Biodegradability, poly

It is evident that the area of water-soluble polymer covets a multitude of appHcations and encompasses a broad spectmm of compositions. Proteins (qv) and other biological materials ate coveted elsewhere in the Eniyclopedia. One of the products of this type, poly(aspartic acid), may be developed into interesting biodegradable commercial appHcations (70,71). 

Poly-P-hydroxybutyrate (PHB) is a biodegradable thermoplastic that is produced by several microorganism. The PHB synthesis has been characterized eutrophus and the operon iavolved ia PHB productioa has beea cloaed. Recombiaant E. coli straias that can produce high levels of... 

There are numerous further appHcations for which maleic anhydride serves as a raw material. These appHcations prove the versatiHty of this molecule. The popular artificial sweetener aspartame [22839-47-0] is a dipeptide with one amino acid (l-aspartic acid [56-84-8]) which is produced from maleic anhydride as the starting material. Processes have been reported for production of poly(aspartic acid) [26063-13-8] (184—186) with appHcations for this biodegradable polymer aimed at detergent builders, water treatment, and poly(acryHc acid) [9003-01-4] replacement (184,187,188) (see Detergency). 

Polymer—polymer iacompatibiHty encapsulation processes can be carried out ia aqueous or nonaqueous media, but thus far have primarily been carried out ia organic media. Core materials encapsulated tend to be polar soHds with a finite degree of water solubiHty. EthylceUulose historically has been the sheU material used. Biodegradable sheU materials such as poly(D,L-lactide) and lactide—glycoHde copolymers have received much attention. In these latter cases, the object has been to produce biodegradable capsules that carry proteias or polypeptides. Such capsules tend to be below 100 p.m ia diameter and are for oral or parenteral administration (9). 

Other bacterial strains identified as biodegrading poly(vinyl alcohol) iaclude Flavobacterium (95) 2in.dFicinetobacter (96) and many others, as well as fungi, molds, and yeasts (97). Industrial evaluations at Du Pont (98) and Air Products (99) iadicate that over 90% of poly(vinyl alcohol) entering wastewater treatment plants is removed, and hence no environmental pollution is likely. 

Poly(vinyl acetate), the precursor of poly(vinyl alcohol), hydroly2ed to less than 70%, is claimed to be nonbio degradable under conditions similar to those that biodegrade the fuUy hydroly2ed polymer (100) (see Vinylpolya rs poly (vinyl ACETATE polya rs). 

Anaerobically, poly(ethylene glycol) degrades slowly, although molecular weights up to 2000 daltons have been reported (177,178) to biodegrade. 

The biodegradation of poly(alkylene glycols) is hindered by their lack of water solubiUty, and only the low oligomers of poly(propylene glycol) are biodegradable with any certainty (179—181), as are those of poly(tetramethylene glycol) (182). A similar xo-oxidation mechanism to that reported for poly(ethylene glycol) has been proposed. 

Similar polyacetals were prepared by BASF scientists from CO-aldehydic aUphatic carboxyUc acids (189,190) and by the addition of poly(hydroxycarboxyhc acid)s such as tartaric acid to divinyl ethers (191) as biodegradable detergent polymers. 

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 Industrial Chemicals. Recendy, as some amino acids (eg, L-glutamic acid, L-lysine, glycine, DL-alanine, DL-methionine) have become less expensive chemical materials, they have been employed in various appHcation fields. Poly(amino acid)s are attracting attention as biodegradable polymers in connection with environmental protection (236). 

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 ... 

Poly(3-hydroxybutyrate—3-hydroxyvalerate) [80181 -31 -3] resin, produced from a bacterium during a sugar fermentation process, has been reported to be biodegradable, and its target markets include "flushables" such as feminine hygiene products and disposable diapers (99). 

Mention should also be made here of the extensive use of poly(vinyl alcohol) in potentially biodegradable applications. At appropriate hydroxyl contents these polymers will dissolve in water (see Chapter 14) and can apparently be conveniently washed away after use as a water-soluble packaging. Biodegradation does, however, appear to be slow and first requires an oxidative step involving enzymatic attack to a ketone such as polyenolketone, which then biodegrades more rapidly. 

Throughout the 1990s a large portion of the research and development effort for hot melt adhesives focused on developing adhesives that are either environmentally friendly or functional [69,81,82]. Environmentally friendly attributes include biodegradability, water dispersibility (repulpability), renewability, and water releasability. Biodegradable adhesives have been developed based on starch esters [83-86] and polyesters such as poly (hydroxy butyrate/hydroxy valerate) [87], poly(lactide) [88-91], and poly(hydroxy ether esters) [92-94]. All but the... 

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. 

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. 

Poly(malic acid) is of pharmaceutical interest because its chemical derivatives may harbor both tissue-specific homing molecules and therapeutic effectors to be used for tissue (tumor) targeting in chemotherapy [2]. Because of its efficient production by fermentation, its biodegradability and nontoxicity, it is also considered as raw material in the industrial production of detergents, glues, and plastic materials. 

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. 

---