Aliphatic polyester

Aliphatic polyesters are typically prepared from aliphatic bifunctional alcohols and acids. 

If the polyester synthesis is performed with equimolar amounts of diol and diacid, then, in addition to hydroxy, carboxy-terminated oligomers, dihydroxy- and dicarboxy-terminated oligomers are formed, as shown below. In a thermodynamic equilibrium, the molar ratios of the three functionality fractions should be 2 1 1, respectively. 

Other structures like cyclic oligomers can also be formed. For the analysis of the functionality-type distribution of the reaction products, different types of interaction chromatography can be used. 

Other interesting polyesters of practical relevance are polylactides that are considered to be biologically degradable. Polylactides are prepared by a ring opening 

FIGURE 17.25 LCCC separation of a poly(l,6-hexanediol adipate) (a) and SEC analysis of the functionality fractions (b) from Kriiger et al., 1994 (Copyright 1994 from Journal of Liquid Chromatography, 1994, p. 17 by Kruger et al. Reproduced by permission of Taylor Francis Group, LLC., http //www.taylorandfrancis.com). 

Aliphatic polyesters are synthetic homopolymers or copolymers of lactic acid, glycolic acid, and s-hydroxycaproic acid. Typically, the molecular weights of homopolymers and copolymers range from 2000 to 100 000. 

Aliphatic polyesters are a group of synthesized homopolymers or copolymers. They are nontoxic and can easily be fabricated into a variety of novel devices, such as rods, screws, nails, and cylinders. The polymers are commercially available in varying molecular weights as both homopolymers and copolymers. Molecular weights of polyesters range from 2000 to greater than 100000. 

Co-monomer ratios of lactic acid and glycolic acid for poly(DL-lactide-co-glycolide) range from 85 15 to 50 50. Table I shows the chemical and trade names of different commercially available aliphatic polyesters. 

For typical physical and mechanical properties of the aliphatic polyesters, see Table II. 

Generic name LacHde Composition (%) Glycolide Caprolactone Synonyms Trade name Manufacturer CAS name CAS number 

The use of aliphatic monomers for hyperbranched polyesters has been debated because aliphatic monomers are said to be prone to thermal degradation reactions such as decarboxylation, cyclization, or dehydration [77]. The only commercial hyperbranched polymer is a hydroxy-functional aliphatic polyester, Boltorn, available from Perstorp AB, Sweden. 

Hawker et al. report on the synthesis of a similar hyperbranched polyester based on the corresponding AB4-monomer that is, the preformed dendron of the second generation was used in the condensation reaction [79]. 

Voit also carried out the melt condensation of bis-MPA using a slightly higher reaction temperature, 200 °C, and acid catalysis [83]. 

A somewhat different approach was presented by Rannard and Davis where they first reacted bis-MPA with carbonyl diimidazole, allowing a highly selective base-catalyzed reaction to form a hyperbranched polyester. The resulting polymers were hydroxy-functional and reported to be water-soluble [84]. 

There is a significant gap of degradation rates and performance properties between the aliphatic and aromatic polyesters. However, taking some hints from nature can fill this gap. Mixtures of polyesters, molecular orientation, substitution of some functional groups, and macro structures have all been proposed as a means to provide a range of application performance properties versus degradation rates. 

Polyesters offer multiple options to meet the complex world of degradable polymers. All polyesters degrade eventually, with hydrolysis being the dominant mechanism. Degradation rates range from weeks for aliphatic polyesters (e.g. polyhydroxyalkanoates) to decades for aromatic polyesters (e.g. PET). Specific local environmental factors such as humidity, pH and temperature significantly influence the rate of degradation. 

Copolyesters (such as BIOMAX ) which combine aromatic esters with aliphatic esters or other polymer units (e.g. ethers and amides) provide the opportunity to adjust and control the degradation rates. These added degrees of freedom on polymer composition provide the opportunity to rebalance the polymer to more specifically match application performance in physical properties, while still maintaining the ability to adjust the copolyesters to complement the degradation of natural products for the production of methane or humic substances. Since application performance requirements and application specific environmental factors and degradation expectations vary broadly, copolyesters are, and will continue to be, an important class of degradable polyesters. 

Handbook of Polymer Degradation, 2nd Edn, Marcel Dekker, New York, 2000, pp. 473-483. 

Polymer Degradation, Van Nostrand Reinhold, New York, 1983. 

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Polyesters were initially discovered and evaluated ia 1929 by W. H. Carothers, who used linear aliphatic polyester materials to develop the fundamental understanding of condensation polymerisation, study the reaction kinetics, and demonstrate that high molecular weight materials were obtainable and could be melt-spun iato fibers (1 5). 

