legacy ®)  
               
             
          
         
       
     
     EXAMPLES 13-16 
     
       
                 
         
             
             
         
      
     
     The results of the reaction of Aldrich poly(4-vinylpyridine) (#22,696-3, 2% cross-linked) with air are given in Table 2. White solids were produced which were shown to be isonicotinic acid by NMR analysis. Maximum observed yield was 65%. The yield included the isonicotinic acid from the solids as well as that present in the filtrate. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Oxidation of poly(4-vinyl)pyridine to isonicotinic acid 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                 Initial 
                   
               
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Conc., 
                 Yield 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 wgt % 
                 mol % 
               
               
                   
               
               
                 13 
                 PVP(1) 
                 407/379/1103/20 
                 8 
                 150 
                 2 
                 1000 
                 3.68 
                 33.3 
               
               
                 14 
                 PVP(1) 
                 407/379/1103/20 
                 8 
                 180 
                 2 
                 1000 
                 3.57 
                 65.2 
               
               
                 15 
                 PVP(1) 
                 407/379/1103/20 
                 8 
                 220 
                 2 
                 1000 
                 3.51 
                 62.0 
               
               
                 16 
                 PVP(1) 
                 407/379/1103/20 
                 8 
                 220 
                 5 
                 1000 
                 8.71 
                 59.3 
               
               
                   
               
               
                 (1)Aldrich poly(4-vinylpyridine) (#22,696-3, 2% cross linked)  
               
             
          
         
       
     
     EXAMPLES 17-19 
     Oxidation of PEN produced solids which C,H-NMR analysis indicated were a mixture of 2,6-naphthalenedicarboxylic acid (NDC) and partially oxidized oligomer. Purer NDC can be obtained by using higher temperatures, longer reaction times, or higher catalyst concentrations. Co-oxidation of PEN with toluene and p-xylene produced solids which were shown by C,H-NMR analysis to be mixtures of NDC and benzoic acid, and NDC and terephthalic acid respectively. Only a trace of oligomer was detected in both cases. The data suggests that co-oxidation with methyl aromatic compounds oxidizes PEN more effectively than it is by itself. The conversion of toluene and p-xylene was &gt;99% with 100% of the toluene being converted to benzoic acid. Based on the results of PET, glycolic and acetoxyacetic acid was also formed during PEN oxidation. Results are shown in Table 3. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Oxidation of polyethylene(naphthenate) (PEN) 
               
             
          
           
               
                   
                   
                   
                   
                 Temp/time/ 
                 Init. 
                   
                 glycolic 
                 acetoxyacetic 
                   
               
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 pressure, C., 
                 Conc. 
                 NDC yld, 
                 acid 
                 acid, mol 
                   
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 Hr, psi 
                 Wgt % 
                 mol % 
                 yld, mol % 
                 % 
                 Foot-notes 
               
               
                   
               
             
          
           
               
                 17 
                 PEN 
                 407/379/1103/20 
                 8 
                 190/2/1000 
                 3.91 
                 100.0 
                 1.48 
                 3.69 
                 1,3 
               
               
                 18 
                 PEN + toluene 
                 407/379/1103/20 
                 8 
                 190/2/1000 
                 3.86 
                 72.0 
                 1.27 
                 5.67 
                 2,5 
               
               
                 19 
                 PEN + p-xylene 
                 407/379/1103/20 
                 8 
                 190/2/1000 
                 3.82 
                 100.0 
                 1.79 
                 11.3 
                 3,5 
               
               
                   
               
               
                 1DuPont Kaladex ® PEN film, 1000/340 gauge  
               
               
                 2DuPont Kaladex ® PEN film with added 9.4 wgt % toluene  
               
               
                 3DuPont Kaladex ® PEN film with added 4.7 wgt % p-xylene  
               
               
                 4NMR analysis indicated mixture of 2,6-NDC and oligomer  
               
               
                 5NMR analysis indicated 2,6-NDC with trace of oligomer  
               
             
          
         
       
     
     EXAMPLES 20-28 
     
       
                 
         
             
             
         
      
     
     Results are shown in Table 4. Oxidation of PBT for 2 hrs produced solids, which upon C,H-NMR analysis d that they were a mixture of terephthalic acid (TA) and a trace of oligomer. Co-oxidation of PBT with toluene and p-xylene for 2 hrs produced solids which upon C,H-NMR analysis indicated that the recovered solids were only terephthalic acid (TA). All of the other solids reported on Table 1 contained a mixture of TA and oligomer. The data indicates that longer reaction times decreased the amount of oligomer in the solids obtained after reaction. The conversion of toluene and p-xylene in these experiments were &gt;99% with 100% of the toluene being converted to benzoic acid. Products from PBT should additionally yield tetrahydrofuran by cyclization and succinic acid by oxidation. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Oxidation of Polylbutylene(terephthalate) 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                 Initial 
                   
                 Succinic 
                   
               
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Conc., 
                 Yield 
                 acid, mol 
                 Foot- 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 wgt % 
                 mol % 
                 % 
                 notes 
               
               
                   
               
             
          
           
               
                 20 
                 PBT 
                 407/379/1103/20 
                 8 
                 190 
                 2 
                 1000 
                 3.77 
                 51.1 
                 16.6 
                 1,5 
               
               
                 21 
                 PBT + 
                 407/379/1103/20 
                 8 
                 190 
                 2 
                 1000 
                 3.56 
                 83.6 
                 18.3 
                 1,2,6 
               
               
                   
                 toluene 
               
               
                 22 
                 PBT + 
                 407/379/1103/20 
                 8 
                 190 
                 2 
                 1000 
                 3.49 
                 84.8 
                 17.50 
                 1,3,6 
               
               
                   
                 p-xylene 
               
               
                 23 
                 PBT 
                 407/379/1103/20 
                 8 
                 190 
                 1 
                 1000 
                 4.49 
                 N/A 
                 8.10 
                 1 
               
               
                 24 
                 PBT + 
                 407/379/1103/20 
                 8 
                 190 
                 1 
                 1000 
                 3.88 
                 N/A 
                 14.0 
                 1,2 
               
               
                   
                 toluene 
               
               
                 25 
                 PBT + 
                 407/379/1103/20 
                 8 
                 190 
                 1 
                 1000 
                 3.72 
                 N/A 
                 19.4 
                 1,3 
               
