Hydrolysis of Polyesters and Polycarbonates

The focus of this review is the degradation of polyesters and polycarbonates in the presence of water or hydroxide ions as a method of recycling. Different methods of hydrolysis using different reaction media and the products obtained from these shall be introduced including the modification of the primary hydrolysis products in further reaction steps. Moreover, it should be provided an overlook about the meehanisms and kinetics as far as available. 

In recent years, the interest in the recycling of polyesters and polycarbonates has increased noticeably. New regulations let to the necessity to reduce the amount of waste and to recover raw materials from plastics. In this view, the hydrolysis of polyesters and PC shows promising results. PET is hydrolysed under different conditions in the range from several minutes to several hours. TPA and EG are recovered in high yields close to 100%. Neutral hydrolysis requires high temperatures and pressures for the recovery of TPA. 

Oligomeric carbodiimides are useful stabilizers for ester based polymers, such as polyesters, polyester based polyurethanes, polyether based polyurethanes, polyether based poly(urethane ureas) and polycarbonates. The scavenging of carboxyl end groups or carboxyl groups, generated in the hydrolysis of polyesters, with carbodiimide prevents hydrolysis of the polymers caused by the catalytic effect of the carboxyl groups. Neumann... 

In addition to the separate or combined effects of heat, oxygen, and radiation, polymers may deteriorate due to exposure to water (hydrolysis) or different types of chemical agents. Condensation polymers like nylons, polyesters, and polycarbonates are susceptible to hydrolysis. Structural alteration of some polymers may occur as a result of exposure to different chemical environments. Most thermoplastics in contact with organic liquids and vapors, which ordinarily may not be considered solvents for the polymers, can undergo environmental stress cracking and crazing. This may result in a loss of lifetime performance or mechanical stability and ultimately contribute to premature mechanical failure of the polymer under stress. 

The specialty class of polyols includes poly(butadiene) and polycarbonate polyols. The poly(butadiene) polyols most commonly used in urethane adhesives have functionalities from 1.8 to 2.3 and contain the three isomers (x, y and z) shown in Table 2. Newer variants of poly(butadiene) polyols include a 90% 1,2 product, as well as hydrogenated versions, which produce a saturated hydrocarbon chain [28]. Poly(butadiene) polyols have an all-hydrocarbon backbone, producing a relatively low surface energy material, outstanding moisture resistance, and low vapor transmission values. Aromatic polycarbonate polyols are solids at room temperature. Aliphatic polycarbonate polyols are viscous liquids and are used to obtain adhesion to polar substrates, yet these polyols have better hydrolysis properties than do most polyesters. 

As previously mentioned, some urethanes can biodegrade easily by hydrolysis, while others are very resistant to hydrolysis. The purpose of this section is to provide some guidelines to aid the scientist in designing the desired hydrolytic stability of the urethane adhesive. For hydrolysis of a urethane to occur, water must diffuse into the bulk polymer, followed by hydrolysis of the weak link within the urethane adhesive. The two most common sites of attack are the urethane soft segment (polyol) and/or the urethane linkages. Urethanes made from PPG polyols, PTMEG, and poly(butadiene) polyols all have a backbone inherently resistant to hydrolysis. They are usually the first choice for adhesives that will be exposed to moisture. Polyester polyols and polycarbonates may be prone to hydrolytic attack, but this problem can be controlled to some degree by the proper choice of polyol. 

Hydrolysis studies compared a polycarbonate urethane with a poly(tetramethyl-ene adipate) urethane and a polyether urethane based on PTMEG. After 2 weeks in 80°C water, the polycarbonate urethane had the best retention of tensile properties [92], Polycarbonates can hydrolyze, although the mechanism of hydrolysis is not acid-catalyzed, as in the case of the polyesters. Polycarbonate polyurethanes have better hydrolysis resistance than do standard adipate polyurethanes, by virtue of the highest retention of tensile properties. It is interesting to note in the study that the PTMEG-based urethanes, renowned for excellent hydrolysis resistance, had lower retention of physical properties than did the polycarbonate urethanes. 

