Poly lacticity

Because lactic acid has both hydroxyl and carboxyl functional groups, it undergoes iatramolecular or self-esterificatioa and forms linear polyesters, lactoyUactic acid (4) and higher poly(lactic acid)s, or the cycUc dimer 3,6-dimethyl-/)-dioxane-2,5-dione [95-96-5] (dilactide) (5). Whereas the linear polyesters, lactoyUactic acid and poly(lactic acid)s, are produced under typical condensation conditions such as by removal of water ia the preseace of acidic catalysts, the formation of dilactide with high yield and selectivity requires the use of special catalysts which are primarily weakly basic. The use of tin and ziac oxides and organostaimates and -titanates has been reported (6,21,22). 

Polylactide is the generaUy accepted term for highly polymeric poly(lactic acid)s. Such polymers are usuaUy produced by polymerization of dilactide the polymerization of lactic acid as such does not produce high molecular weight polymers. The polymers produced from the enantiomeric lactides are highly crystalline, whereas those from the meso lactide are generaUy amorphous. UsuaUy dilactide from L-lactic acid is preferred as a polymerization feedstock because of the avaUabUity of L-lactic acid by fermentation and for the desirable properties of the polymers for various appUcations (1,25). 

Polymer Blends. The miscibility of poly(ethylene oxide) with a number of other polymers has been studied, eg, with poly (methyl methacrylate) (18—23), poly(vinyl acetate) (24—27), polyvinylpyrroHdinone (28), nylon (29), poly(vinyl alcohol) (30), phenoxy resins (31), cellulose (32), cellulose ethers (33), poly(vinyl chloride) (34), poly(lactic acid) (35), poly(hydroxybutyrate) (36), poly(acryhc acid) (37), polypropylene (38), and polyethylene (39). 

Other blends such as polyhydroxyalkanoates (PHA) with cellulose acetate (208), PHA with polycaprolactone (209), poly(lactic acid) with poly(ethylene glycol) (210), chitosan and cellulose (211), poly(lactic acid) with inorganic fillers (212), and PHA and aUphatic polyesters with inorganics (213) are receiving attention. The different blending compositions seem to be limited only by the number of polymers available and the compatibiUty of the components. The latter blends, with all natural or biodegradable components, appear to afford the best approach for future research as property balance and biodegradabihty is attempted. Starch and additives have been evaluated ia detail from the perspective of stmcture and compatibiUty with starch (214). 

In order to become useful dmg delivery devices, biodegradable polymers must be formable into desired shapes of appropriate size, have adequate dimensional stability and appropriate strength-loss characteristics, be completely biodegradable, and be sterilizahle (70). The polymers most often studied for biodegradable dmg delivery applications are carboxylic acid derivatives such as polyamides poly(a-hydroxy acids) such as poly(lactic acid) [26100-51-6] and poly(glycolic acid) [26124-68-5], cross-linked polyesters poly(orthoesters) poly anhydrides and poly(alkyl 2-cyanoacrylates). The relative stabiUty of hydrolytically labile linkages ia these polymers (70) is as follows ... 

FIGURE 9.32 Analysis of biodegradable poly(lactic acid). Columns PSS PFG 100 + 1000. Eluent TFE + 0.1 M NatFat. Temp 2S°C. Detection UV 230 nm, Rl. Calibration PSS PMMA ReadyCal kit. 

Most of the chiral membrane-assisted applications can be considered as a modality of liquid-liquid extraction, and will be discussed in the next section. However, it is worth mentioning here a device developed by Keurentjes et al., in which two miscible chiral liquids with opposing enantiomers of the chiral selector flow counter-currently through a column, separated by a nonmiscible liquid membrane [179]. In this case the selector molecules are located out of the liquid membrane and both enantiomers are needed. The system allows recovery of the two enantiomers of the racemic mixture to be separated. Thus, using dihexyltartrate and poly(lactic acid), the authors described the resolution of different drugs, such as norephedrine, salbu-tamol, terbutaline, ibuprofen or propranolol. 

Table 5-1. Enantioselectivities determined for several drugs. All experiments were performed at room temperature, except those marked with, which were performed at 4 °C. In some cases a lipophilic anion was used to facilitate the solubilization of the drug in the organic phases (PFj = hexafluorophosphate BPh = tetraphenyl borate). DHT = dihexyl tartrate DBT = dibenzoyl tartrate PLA = poly (lactic acid). ...