               
                   
                 p-xylene 
               
               
                 26 
                 PBT 
                 407/379/1103/20 
                 8 
                 190 
                 0.5 
                 1000 
                 4.9 
                 85.5 
                 2.8 
                 1,4 
               
               
                 27 
                 PBT + 
                 407/379/1103/20 
                 8 
                 190 
                 0.5 
                 1000 
                 4.29 
                 56.0 
                 6.7 
                 1,2,4 
               
               
                   
                 toluene 
               
               
                 28 
                 PBT + 
                 407/379/1103/20 
                 8 
                 190 
                 0.5 
                 1000 
                 3.75 
                 82.6 
                 9.9 
                 1,3,4 
               
               
                   
                 p-xylene 
               
               
                   
               
               
                 1Crastin ® 6134 PBT (E.I. DuPont de Nemours, Wilmington, DE) Intrinsic viscosity is 0.75 to 0.8.  
               
               
                 2Crastin ® 6134 PBT with added 9.4 wgt % toluene  
               
               
                 3Crastin ® 6134 PBT with added 4.7 wgt % p-xylene  
               
               
                 4NMR analysis indicated mixture of TA and oligomer  
               
               
                 5NMR analysis indicated TA with trace of oligomer  
               
               
                 6NMR analysis indicated only TA present.  
               
             
          
         
       
     
     EXAMPLES 29-97 
     
       
                 
         
             
             
         
      
     
     The PET samples were oxidized by themselves and co-oxidized with toluene and p-xylene. Liquid GC analysis of the filtrates indicated that the conversion of p-xylene and toluene (when present) were greater than 100%. Benzoic acid yield (when toluene was present) was nearly 100%. 
     The description of the reactions is given in Table 5 and the results in Table 6. The table exemplifies that more efficient conversion of PET to terephthalic acid occurs at 1) higher temperatures, 2) longer residence times, 3) higher initial PET concentrations, 4) co-oxidation with toluene and 5) co-oxidation with p-xylene. 
     The oxidation of cotton and paper was also evaluated in Comparative Examples 87-97. These samples were initially insoluble in the initial catalyst/acetic acid solution. After the oxidation, there were no solids remaining and it is assumed that the cotton and paper was oxidized to carbon oxides (carbon dioxide and carbon monoxide). This illustrates that fibers, such as clothes, that contain PET, when oxidized will result in solids that are essentially terephthalic acid. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Oxidation of Polyethylene(terephthalate) (PET) 
               
             
          
           
               
                   
                   
                 Type Of 
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Initial Conc. 
                 [co-oxidant] 
               
               
                 Ex. 
                 Feedstock 
                 PET 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 wgt % 
                 wgt % 
               
               
                   
               
             
          
           
               
                 29 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 8.53 
                 0.00 
               
               
                 30 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.26 
                 2.36 
               
               
                 31 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.26 
                 2.36 
               
               
                 32 
                 PET 
                 blue film 
                 407/279/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 8.53 
                 0.00 
               
               
                 33 
                 PET 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 0.5 
                 1000 
                 3.93 
                 0.00 
               
               
                 34 
                 PET + p-xylene 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 0.5 
                 1000 
                 4.03 
                 4.72 
               
               
                 35 
                 PET 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.01 
                 0.00 
               
               
                 36 
                 PET + p-xylene 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.75 
                 4.75 
               
               
                 37 
                 PET 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 2.0 
                 1000 
                 3.76 
                 0.00 
               
               
                 38 
                 PET + p-xylene 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 2.0 
                 1000 
                 3.87 
                 4.69 
               
               
                 39 
                 PET 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 3.0 
                 1000 
                 3.94 
                 0.00 
               
               
                 40 
                 PET + p-xylene 
                 lid 
                 407/379/1103/0 
                 8 
                 205 
                 3.0 
                 1000 
                 4.11 
                 4.92 
               
               
                 41 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.01 
                 0.00 
               
               
                 42 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 7.69 
                 0.00 
               
               
                 43 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 11.51 
                 0.00 
               
               
                 44 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 15.25 
                 0.00 
               
               
                 45 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 19.03 
                 0.00 
               
               
                 46 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.79 
                 2.18 
               
               
                 47 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 7.64 
                 6.18 
               
               
                 48 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 11.39 
                 9.15 
               
               
                 49 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 0.5 
                 1000 
                 3.75 
                 0.00 
               
               
                 50 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 0.5 
                 1000 
                 3.82 
                 0.00 
               
               
                 51 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 0.5 
                 1000 
                 3.81 
                 4.82 
               
               
                 52 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 0.5 
                 1000 
                 3.88 
                 4.80 
               
               
                 53 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.80 
                 0.00 
               
               
                 54 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.85 
                 0.00 
               
               
                 55 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.87 
                 4.80 
               
               
                 56 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.74 
                 4.74 
               
               
                 57 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.5 
                 1000 
                 3.78 
                 0.00 
               
               
                 58 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.5 
                 1000 
                 3.80 
                 0.00 
               
               
                 59 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.5 
                 1000 
                 3.77 
                 4.81 
               
               
                 60 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.5 
                 1000 
                 3.85 
                 4.73 
               
               
                 61 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.81 
                 0.0 
               
               
                 62 
                 PET 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.90 
                 0.0 
               
               
                 63 
                 PET + toluene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.86 
                 9.4 
               
               
                 64 
                 PET + p-xylene 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.80 
                 5.1 
               
               
                 65 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.89 
                 5.1 
               
               
                 66 
                 PET 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.91 
                 0.0 
               
               
                 67 
                 PET 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.78 
                 5.1 
               
               
                 68 
                 PET + toluene 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.82 
                 9.4 
               
               
                 69 
                 PET + p-xylene 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.80 
                 5.1 
               
               
                 70 
                 PET + p-xylene 
                 barium 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.88 
                 5.1 
               
               
                 71 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.81 
                 0.0 
               
               
                 72 
                 PET 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.88 
                 0.0 
               
               
                 73 
                 PET + toluene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 3.86 
                 9.4 
               
               
                 74 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.89 
                 5.1 
               
               
                 75 
                 PET + p-xylene 
                 blue film 
                 407/379/1103/0 
                 8 
                 205 
                 1.0 
                 1000 
                 4.82 
                 5.1 
               
