Aliphatic polyesters copolymers

A number of commercially significant PC copolymers are produced. In addition to the previously discussed branched PCs (for extrusion and blow-molding applications) and copolymers of BPA with tetrabromo-BPA for enhanced flame retardancy, high-Tg polyester carbonate copolymers have been produced for a number of years (Bayer Apec , GE LEXAN PPC Tg approximately 190°C). Polyester carbonate copolymers can be produced via copolymerization of BPA with diacyl chlorides. Aromatic diadds produce high-Tg copolymers, while aliphatic diadds yield lower-Tg copolymers. A lower-Tg PC aliphatic polyester copolymer (GE LEXAN SP resin) exhibits enhanced flow and ductility in comparison to standard PC and is useful for thin-wall injection molding applications requiring ductility and ease of melt processability, such as personal communication devices. GE has recently introduced two new PC copolymers, a PC-siloxane copolymer (LEXAN EXL) and a copolymer of... 

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. 

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). 

Aliphatic polyesters based on monomers other than a-hydroxyalkanoic acids have also been developed and evaluated as drug delivery matrices. These include the polyhydroxybutyrate and polyhydroxy valerate homo- and copolymers developed by Imperial Chemical Industries (ICI) from a fermentation process and the polycaprolactones extensively studied by Pitt and Schindler (14,15). The homopolymers in these series of aliphatic polyesters are hydrophobic and crystalline in structure. Because of these properties, these polyesters normally have long degradation times in vivo of 1-2 years. However, the use of copolymers and in the case of polycaprolactone even polymer blends have led to materials with useful degradation times as a result of changes in the crystallinity and hydrophobicity of these polymers. An even larger family of polymers based upon hydroxyaliphatic acids has recently been prepared by bacteria fermentation processes, and it is anticipated that some of these materials may be evaluated for drug delivery as soon as they become commercially available. 

If the homopolymer decomposes at the fabrication temperature another approach is to make a copolymer that can be melt processed at a lower temperature. For example, polyhydroxybutyrate decomposes at the processing temperature (190°C), whereas the copolymer with valeric acid can be processed at 160°C without decomposition. These aliphatic polyesters are biodegradable and most importantly, the decomposition products are not toxic, hence their use in medical applications (e.g., sutures). 

To design amphiphilic and/or reactive copolymers containing aliphatic polyesters, one of the most promising approaches is copolymerization with functional monomers having protected reactive side-chain groups. Some kinds of monomers having reactive (hydrophilic) side-chain groups have been reported (Fig. 3). Recently, the synthesis of various types of functional polyesters has been reviewed [15-19],... 

The synthesis of block copolymers of polysaccharides and aliphatic polyesters has also been tried. But, many successful results were not reported because the reactivity of many hydroxyl groups on polysaccharides was an obstacle to the ROP of cyclic polyester or coupling reactions using terminal-activated polysaccharides. Li and Zhang reported the synthesis of maltoheptaose-b-PCL copolymers by ROP... 

Many kinds of nonbiodegradable vinyl-type hydrophilic polymers were also used in combination with aliphatic polyesters to prepare amphiphilic block copolymers. Two typical examples of the vinyl-polymers used are poly(/V-isopropylacrylamide) (PNIPAAm) [149-152] and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) [153]. PNIPAAm is well known as a temperature-responsive polymer and has been used in biomedicine to provide smart materials. Temperature-responsive nanoparticles or polymer micelles could be prepared using PNIPAAm-6-PLA block copolymers [149-152]. PMPC is also a well-known biocompatible polymer that suppresses protein adsorption and platelet adhesion, and has been used as the hydrophilic outer shell of polymer micelles consisting of a block copolymer of PMPC -co-PLA [153]. Many other vinyl-type polymers used for PLA-based amphiphilic block copolymers were also introduced in a recent review [16]. 

Nonionic hydrophilic PEO blocks have also been combined with a variety of other hydrophobic blocks, including PI [135], poly(amino acids) [136], aliphatic polyesters [137], etc. It is not possible to review all the published works on these copolymers due to space limitations. We will therefore only present a selected example. 

It is known that increased char yield is usually associated with improved flammability behavior ( 1). This can be understood if one considers that the volatile flammable products can only diffuse with difficulty through the char, and that the thermal conductivity of a porous char layer is relatively poor (2). The structure of the polymer can contribute to the amount of char formed based on the character of the functional groups present and the nature of the backbone (2,3). Ritchie ( ) found that for a series of unsaturated polyesters and their copolymers, the temperatures at which carbon dioxide is eliminated was in the range of 280 to 345°C depending on the structure of the polyester. Aliphatic polyesters and their copolymers have less thermal... 

The purpose of this review is to report on the recent developments in the macromolecular engineering of aliphatic polyesters. First, the possibilities offered by the living (co)polymerization of (di)lactones will be reviewed. The second part is devoted to the synthesis of block and graft copolymers, combining the living coordination ROP of (di)lactones with other living/controlled polymerization mechanisms of other cyclic and unsaturated comonomers. Finally, several examples of novel types of materials prepared by this macromolecular engineering will be presented. 

Last but not least, some of us have recently synthesized polyimide-aliphatic polyester triblock and graft copolymers in collaboration with Hedrick and his coworkers [ 97,98]. Well-defined aminophenyl or diaminophenyl end-functional polyester oligomers have been synthesized on purpose and used as end-cappers or macromonomers leading to the aforementioned triblock or graft copolymers, respectively. The polyimide-polyester copolymers so obtained proved to be highly efficient promoters of polyimide nanofoams (for more details see Sect. 4.2). 

Biodegradable polyester-based nanoparticles have also been studied, especially in the biomedical domain. Like microelectronics, biomedical research follows the rule smaller is better . A typical example of nanoparticles based on the aliphatic polyester engineering by living ROP is provided by the poly(CL-h-GA) copolymers which form stable colloidal dispersions in organic solvents such as toluene and THF without the need of any additional surfactant [27]. The poly(CL-h-GA) particles form a new class of stable non-aqueous dispersions in... 

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