Alan Wayne White

The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends

In this account, we report our findings on blends of cellulose acetate having a degree of substitution (DS) of 2.49 (CA2.5) with a cellulose acetate having a DS of 2.06 (CA2.0). This blend system was examined over the composition range of 0–100% CA2.0 employing both solvent casting of films (no plasticizer) and thermal processing (melt-compressed films and injection molding) using poly(ethylene glycol) as a common plasticizer. All thermally processed blends were optically clear and showed no loss in optical quality after storage for several months. Thermal analysis and measurement of physical properties indicate that blends in the middle composition range are partially miscible, while those at the ends of the composition range are miscible. We suggest that the miscibility of these cellulose acetate blends is influenced primarily by the monomer composition of the copolymers. Bench-scale simulated municipal composting confirmed the biodestructability of these blends and indicated that incorporation of a plasticizer accelerated the composting rates of the blends.In vitro aerobic biodegradation testing involving radiochemical labeling conclusively demonstrated that both the lower DS CA2.0 and the plasticizer significantly enhanced the biodegradation of the more highly substituted CA2.5.

Biodegradation of Cellulose Esters: Composting of Cellulose Ester-Diluent Mixtures

Abstract A number of polymers such as polylactic acid (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB), Matter-Bi, cellulose acetate (CA) with different degrees of substitution (DS), and cellulose ester–diluent mixtures have been evaluated in a static, bench-scale simulated municipal compost environment. Of the polymers evaluated, cellulose acetate (DS > 2.2), poly(hydroxybutyrate-co-valerate) (PHBV), and PCL exhibited the fastest composting rates, completely disappearing after 14 days. Optically clear resins were prepared from CA (DS = 2.06) and triethylcitrate (TEC) by thermal compounding, and the resins were converted to compression-molded film and injection-molded bars for composting studies. A series of miscible blends consisting of cellulose acetate propionate (CAP) and poly(ethylene glutarate) (PEG) or poly(-tetramethylene glutarate) (PTG) were also prepared and evaluated in composting. In addition to measured weight loss, samples were removed from the compost at different intervals and eva...

Composting of miscible cellulose acetate propionate-aliphatic polyester blends

A series of miscible blends consisting of cellulose acetate propionate (CAP) and poly(ethylene glutarate) (PEG) or poly(tetramethylene glutarate) (PTG) were evaluated in a static bench-scale simulated municipal compost environment. Samples were removed from the compost at different intervals, and the weight loss was determined before evaluation by gel permeation chromatography, scanning electron microscopy, and1H NMR. The type of polyester (PEG versus PTG) in the blend made no difference in composting rates. At fixed CAP degree of substitution (DS), when the content of polyester in the blend was increased, the rate of composting and the weight loss due to composting increased. When the CAP was highly substituted, little degradation was observed within 30 days and almost all of the weight loss was ascribed to loss of polyester. Although the polyester was still observed to degrade faster, when the CAP DS was below approximately 2.0, both components are observed to degrade. The data suggests that initial degradation of the polyester is by chemical hydrolysis and the rate of this hydrolysis is very dependent upon the temperature profile of the compost and upon the DS of the CAP.

The relationship between blend miscibility and biodegradation of cellulose acetate and poly(ethylene Succmate) blends

The miscibility of cellulose acetate (CA; degree of substitution = 2.5) and poly(ethylene succinate) (PES) has been investigated using a variety of thermal techniques and by solid-state carbon13 NMR spectroscopy. The blends containing greater than ca. 70% CA were found to be miscible. In the case of blends containing less than ca. 70% CA, a combination of thermal and NMR analyses suggests that these blends are not fully miscible on a 2.5- to 5-nm scale. On the scale which can be probed by dynamic mechanical thermal analysis (15 nm), the low-percentage CA blends exhibit “significant local concentration fluctuations≓. Investigation of the biodegradation of the blend components and of the blends revealed that PES degraded relatively rapidly and that CA degraded slowly. The blends degraded at a rate essentially identical to that of CA. Miscibility (75% CA blend) or crystallization of PES (30% CA blend) had no significant effect. These data suggest that a significant mode of degradation ofPES during composting involves chemical hydrolysis of the polymer followed by biological assimilation of monomers. Degradation of the blends is initiated in the amorphous phase. Because CA is a significant component of the amorphous phase, a small amount of CA significantly impacts the biodegradation rates of the blends.