               
                 76 
                 PET 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 2.0 
                 1000 
                 3.93 
                 0.00 
               
               
                   
                   
                 resin 
                   
               
               
                 77 
                 PET + toluene 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 2.0 
                 1000 
                 4.02 
                 9.43 
               
               
                   
                   
                 resin 
                   
               
               
                 79 
                 PET + p-xylene 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 2.0 
                 1000 
                 4.34 
                 4.80 
               
               
                   
                   
                 resin 
                   
               
               
                 80 
                 PET 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 1.0 
                 1000 
                 4.13 
                 0.00 
               
               
                   
                   
                 resin 
                   
               
               
                 81 
                 PET + toluene 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 1.0 
                 1000 
                 4.15 
                 9.43 
               
               
                   
                   
                 resin 
                   
               
               
                 82 
                 PET + p-xylene 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 1.0 
                 1000 
                 3.95 
                 5.96 
               
               
                   
                   
                 resin 
                   
               
               
                 83 
                 PET 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 0.5 
                 1000 
                 4.13 
                 0.00 
               
               
                   
                   
                 resin 
                   
               
               
                 84 
                 PET + toluene 
                 recycled 
                  407/329/1103/20 
                 8 
                 190 
                 0.5 
                 1000 
                 3.96 
                 9.43 
               
               
                   
                   
                 resin 
                   
               
               
                 85 
                 PET + p-xylene 
                 recycled 
                  407/379/1103/20 
                 8 
                 190 
                 0.5 
                 1000 
                 3.86 
                 4.97 
               
               
                   
                   
                 resin 
                   
               
               
                 86 
                 PET 
                 shirt 
                  407/379/1103/20 
                 8 
                 150 
                 2.0 
                 1000 
                 2.82 
                 0 
               
               
                 87 
                 cotton 
                 — 
                 407/379/1103/0 
                 8 
                 150 
                 2.0 
                 1000 
                 — 
                 — 
               
               
                 88 
                 paper 
                 — 
                 407/379/1103/0 
                 8 
                 150 
                 2.0 
                 1000 
                 — 
                 — 
               
               
                 89 
                 PET 
                 shirt 
                 407/379/1103/0 
                 8 
                 180 
                 2.0 
                 1000 
                 3.16 
                 0 
               
               
                 90 
                 cotton 
                 — 
                  407/379/1103/20 
                 8 
                 180 
                 2.0 
                 1000 
                 — 
                 — 
               
               
                 91 
                 paper 
                 — 
                  407/379/1103/20 
                 8 
                 180 
                 2.0 
                 1000 
                 — 
                 — 
               
               
                 92 
                 PET 
                 shirt 
                  407/319/1103/20 
                 8 
                 220 
                 2.0 
                 1000 
                 3.05 
                 0 
               
               
                 93 
                 cotton 
                 — 
                  407/379/1103/20 
                 8 
                 220 
                 2.0 
                 1000 
                 — 
                 — 
               
               
                 94 
                 paper 
                 — 
                  407/319/1103/20 
                 8 
                 220 
                 2.0 
                 1000 
                 — 
                 — 
               
               
                 95 
                 PET 
                 shirt 
                  407/379/1103/20 
                 8 
                 220 
                 5.0 
                 1000 
                 3.86 
                 0 
               
               
                 96 
                 cotton 
                 — 
                  407/379/1103/20 
                 8 
                 220 
                 5.0 
                 1000 
                 — 
                 — 
               
               
                 97 
                 paper 
                 — 
                  407/379/1103/20 
                 8 
                 220 
                 5.0 
                 1000 
                 — 
                 — 
               
               
                   
               
               
                 Polymer sources:  
               
               
                 PET blue film: scrap NuPET ® x-ray film containing blue anthraquinone dye. E.I. DuPont de Nemours, Wilmington DE  
               
               
                 PET scrap white film filled with 18% barium sulfate. It also contains 137 ppm Mn, 2.6 ppm Sr and 300 ppm Sb. E.I. DuPont de Nemours, Wilmington DE  
               
               
                 Lid: Clear rigid plate lid, Boston Market ®, Golden, CO, washed before use.  
               
               
                 Shirt: Used TownCraft white shirt composed of 50% Fortrel ® polyester and 50% combed cotton.  
               
               
                 Ground, recycled PET bottle resin: from Reprise Technology, EVC Compounds Ltd., Cheshire, UK  
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Results from the Co/Mn/Br catalyzed Oxidation of Polyethylene(terephthalate) 
               
               
                 (PET) 
               
             
          
           
               
                   
                   
                 TA Yield 
                 Glycolic Acid 
                 Acetoxyacetic Acid 
                 % Oligomer In 
               
               
                 Ex. 
                 Feedstock 
                 % 
                 Yld % 
                 Yld, % 
                 Solids 
               
               
                   
               
             
          
           
               
                 29 
                 PET 
                 76.7 
                 — 
                 — 
                 &gt;26 
               
               
                 30 
                 PET + p-xylene 
                 66.9 
                 — 
                 — 
                 7.8 
               
               
                 31 
                 PET + p-xylene 
                 77.7 
                 — 
                 — 
                 3.0 
               
               
                 32 
                 PET 
                 79.3 
                 — 
                 — 
                 2.9 
               
               
                 33 
                 PET 
                 63.4 
                 1.29 
                 5.58 
                 &gt;32 
               
               
                 34 
                 PET + p-xylene 
                 85.3 
                 2.61 
                 6.51 
                 7.5 
               
               
                 35 
                 PET 
                 63.7 
                 0.81 
                 2.02 
                 20.2 
               
               
                 36 
                 PET + p-xylene 
                 88.5 
                 1.31 
                 — 
                 0 
               
               
                 37 
                 PET 
                 76.5 
                 0.83 
                 5.91 
                 10.3 
               
               
                 38 
                 PET + p-xylene 
                 89.0 
                 0.88 
                 4.54 
                 1.3 
               
               
                 39 
                 PET 
                 85.3 
                 0.35 
                 2.61 
                 3.2 
               
               
                 40 
                 PET + p-xylene 
                 90.6 
                 0.61 
                 2.87 
                 1.1 
               