Table 6. Properties of Aromatic—Aliphatic Polyester Resins ...

For an aliphatic polyester, poly(pivalolactone) has a rather high of 245°C and for such a an unexpectedly low of -10°C. It is also claimed to have good hydrolysis resistance for a polyester and this appears to be one of the reasons for its manufacture on an experimental scale by Shell with a view for use as both a fibre and as a thermoplastics moulding material. 

The activation energy of thermolysis of the azo group was measured by DSC [14]. Type II MAIs, which are composed of various prepolymers such as aliphatic polyester, poly(caprolactone), and aliphatic poly (carbonate), showed almost the same activation energy irrespective of difference in prepolymer structure, suggesting that the neighboring group only affects the active site. 

Aldiough they were the first step-growth polymers fully characterized, it is interesting to note that die first commercial applications of aliphatic polyesters appeared only in the late 1950s and the 1960s, widi die development of polyurediane foams and elastomers (see Chapter 5). 

Aliphatic polyesters are low-melting (40-80°C) semicrystalline polymers or viscous fluids and present inferior mechanical properties. Notable exceptions are poly (a-hydroxy acid)s and poly (ft -hydroxy acid)s. 

Aromatic-aliphatic polyesters, in which either R1 or R2 is aromatic, are generally high-melting (150-270°C) semicrystalline materials that find applications as engineering thermoplastics, films, or fibers. 

In the poly(alkylene arylate) series, Tm decreases with increasing length of flexible — (CH2) — moieties and, as in the aliphatic series, approaches the limiting value of polyethylene melting point for large n values (Table 2.6). Aromatic -aliphatic polyesters with even numbers of methylene groups melt at higher... 

C and is easily processable, whereas the homopolymers do not melt before the onset of thermal degradation, at temperatures as high as 500°C.73,74 Varying copolymer composition permits the adjustment of melting temperature and of other properties (e.g., solubility) to desired values. This method is frequently used for aliphatic and aromatic-aliphatic polyesters as well. 

TABLE 2.9 Melting Point, Tm (°C), of Unsubstituted and Methyl-substituted Aliphatic and Aromatic-Aliphatic Polyesters... 

In addition to the pathways depicted above, a 4-center concerted mechanism yielding ketenes has been reported during die vacuum pyrolysis of aliphatic polyesters (Scheme 2.4).89,90... 

Structure and Properties of Important Polyesters 2.2.2.1 Aliphatic Polyesters... 

Due to low hydrolytic and chemical resistance and to low melting point, aliphatic polyesters have long been considered to be limited to applications such as plasticizers or macromonomers for the preparation of polyurethane foams, coatings, or... 

PET, PTT, and PBT have similar molecular structure and general properties and find similar applications as engineering thermoplastic polymers in fibers, films, and solid-state molding resins. PEN is significantly superior in terms of thermal and mechanical resistance and barrier properties. The thermal properties of aromatic-aliphatic polyesters are summarized in Table 2.6 and are discussed above (Section 2.2.1.1). 

Polyester block copolymers can be defined as (AB) -type alternating multiblock copolymers composed of flexible aliphatic polyester or polyether blocks (A-type blocks) and rigid high-melting aromatic-aliphatic polyester blocks IB-type blocks) (Formula 2.2). 

TPEs associating both rigid and soft polyester blocks have also been described. They cannot be obtained by the melt polyesterification used for polyesterether TPEs, since interchange reactions would yield random—rather than block — copolyesters. The preferred method involves the reaction of OH-terminated aliphatic and aromatic-aliphatic polyesters with chain extenders such as diisocyanates and results in copoly(ester-ester-urethane)s. 

Although low-molar-mass aliphatic polyesters and unsaturated polyesters can be synthesized without added catalyst (see Sections 2.4.1.1.1 and 2.4.2.1), the presence of a catalyst is generally required for the preparation of high-molar-mass polyesters. Strong acids are very efficient polyesterification catalysts but also catalyze a number of side reactions at elevated temperature (>160°C), leading to polymers of inferior quality. Acid catalysts are, therefore, not much used. An exception is the bulk synthesis of hyperbranched polyesters reported in Section 2.4.5.1, which is carried out at moderate temperature (140°C) under vacuum in the presence of p-toluene sulfonic acid catalyst. The use of strongly acidic oil-soluble catalysts has also been reported for the low-temperature synthesis of polyester oligomers in water-in-oil emulsions.216... 

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