Lipase is an enzyme which catalyzes the hydrolysis of fatty acid esters normally in an aqueous environment in living systems. However, hpases are sometimes stable in organic solvents and can be used as catalyst for esterifications and transesterifications. By utihzing such catalytic specificities of lipase, functional aliphatic polyesters have been synthesized by various polymerization modes. Typical reaction types of hpase-catalyzed polymerization leading to polyesters are summarized in Scheme 1. Lipase-catalyzed polymerizations also produced polycarbonates and polyphosphates. 

Enzymes that belong to the class of hydrolases are by far the most frequently-applied enzymes in polymer chemistry and are discussed in Chaps. 3-6. Although hydrolases typically catalyse hydrolysis reactions, in synthetic conditions they have also been used as catalysts for the reverse reaction, i.e. the bond-forming reaction. In particular, lipases emerged as stable and versatile catalysts in water-poor media and have been applied to prepare polyesters, polyamides and polycarbonates, all polymers with great potential in a variety of biomedical applications. 

Polyesters produce tough, oil-resistant polyurethanes, with the major drawback being lower hydrolysis resistance compared to polyurethanes made using polyethers. The two newer groups of polyesters (polycaprolac-tone- and polycarbonate-based) both have better resistance to hydrolysis. Their toughness is very close to the basic polyester polyurethanes. Their disadvantage is cost. 

The acid and base sensitivity of condensation polymers whether or not under stress, e.g. polycarbonate, polyesters, polyamides and polysilanes under influence of acid or base the condensation bonds are hydrolysed under the cooperative action of mechanical stresses and the environment. A striking example is shown in Fig. 26.11, where the strength retention of PpPTA fibres is plotted versus pH after an exposure of 3 months at room temperature (Van den Heuvel and Klop). The hydrolysis of the polyamide is acid or alkali catalysed, in particular below pH = 3 and above pH = 9. 

Alkyl carbonates are relatively labile concerning the hydrolysis reaction. Surprisingly, polycarbonate polyols give PU that are extremely resistant to hydrolysis, superior to those PU derived from polyesters based on adipic acid and diethylene glycol. The explanation of this paradox, mentioned before, is that between the hydrolysis products of polycarbonate polyols, acidic groups which are able to further catalyse hydrolysis reactions are not formed. The products of polyester polyol hydrolysis are diacids and glycols. The products of polycarbonate polyols hydrolysis are carbon dioxide (a gas which is eliminated easily) and glycols [76] ... 

The chemical resistance of polyester materials is generally limited due to the comparative ease of hydrolysis of the ester groups, but the bisphenol A polycarbonates are somewhat more resistant. This resistance maybe attributed to the shielding of the carbonate group by the hydrophobic benzene rings on either side. The resin thus shows resistance to dilute mineral acids however, it has poor resistance to alkali and to aromatic and chlorinated hydrocarbons. 

Interfacial polycondensation is an interesting procedure that is often used in demonstrations in polymer chemistry courses. Polyamides are prepared rapidly, in fiont of the class, from diacid chlorides and diamines. The products are removed quickly as they form, by pulling them out as a string from the interface." Polyesters can also be prepared from diacid chlorides and bisphenols. On the other hand, preparation of polyesters from glycols and diacid chlorides is usually unsuccessful due to low reactivity of the dialcohols. The diacid chlorides tend to undergo hydrolysis instead. Commercially, this procedure is so far confined mainly to preparations of polycarbonates (discussed further in this chapter). 

Polyurethanes, particularly those based on polyesters, are well known for their oil and grease resistance however, they are susceptible to attack by moisture. The structure of the backbone has a profound influence on the hydrolytic stability. The more hydrophobic the backbone, the greater the resistance of the polyurethane towards hydrolysis. Thus, polyether polyurethanes are inherently more stable to hydrolysis than polyester-based materials, and HTPBD-based polyurethanes are even more stable than the polyether materials. Polyurethanes prepared from polycarbonate diols have also been reported to display very good hydrolytic stability. " ... 

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