               
                 41 
                 PET 
                 77.9 
                 — 
                 — 
                 30.0 
               
               
                 42 
                 PET 
                 79.9 
                 — 
                 — 
                 18.2 
               
               
                 43 
                 PET 
                 86.4 
                 — 
                 — 
                 12.3 
               
               
                 44 
                 PET 
                 87.2 
                 — 
                 — 
                 5.9 
               
               
                 45 
                 PET 
                 88.4 
                 — 
                 — 
                 3.8 
               
               
                 46 
                 PET + p-xylene 
                 136.3 
                 — 
                 — 
                 9.0 
               
               
                 47 
                 PET + p-xylene 
                 116.8 
                 — 
                 — 
                 — 
               
               
                 48 
                 PET + p-xylene 
                 81.5 
                 — 
                 — 
                 4.6 
               
               
                 49 
                 PET 
                 66 
                 1.78 
                 4.64 
                 &gt;33 
               
               
                 50 
                 PET 
                 64 
                 0.69 
                 1.78 
                 &gt;29 
               
               
                 51 
                 PET + p-xylene 
                 87 
                 1.76 
                 3.80 
                 1.7 
               
               
                 52 
                 PET + p-xylene 
                 86 
                 1.55 
                 2.24 
                 0.6 
               
               
                 53 
                 PET 
                 60 
                 1.47 
                 3.66 
                 &gt;33 
               
               
                 54 
                 PET 
                 68 
                 1.23 
                 5.62 
                 22.8 
               
               
                 55 
                 PET + p-xylene 
                 85 
                 0.37 
                 3.80 
                 4.9 
               
               
                 56 
                 PET + p-xylene 
                 81 
                 0.35 
                 0.24 
                 3.9 
               
               
                 57 
                 PET 
                 67 
                 1.72 
                 5.00 
                 27.6 
               
               
                 58 
                 PET 
                 72 
                 1.07 
                 5.30 
                 23.2 
               
               
                 59 
                 PET + p-xylene 
                 82 
                 1.69 
                 4.40 
                 4.6 
               
               
                 60 
                 PET + p-xylene 
                 86 
                 1.60 
                 4.83 
                 6.0 
               
               
                 61 
                 PET 
                 89.6 
                 1.83 
                 5.16 
                 29.0 
               
               
                 62 
                 PET 
                 73.9 
                 1.25 
                 5.08 
                 &gt;21 
               
               
                 63 
                 PET + toluene 
                 106.6 
                 — 
                 — 
                 9.9 
               
               
                 64 
                 PET + p-xylene 
                 83.3 
                 — 
                 — 
                 2.1 
               
               
                 65 
                 PET + p-xylene 
                 87.8 
                 — 
                 — 
                 0.6 
               
               
                 66 
                 PET 
                 71.4 
                 — 
                 — 
                 &gt;29 
               
               
                 67 
                 PET 
                 67.5 
                 1.49 
                 7.02 
                 &gt;23 
               
               
                 68 
                 PET + toluene 
                 105.9 
                 — 
                 — 
                 &gt;16 
               
               
                 69 
                 PET + p-xylene 
                 88.1 
                 — 
                 — 
                 3.6 
               
               
                 70 
                 PET + p-xylene 
                 90.1 
                 1.39 
                 4.90 
                 3.0 
               
               
                 71 
                 PET 
                 73.4 
                   
                   
                 &gt;37 
               
               
                 72 
                 PET 
                 74.0 
                 0.92 
                 7.95 
                 33.6 
               
               
                 73 
                 PET + toluene 
                 105.9 
                 — 
                 — 
                 26.5 
               
               
                 74 
                 PET + p-xylene 
                 92.3 
                 — 
                 — 
                 8.0 
               
               
                 75 
                 PET + p-xylene 
                 89.2 
                 0.68 
                 3.29 
                 10.3 
               
               
                 76 
                 PET 
                 75.1 
                 0.91 
                 6.41 
                 &gt;25 
               
               
                 77 
                 PET + toluene 
                 66.7 
                 0.22 
                 1.54 
                 4.4 
               
               
                 79 
                 PET + p-xylene 
                 82.4 
                 0.21 
                 1.41 
                 0.3 
               
               
                 80 
                 PET 
                 86.0 
                 — 
                 — 
                 &gt;38 
               
               
                 81 
                 PET + toluene 
                 99.8 
                 — 
                 — 
                 &gt;17 
               
               
                 82 
                 PET + p-xylene 
                 83.7 
                 — 
                 — 
                 8.2 
               
               
                 83 
                 PET 
                 88.1 
                 — 
                 — 
                 &gt;37 
               
               
                 84 
                 PET + toluene 
                 108.7 
                 — 
                 — 
                 &gt;8 
               
               
                 85 
                 PET + p-xylene 
                 70.3 
                 — 
                 — 
                 &gt;10 
               
               
                 86 
                 PET 
                 190.8 
                 — 
                 — 
                 — 
               
               
                 87 
                 cotton 
                 — 
                 — 
                 — 
                 — 
               
               
                 88 
                 paper 
                 — 
                 — 
                 — 
                 — 
               
               
                 89 
                 PET 
                 84.5 
                 — 
                 — 
                 25.5 
               
               
                 90 
                 cotton 
                 — 
                 — 
                 — 
                 — 
               
               
                 91 
                 paper 
                 — 
                 — 
                 — 
                 — 
               
               
                 92 
                 PET 
                 93.6 
                 — 
                 — 
                 0.0 
               
               
                 93 
                 cotton 
                 — 
                 — 
                 — 
                 — 
               
               
                 94 
                 paper 
                 — 
                 — 
                 — 
                 — 
               
               
                 95 
                 PET 
                 95.1 
                 — 
                 — 
                 0.0 
               
               
                 96 
                 cotton 
                 — 
                 — 
                 — 
                 — 
               
               
                 97 
                 paper 
                 — 
                 — 
                 — 
                 — 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 98-105 
     
       
                 
         
             
             
         
      
     
     Aldrich polypropylene (#42,811-6, Average M w , 12,000, Average M n =5,000, viscosity at 190 C, 6.0 poise, density 0.902, m.p. 157 C, fine powder) was oxidized and the results given in Table 7. Yields to acetic acid as high as 70% are observed. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Oxidation of Polypropylene (PP) to Acetic acid 
               
             
          