Lactic acid and levulinic acid are two key intermediates prepared from carbohydrates [7]. Lipinsky [7] compared the properties of the lactide copolymers [130] obtained from lactic acid with those of polystyrene and polyvinyl chloride (see Scheme 4 and Table 5) and showed that the lactide polymer can effectively replace the synthetics if the cost of production of lactic acid is made viable. Poly(lactic acid) and poly(l-lactide) have been shown to be good candidates for biodegradeable biomaterials. Tsuji [131] and Kaspercejk [132] have recently reported studies concerning their microstructure and morphology. 

RAFT polymerization has been used to prepare poly(ethylene oxide)-/ /wA-PS from commercially available hydroxy end-functional polyethylene oxide).4 5 449 Other block copolymers that have been prepared using similar strategies include poly(ethylene-co-butylene)-6/oci-poly(S-eo-MAH), jl poly(ethylene oxide)-block-poly(MMA),440 polyethylene oxide)-Moe -poly(N-vinyl formamide),651 poly(ethylene oxide)-Wot A-poly(NlPAM),651 polyfethylene ox de)-b ock-polyfl,1,2,2-tetrahydroperfluorodecyl acrylate),653 poly(lactic acid)-block-poly(MMA)440 and poly( actic acid)-6focA-poly(NIPAM),4 8-<>54... 

Polyester chemistry is the same as studied by Carothers long ago, but polyester synthesis is still a very active field. New polymers have been very recently or will be soon commercially introduced PTT for fiber applications poly(ethylene naph-thalate) (PEN) for packaging and fiber applications and poly(lactic acid) (PLA), a biopolymer synthesized from renewable resources (corn syrup) introduced by Dow-Cargill for large-scale applications in textile industry and solid-state molding resins. Polyesters with unusual hyperbranched architecture also recently appeared and are claimed to find applications as crosstinkers, surfactants, or processing additives. 

Special mention must be made of poly(lactic acid), a biodegradable/bio-resorbable polyester, obtained from renewable resources through fermentation of com starch sugar. This polymer can compete with conventional thermoplastics such as PET for conventional textile fibers or engineering plastics applications. Hie first Dow-Cargill PLA manufacturing facility is scheduled to produce up to 140,000 tons of Nature Works PLA per year beginning in 200245 at an estimated price close to that of other thermoplastic resins U.S. l/kg.46 Other plants are planned to be built in the near future.45... 

Poly(Lactic Acid) as a Biopolymer-Based Nano-Composite... 

Ali, F., Chang, Y., Kang, S.C., Yoon, J.Y. 2009. Thermal, mechanical and rheological properties of poly (lactic add)/epoxidized soybean oil blends. Polymer Bulletin. 62 91-98. 

Al-Mulla, E.A.J., Suhail, A. H. and Aowda, S. 2011. A. New biopolymer nanocomposites based on epoxidized soybean oil plastidzed poly(lactic add)/fatty nitrogen compounds modified clay Preparation and characterization. Industrial Crops and Products 33. 23-29. 

Noda, L, Satkowski, M.M., Dowrey, A.E. and Marcott, C. 2004. Polymer alloys of nodax copolymers and poly(lactic acid). Macromolecular Bioscience 4 269-275. 

Rasal, R.M., Janorkar, A.V. and Hirt, D.E. 2010. Poly(lactic acide) modifications. Progress in Polymer Science 33 338-356. 

Xu, Y. and Qu, J. 2009. Mechanical and rheological properties of epoxidized soybean oil plasticized poly(lactic acid). Journal of Applied Polymer Science 112 3185 - 3191. 

Biopolymers conventionally and chemically synthesised and the monomers are obtained from agro-resources, e.g., the poly-lactic acids or PL As... 

Lactic acid oligomer microspheres containing aclarubicin have been studied for selective lymphatic delivery. Low (less than 10,000 molecular weight oligomers were used to produce microspheres designed to release drug over a 30-day period (99). Additives have been used to alter the release rate of aclarubicin-loaded poly(lactide) microspheres (100). Mitomycin C was incorporated into poly(lactic... 

Hydrocortisone microspheres (108,109) and films (110) based on poly(lactic acid) have been investigated. A cage implant technique was used to study the performance of monolithic poly (DL-lactide) films loaded with hydrocortisone acetate (110). Films 1.5 x 0.6 cm were inserted into titanium wire-mesh cages 3.5 x 1.0 cm. The cages were implanted in the backs of rats and the inflammatory exudate was sampled periodically. The white cell concentration in the samples was lower than that of controls at all times during the 21-day test. 

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