Polyesters chemical depolymerization

High-resolution 13C NMR studies have been conducted on intact cuticles from limes, suberized cell walls from potatoes, and insoluble residues that remain after chemical depolymerization treatments of these materials. Identification and quantitation of the major functional moieties in cutin and suberin have been accomplished with cross-polarization magic-angle spinning as well as direct polarization methods. Evidence for polyester crosslinks and details of the interactions among polyester, wax, and cell-wall components have come from a variety of spin-relaxation measurements. Structural models for these protective plant biopolymers have been evaluated in light of the NMR results. 

Isolation of the Biopolyesters. Cutin was obtained from the skin of limes using published methods (8,9). The final solvent extractions were omitted in studies of cutin-wax interactions. Typically, 20 limes provided 800 mg of powdered polymer. Suberized cell walls were isolated from wound-healing potatoes after seven days of growth (10), with a yield of 4.5 g from 22 kg of potatoes. Chemical depolymerization of both polyesters was accomplished via transesterification with BF3/CH3OH (11). 

Preliminary structural studies of cutin and suberin breakdown involved examination of 13C NMR spectra for insoluble residues that were resistant to chemical depolymerization. In cutin samples, flexible CH2 moieties in particular were removed by such treatments, but CHOCOR crosslinks and polysaccharide impurities were retained preferentially. A concomitant narrowing of NMR spectral lines suggested that the treatments produced more homogeneous polyester structures in both cases. Our current studies of cu-ticular breakdown also employ selective depolymerization strategies with appropriate enzymes (1,28). 

The major disadvantage of chemical depolymerization is that it is almost completely restricted to the recycling of condensation polymers, and is of no use for the decomposition of most addition polymers, which are the main components of the plastic waste stream. Condensation polymers are obtained by the random reaction of two molecules, which may be monomers, oligomers or higher molecular weight intermediates, which proceeds with the liberation of a small molecule as the chain bonds are formed. Chemical depolymerization takes place by promoting the reverse reaction of the polymer formation, usually through the reaction of those small molecules with the polymeric chains. Several resins widely used on a commercial scale are based on condensation polymers, such as polyesters, polyamides, polyacetals, polycarbonates, etc. However, these polymers account for less than 15% of the total plastic wastes (see Chapter 1). 

Chemical depolymerization of polyesters has been mainly applied to polyethylene terephthalate (PET), the most common polyester on the market. Chemo-lysis of PET by a variety of methods has been known for many years. In fact, the chemical depolymerization of PET can be considered the starting point of plastic chemical recycling. 

Chapter 2 discusses depolymerization processes based on the chemical cleavage of polymer molecules to convert them back into the raw monomers. The latter can be reused in the manufacture of new polymers, with properties similar to those of the virgin resins. However, this alternative is mainly used for condensation polymers, and is not successful for the degradation of most addition polymers. Glycolysis, methanolysis, hydrolysis and ammonolysis are the main treatments considered. Chemical depolymerization of polyesters, polyurethanes and polyamides is reviewed. 

A process for depolymerizing nylon-6 and polyester-nylon-6 mixed scrap was patented by Allied Chemical Corporation in 19656 and 1967.7 Ground scrap was dissolved with high-pressure steam at 125-130 psig (963-997 kPa) pressure and 175-180°C for 0.5 h in a batch process and then continuously hydrolyzed with superheated steam at 350°C and 100 psig (790 kPa) to form -caprolactam at an overall recovery efficiency of 98%. The recovered monomer could be repolymerized without additional purification. 

The major PET manufacturers are depolymerizing scrap PET with glycols (glycolysis) or methanol (methanolysis) to form low-molecular-weight polyester diols (and BHET) and dimethyl terephthalate.3 The purified products are then used to make new products. Goodyear uses glycolysis to make REPETE, a new product which contains 10-20% recycled PET. Hoechst Celanese used methanolysis to produce DMT for repolymerization. Eastman Chemicals uses depolymerization of PET to recover used X-ray scrap. 

The polyester domains of suberized walls can also be depolymerized using chemical and/or enzymatic approaches similar to those used for cutin. The aromatic domains are far more difficult to depolymerize as C-C and C-O-C crosslinks are probably present in such domains. Therefore, more drastic degradation procedures such as nitrobenzene, CuO oxidation, or thioglycolic... 

Fig. 3. (Top left) Chemical methods used to depolymerize the polyesters. (Top right) Thin-layer and gas-liquid chromatograms (as trimethylsilyl derivatives) of the monomer mixture obtained from the cutin of peach fruits by LiAlD4 treatment. In the thin-layer chromatogram the five major spots are, from the bottom, C18 tetraol, C16 triol, and C18 triol (unresolved), diols, and primary alcohol. Nx = C16 alcohol N2= C18 alcohol Mj = C16 diol M2 = C18 diol D = C16 triol D2 and D3 = unsaturated and saturated C18 triol, respectively, T4 and T2, unsaturated and saturated C18 tetraol, respectively. (Bottom) Mass spectrum of component D3 in the gas chromatogram. BSA = bis-N,O-trimethylsilyl acetamide...

Because all depolymerization processes will generate waste that may be classified as hazardous waste or at least chemical waste, it will always be economically preferable to separate as much non-PET material from the PET material as is practical. Traditional bottle washing procedures can produce used bottle flake that is clean enough to be used to make more bottles or somewhat less clean and less expensive material. Technologies have been proposed to dissolve the polyester scrap in appropriate solvents to separate PET from other materials such as cotton fiber or magnetic tape components [19]. 

Suberized Cell Walls. An analogous set of CPMAS experiments is presented for suberin in Figure 6. Because this polymer is an integral part of the plant cell wall, the 13C NMR spectrum had contributions from both polysaccharide and polyester components. Chemical-shift assignments, summarized in Table IV, demonstrated the feasibility of identifying major polyester and sugar moieties despite serious spectral overlap. Semiquantitative estimates for the various carbon types indicated that, as compared with cutin, the suberin polyester had dramatically fewer aliphatic and more aromatic residues. A similar observation was made previously for the soluble depolymerization products of these plant polymers (1,8,11). 

Different PET chemolysis methods have been developed aimed at the production of TPA, DMT or BHET, all of them being possible monomers for the reconstruction of fresh polyesters. The exact monomer formed by PET depolymerization depends on the type of chemical agent used to break down the polymeric chains. In certain processes, the final product of PET chemolysis is a mixture of polyols, useful in the formulation of other polymers such as unsaturated polyesters, polyurethanes and polyisocyanurates. This is an interesting case of chemical recycling because the breakdown of one polymer leads to the raw materials for the preparation of a quite different class of plastics. 

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