           
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Initial Conc. 
                 Conversion 
                 Yield 
                 Foot 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 wgt % 
                 % 
                 % 
                 Note 
               
               
                   
               
             
          
           
               
                 98 
                 PP 
                 407/379/1103/0 
                 0 
                 150 
                 2 
                 1000 
                 7.55 
                 — 
                 26 
                 1 
               
               
                 99 
                 PP 
                 407/379/1103/0 
                 0 
                 180 
                 2 
                 1000 
                 7.55 
                 — 
                 70 
                 1 
               
               
                 100 
                 PP 
                 407/379/1103/0 
                 0 
                 220 
                 2 
                 1000 
                 9.43 
                 73 
                 14 
                 2 
               
               
                 101 
                 PP 
                 407/379/1103/0 
                 0 
                 220 
                 2 
                 1000 
                 18.87 
                 45 
                 23 
                 2 
               
               
                 102 
                 PP 
                 407/379/1103/0 
                 0 
                 150 
                 6 
                 1000 
                 9.43 
                 96 
                 56 
                 2 
               
               
                 103 
                 PP 
                 407/379/1103/0 
                 0 
                 180 
                 4 
                 1000 
                 9.43 
                 91 
                 57 
                 2 
               
               
                 104 
                 PP 
                 407/379/1103/0 
                 0 
                 120 
                 2 
                 1000 
                 7.55 
                 — 
                 20 
                 3 
               
               
                 105 
                 PP 
                 407/379/1103/0 
                 0 
                 180 
                 2 
                 1000 
                 7.55 
                 — 
                 22 
                 3 
               
               
                   
               
               
                 1 Yield determined by performing reaction in deuteroacetic acid and adding an internal standard (toluene) and measuring its hydrogen NMR spectrum. Conversion of polypropylene is determined by isolated weight of unreacted polypropylene after reaction.  
               
               
                 2 Yield determined by weight gain after subtracting the amount of water formed in reaction.  
               
               
                 3 Yield determined by performing the reaction in propionic acid and measuring the amount of acetic acid formed by liquid GC.  
               
             
          
         
       
     
     EXAMPLES 106-113 
     
       
                 
         
             
             
         
      
     
     Aldrich 33/211-9 polyethylene (medium density/ m.p. 109-111° C./ d0.940/fine powder) was oxidized to significant yields of succinic/glutaric and adipic acids, see Table 8. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Oxidation of Polyethylene (PE) to Succinic, fumaric, glutaric and adipic acids 
               
             
          
           
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Init. Conc. 
                 Succinic, 
                 Fumaric, 
                 Glutaric, 
                 Adipic, 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 Wgt % 
                 Yld, % 
                 Yld, % 
                 Yld, % 
                 Yld, % 
               
               
                   
               
             
          
           
               
                 106 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 150 
                 2 
                 1000 
                 3.86 
                 11.76 
                 0.18 
                 10.04 
                 7.05 
               
               
                 107 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 150 
                 2 
                 1000 
                 7.67 
                 10.36 
                 0.14 
                 6.51 
                 8.12 
               
               
                 108 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 180 
                 2 
                 1000 
                 3.88 
                 15.36 
                 0.10 
                 4.68 
                 1.08 
               
               
                 109 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 180 
                 2 
                 1000 
                 7.69 
                 8.91 
                 0.43 
                 0.46 
                 5.04 
               
               
                 110 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 220 
                 2 
                 1000 
                 3.82 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
               
               
                 111 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 220 
                 2 
                 1000 
                 7.63 
                 1.47 
                 0.10 
                 1.06 
                 1.24 
               
               
                 112 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 220 
                 5 
                 1000 
                 3.84 
                 13.12 
                 0.34 
                 3.13 
                 0.21 
               
               
                 113 
                 polyethylene 
                 407/379/1103/20 
                 8 
                 220 
                 5 
                 1000 
                 7.62 
                 6.79 
                 0.27 
                 4.80 
                 4.20 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 114-115 
     
       
                 
         
             
             
         
      
     
     Conditions and results are shown in Tables 9 and 10. Polyvinylchloride used was Aldrich #18,261-3, a fine powder with an inherent viscosity of 1.26, density of 1.385 and a molecular weight of 300,000. The mono- and di-chloroacetic acid was formed by the chlorine, from the PVC, reacting with the acetic acid solvent. The PVC also catalyzed the oxidation of the acetic acid to acetoxyacetic acid and glycolic acid. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Oxidation of Polyvinylchloride to Chloroacetic acid, Glycolic acid, 
               
               
                 Acetoxyacetic acid, Dichloroacetic acid and Formic acid 
               
             
          
           
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Initial Conc. 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 wgt % 
               
               
                   
               
               
                 114 
                 PVP 
                 407/379/1103/0 
                 0 
                 180 
                 2 
                 1000 
                 7.65 
               
               
                 115 
                 PVP 
                 407/379/1103/0 
                 0 
                 210 
                 2 
                 1000 
                 7.77 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 10 
               
               
                   
               
               
                   
                 Chloroacetic 
                 Acetoxyacetic 
                 Glycolic Acid Yld, 
                 Formic Acid 
               
               
                 Ex. 
                 Acid Yld, % 
                 Acid Yld, % 
                 % 
                 Yld, % 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 114 
                 35 
                 8.0 
                 3.3 
                 12.5 
               
               
                 115 
                 14 
                 0.0 
                 0.0 
                 0.86 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 116-123 
     Results from the oxidation of poly(bisphenol A carbonate) to p-hydroxybenzoic acid and 4-acetoxybenzoic acid are given on Table 11. The yields were based on the analysis of the filtrates only. There were substantial amounts of solids after the reaction which were not been analyzed. The poly(bisphenol A carbonate) was obtained from Aldrich #43,512-0. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 11 
               
             
             
               
                   
               
               
                 Oxidation of Poly(bisphenol A)carbonate to p-Hydroxybenzoic acid (PHBA), 
               
               
                 4-acetoxybenzoic acid (PABA) and Bisphenol A (BPA) 
               
             
          
           
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                 Init. Conc. 
                 4-PHBA 
                 PABA 
                 BPA 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 hr 
                 psi 
                 Wgt % 
                 yld % 
                 yld, % 
                 yld % 
               
               
                   
               
             
          
           
               
                 116 
                 PBAC 
                 407/379/1103/20 
                 8 
                 150 
                 2 
                 1000 
                 7.62 
                 0.06 
                 0.00 
                 3.61 
               
               
                 117 
                 PBAC 
                 407/379/1103/20 
                 0 
                 180 
                 5 
                 1000 
                 7.30 
                 4.85 
                 0.73 
                 0.82 
               
               
                 118 
                 PBAC 
                 407/379/1103/20 
                 10 
                 180 
                 5 
                 1000 
                 7.04 
                 10.3 
                 0.15 
                 0.71 
               
               
                 119 
                 PBAC 
                 407/379/1103/20 
                 8 
                 180 
                 2 
                 1000 
                 7.67 
                 6.63 
                 0.43 
                 1.52 
               
               
                 120 
                 PBAC 
                 407/379/1103/20 
                 0 
                 220 
                 2 
                 1000 
                 7.45 
                 6.91 
                 0.50 
                 3.58 
               
               
                 121 
                 PBAC 
                 407/379/1103/20 
                 10 
                 220 
                 2 
                 1000 
                 7.39 
                 10.1 
                 0.0 
                 1.23 
               
               
                 122 
                 PBAC 
                 407/379/1103/20 
                 8 
                 220 
                 2 
                 1000 
                 7.69 
                 9.26 
                 0.100 
                 0.290 
               
               
                 123 
                 PBAC 
                 407/379/1103/20 
                 8 
                 220 
                 5 
                 1000 
                 8.03 
                 9.37 
                 0.088 
                 .245 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 124-129 
     
       
                 
         
             
             
         
      
     
     Oxidation of 2-poly(vinyl)pyridine co-polymerized with 30% styrene is given on Table 12. Poly(2-vinylpyridine-co-styrene) was Aldrich #18,460,-8 which was granular with an average Mw of approximately 220,000 having a styrene content of 30%. Results of the reaction is given on Table 12. There were substantial amounts of solids after the reaction which had not been analyzed. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 12 
               
             
             
               
                   
               
               
                 Oxidation of 2-poly(vinyl)pyridine co styrene to 
               
               
                 Benzoic acid and Picolinic acid 
               
             
          
           
               
                   
                   
                 Co/Mn/Br/Zr 
                 Water 
                 Temp 
                 Time 
                 Pressure 
                   
                 Benzoic 
                 Piccolinic 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 % 
                 ° C. 
                 Hr 
                 Psi 
                 Solids 
                 Acid Yld 
                 Acid Yld 
               
               
                   
               
             
          
           
               
                 124 
                 PVP/PS 
                 407/379/1103/20 
                 8 
                 150 
                 2 
                 1000 
                 3.86 
                 10.23 
                 0.61 
               
               
                 125 
                 PVP/PS 
                 407/379/1103/20 
                 8 
                 150 
                 2 
                 1000 
                 13.18 
                 1.26 
                 0.45 
               
               
                 126 
                 PVP/PS 
                 407/379/1103/20 
                 8 
                 180 
                 2 
                 1000 
                 3.84 
                 20.81 
                 4.32 
               
               
                 127 
                 PVP/PS 
                 407/379/1103/20 
                 8 
                 220 
                 2 
                 1000 
                 3.79 
                 80.99 
                 1.47 
               
               
                 128 
                 PVP/PS 
                 407/379/1103/20 
                 8 
                 220 
                 2 
                 1000 
                 13.39 
                 20.25 
                 0.18 
               
               
                 129 
                 PVP/PS 
                 407/379/1103/20 
                 8 
                 220 
                 5 
                 1000 
                 3.73 
                 74.68 
                 0.69 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 130-149 
     The oxidation of polystyrene using non-bromide containing catalysts is given on Table 13. The feedstock was Aldrich polystyrene (18,242-7 Average Mw, 280,000). All metals were used as described previously. Ni was nickel(II); added as the acetate. NHPI is N-hydroxyphthalimide. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 13 
               
             
             
               
                   
               
               
                 Oxidation of Polystyrene (PS) using Non-bromide Containing catalysts 
               
             
          
           
               
                   
                   
                 Catalyst, 
                   
                 Time, Hr/Temp, C./ 
                 Polymer, 
                 Benzoic Acid 
                 Benzil Yield, 
               
               
                 Ex. 
                 Feedstock 
                 ppm 
                 Water, % 
                 Air Pressure, Psi 
                 Wgt % 
                 Yield, Mol % 
                 Mol % 
               
               
                   
               
             
          
           
               
                 130 
                 PS 
                 Co, 
                 0 
                 5/140/1000 
                 3.83 
                 1.0 
                 0.04 
               
               
                   
                   
                 2950 
                   
               
               
                 131 
                 PS 
                 Co/Zr, 
                 0 
                 5/140/1000 
                 3.80 
                 1.1 
                 0.04 
               
               
                   
                   
                 2950,47  
                   
               
               
                 132 
                 PS 
                 Co/Mn, 
                 0 
                 5/140/1000 
                 3.80 
                 12.3 
                 0.38 
               
               
                   
                   
                 2950,137 
                   
               
               
                 133 
                 PS 
                 Co/Ce, 
                 0 
                 5/140/1000 
                 3.85 
                 14.2 
                 0.61 
               
               
                   
                   
                 2950,250 
                   
               
               
                 134 
                 PS 
                 Co/Ni, 
                 0 
                 5/140/1000 
                 3.85 
                 1.2 
                 0.04 
               
               
                   
                   
                 2950,250 
                   
               
               
                 135 
                 PS 
                 Ni, 
                 0 
                 5/140/1000 
                 3.82 
                 0.2 
                 0.01 
               
               
                   
                   
                 2950 
                   
               
               
                 136 
                 PS 
                 Co/NHPI, 
                 0 
                 5/140/1000 
                 3.85 
                 3.7 
                 0.16 
               
               
                   
                   
                 2950,200 
                   
               
               
                 137 
                 PS 
                 Co, 
                 0 
                 5/140/1000 
                 3.84 
                 2.0 
                 0.08 
               
               
                   
                   
                 2950 
                   
               
               
                 138 
                 PS 
                 Co/Zr, 
                 0 
                 5/140/1000 
                 3.82 
                 2.4 
                 0.07 
               
               
                   
                   
                 2950,47  
                   
               
               
                 139 
                 PS 
                 Co/Mn, 
                 0 
                 5/140/1000 
                 3.84 
                 38.3 
                 0.66 
               
               
                   
                   
                 2950,137 
                   
               
               
                 140 
                 PS 
                 Co, 
                 0 
                 5/180/1000 
                 3.78 
                 9.1 
                 0.21 
               
               
                   
                   
                 2950 
                   
               
               
                 141 
                 PS 
                 Co/Zr, 
                 0 
                 5/180/1000 
                 3.79 
                 8.6 
                 0.19 
               
               
                   
                   
                 2950,47  
                   
               
               
                 142 
                 PS 
                 Co/Mn, 
                 0 
                 5/180/1000 
                 3.80 
                 56.3 
                 0.05 
               
               
                   
                   
                 2950,137 
                   
               
               
                 143 
                 PS 
                 Co/Ce, 
                 0 
                 5/180/1000 
                 3.81 
                 47.2 
                 0.28 
               
               
                   
                   
                 2950,250 
                   
               
               
                 144 
                 PS 
                 Co/Ni, 
                 0 
                 5/180/1000 
                 3.80 
                 8.2 
                 0.15 
               
               
                   
                   
                 2950,250 
                   
               
               
                 145 
                 PS 
                 Ni, 
                 0 
                 5/180/1000 
                 3.89 
                 1.2 
                 0.09 
               
               
                   
                   
                 2950 
                   
               
               
                 146 
                 PS 
                 Co/NHPI, 
                 0 
                 5/180/1000 
                 3.89 
                 11.3 
                 0.39 
               
               
                   
                   
                 2950,200 
                   
               
               
                 147 
                 PS 
                 Co, 
                 0 
                 5/180/1000 
                 3.81 
                 5.3 
                 0.10 
               
               
                   
                   
                 2950 
                   
               
               
                 148 
                 PS 
                 Co/Zr, 
                 0 
                 5/180/1000 
                 3.82 
                 4.2 
                 0.06 
               
               
                   
                   
                 2950,47  
                   
               
               
                 149 
                 PS 
                 Co/Mn, 
                 0 
                 5/180/1000 
                 3.80 
                 48.6 
                 0.06 
               
               
                   
                   
                 2950,137 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 150-169 
     Polypropylene (PP) can be oxidized in water using vanadium (as ammonium metavanadate) and vanadium/bromide catalysts (bromide as 48 wgt % hydrobromic acid in water), see table 14. The same source of PP used in examples 98-105 were used in table 14. Yields to acetic acid as high as 50% are observed. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 14 
               
             
             
               
                   
               
               
                 Oxidation of Polypropylene (PP) to Acetic acid in Water Solvent using Vanadium 
               
               
                 and Vanadium Bromide Catalysts 
               
             
          
           
               
                 example 
                 feedstock 
                 catalyst 
                 Catalyst conc., ppm 
                 temp, C. 
                 time, hr 
                 [PP], wgt % 
                 HOAc, yld, % 
               
               
                   
               
               
                 150 
                 PP 
                 V 
                  204 
                 160 
                 4 
                 3.83 
                 38.1 
               
               
                 151 
                 PP 
                 V 
                 4330 
                 160 
                 4 
                 3.92 
                 42.6 
               
               
                 152 
                 PP 
                 V/Br 
                 204/300 
                 160 
                 4 
                 3.78 
                 38.8 
               
               
                 153 
                 PP 
                 V/Br 
                 1019/4330 
                 160 
                 4 
                 3.80 
                 42.2 
               
               
                 154 
                 PP 
                 V/Br 
                 1600/6800 
                 160 
                 4 
                 3.82 
                 46.3 
               
               
                 155 
                 PP 
                 V 
                  204 
                 180 
                 4 
                 3.75 
                 42.2 
               
               
                 156 
                 PP 
                 V 
                 4330 
                 180 
                 4 
                 3.82 
                 42.1 
               
               
                 157 
                 PP 
                 V/Br 
                 204/300 
                 180 
                 4 
                 3.91 
                 38.7 
               
               
                 158 
                 PP 
                 V/Br 
                 1019/4330 
                 180 
                 4 
                 3.90 
                 35.0 
               
               
                 159 
                 Pp 
                 V/Br 
                 1600/6800 
                 180 
                 4 
                 3.78 
                 52.0 
               
               
                 160 
                 PP 
                 V 
                  204 
                 220 
                 2 
                 3.93 
                 36.1 
               
               
                 161 
                 PP 
                 V 
                 4330 
                 220 
                 2 
                 3.80 
                 39.8 
               
               
                 162 
                 PP 
                 V/Br 
                 204/300 
                 220 
                 2 
                 3.77 
                 43.3 
               
               
                 163 
                 PP 
                 V/Br 
                 1019/4330 
                 220 
                 2 
                 3.78 
                 44.5 
               
               
                 164 
                 PP 
                 V/Br 
                 1600/6800 
                 220 
                 2 
                 3.76 
                 49.8 
               
               
                 165 
                 PP 
                 V 
                  204 
                 220 
                 4 
                 3.89 
                 35.7 
               
               
                 166 
                 PP 
                 V 
                 4330 
                 220 
                 4 
                 3.82 
                 35.7 
               
               
                 167 
                 PP 
                 V/Br 
                 204/300 
                 220 
                 4 
                 3.89 
                 40.9 
               
               
                 168 
                 PP 
                 V/Br 
                 1019/4330 
                 220 
                 4 
                 3.86 
                 44.3 
               
               
                 169 
                 PP 
                 V/Br 
                 1600/6800 
                 220 
                 4 
                 3.77 
                 50.7 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 170-182 
     Polyethylene can be oxidized in water using vanadium (as ammonium metavanadate) and vanadium/bromide catalysts (bromide as 48 wgt % hydrobromic acid in water), see table 15. The same source of PE used in examples 106-113 were used in Table 15. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 15 
               
             
             
               
                   
               
               
                 Oxidation of Polyethylene (PE) to Succinic, Glutaric and Adipic acid in Water 
               
               
                 Solvent using Vanadium and Vanadium Bromide Catalysts 
               
             
          
           
               
                   
                   
                   
                 catalyst 
                 temp, 
                 time, 
                 PE, wgt 
                 succinic 
                 glutaric, 
                 adipic, yld. 
               
               
                 Exa, 
                 reagent 
                 catalyst 
                 conc., ppm 
                 C. 
                 hr 
                 % 
                 yld, % 
                 yld % 
                 % 
               
               
                   
               
             
          
           
               
                 170 
                 PE 
                 V 
                 12990 
                 180 
                 2.0 
                 3.8 
                 7.2 
                 14.0 
                 8.6 
               
               
                 171 
                 PE 
                 V/Br 
                 204/300 
                 150 
                 8.0 
                 3.8 
                 9.7 
                 5.6 
                 7.8 
               
               
                 172 
                 PE 
                 V 
                  4330 
                 200 
                 1.0 
                 3.8 
                 6.3 
                 7.2 
                 8.6 
               
               
                 173 
                 PE 
                 V 
                  204 
                 150 
                 2.0 
                 3.8 
                 7.4 
                 6.5 
                 8.1 
               
               
                 174 
                 PE 
                 V 
                  4330 
                 150 
                 4.0 
                 3.8 
                 6.2 
                 9.0 
                 5.6 
               
               
                 175 
                 PE 
                 V/Br 
                  4330/23650 
                 200 
                 2.0 
                 7.5 
                 15.2 
                 1.6 
                 3.4 
               
               
                 176 
                 PE 
                 V/Br 
                 300/204 
                 180 
                 2.0 
                 3.8 
                 8.9 
                 4.7 
                 5.9 
               
               
                 177 
                 PE 
                 V 
                  204 
                 150 
                 8.0 
                 3.8 
                 9.3 
                 5.4 
                 4.6 
               
               
                 178 
                 PE 
                 V 
                  204 
                 150 
                 6.0 
                 3.8 
                 9.1 
                 5.7 
                 4.5 
               
               
                 179 
                 PE 
                 V 
                  4330 
                 180 
                 2.0 
                 3.8 
                 6.5 
                 5.8 
                 6.5 
               
               
                 180 
                 PE 
                 V 
                  4330 
                 200 
                 2.0 
                 3.8 
                 12.3 
                 6.5 
                 0.0 
               
               
                 181 
                 PE 
                 V 
                 12990 
                 200 
                 1.0 
                 3.8 
                 5.9 
                 12.5 
                 0.0 
               
               
                 182 
                 PE 
                 V 
                  204 
                 150 
                 4.0 
                 3.8 
                 4.4 
                 13.9 
                 0.0 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 183-184 
     Polyethylene can be oxidized in a 20 wgt % acetic acid- 80 wgt % ortho-dichlorobenzene solution using a cobalt, manganese, bromine catalyst. 5 wgt % of PE was dissolved in this mixture by heating. It was subsequently oxidized in air, see Table 16. The same source of PE used in examples 106-113 was used in table 16. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 16 
               
             
             
               
                   
               
               
                 Oxidation of Polyethylene (PE) to Succinic, Glutaric and Adipic acid in 20% 
               
               
                 acetic acid/Ortho-dichlorobenzene solvent using a Co/Mn/Br catalyst 
               
             
          
           
               
                   
                   
                   
                 catalyst conc., 
                 temp, 
                 time, 
                 PE, 
                 succinic 
                 glutaric 
                 adipic 
               
               
                 Example 
                 feedstock 
                 catalyst 
                 ppm 
                 C. 
                 hr 
                 wgt % 
                 acid yld, % 
                 acid, yld % 
                 acid, yld. % 
               
               
                   
               
             
          
           
               
                 183 
                 PE 
                 Co/Mn/Zr/ 
                 589/549/1598/ 
                 150 
                 6.0 
                 2.0 
                 0.0 
                 10.7 
                 9.3 
               
               
                   
                   
                 Br 
                 93 
                   
               
               
                 184 
                 PE 
                 Co/Mn/Zr/ 
                 589/549/1598/ 
                 150 
                 8.0 
                 2.0 
                 12.3 
                 15.8 
                 10.7 
               
               
                   
                   
                 Br 
                 93 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 185-190 
     Polyvinylchloride (PVC) can be oxidized in water using vanadium (as ammonium metavanadate) and vanadium/bromide catalysts (bromide as 48 wgt % hydrobromic acid in water), see table 17. The same source of PVC was used in examples 114-115 was used in table 17. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 17 
               
             
             
               
                   
               
               
                 Oxidation of Polyvinylchloride (PVC) to Formic, Glycolic, Succinic and Adipic 
               
               
                 acids in Water Solvent using Vanadium and Vanadium Bromide Catalysts 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                 formic 
                 glycolic 
                 succinic 
                 adipic 
               
               
                   
                   
                   
                 catalyst 
                 time, 
                 temp, 
                 [PVC], 
                 acid, 
                 acid, 
                 acid, 
                 acid, 
               
               
                 ex. 
                 reagent 
                 catalyst 
                 conc., ppm 
                 hr 
                 C. 
                 wgt % 
                 yld, % 
                 yld, % 
                 yld, % 
                 yld, % 
               
               
                   
               
             
          
           
               
                 185 
                 PVC 
                 Co/Mn/Br 
                 1179/1099/ 
                 2 
                 200 
                 7.61 
                 2.87 
                 9.00 
                 1.8 
                 0.00 
               
               
                   
                   
                   
                  3196 
                   
               
               
                 186 
                 PVC 
                 V/Br 
                 4330/23650 
                 2 
                 200 
                 7.60 
                 1.06 
                 9.00 
                 30.8 
                 1.27 
               
               
                 187 
                 PVC 
                 Co 
                  7366 
                 4 
                 200 
                 7.65 
                 3.82 
                 0.08 
                 8.8 
                 1.74 
               
               
                 188 
                 PVC 
                 Co/Mn/Br 
                 1179/1099/ 
                 4 
                 200 
                 7.66 
                 2.46 
                 0.44 
                 5.9 
                 1.15 
               
               
                   
                   
                   
                  3196 
                   
               
               
                 189 
                 PVC 
                 HBr 
                 23650 
                 4 
                 200 
                 7.63 
                 0.69 
                 0.86 
                 2.9 
                 1.75 
               
               
                 190 
                 PVC 
                 V/Br 
                 4330/23650 
                 4 
                 200 
                 7.59 
                 0.71 
                 0.00 
                 38.4 
                 1.34