and that the grafting density was enough to enhance the mobility of XG chains, resulting in decreased Tg. This observation was consistent with previous results (from SEC and FTIR) and further proves that the grafting reaction was successful. In addition to this,
the glass transition (Tg), the crystallization (Tc ) and the melting (Tm) temperatures of the grafted PLLA are visible in Fig. 7. The melting point was the same as that for non-grafted PLLA. However,the glass transition, as well as the crystallization temperature,was significantly increased by the grafting. The main reason why these temperatures are increased is that grafted PLLA is covalently attached and the chain mobility is restricted compared with pure PLLA. Thermal analysis via TGA was used to study the degradation behavior of grafted XG compared with the unmodified XG and
free PLLA. The thermogram and its first derivative (DTGA) are shown in Fig. 8 for native XG, grafted XG and free PLLA from the grafting reaction. As can be seen, the curves of grafted XG were between PLLA and native XG in the degradation temperature region (around 300 ◦C). This once again confirms that PLLA chains were grafted to XG, resulting in a decrease in the degradation temperature.
Fig. 9. Moisture sorption isotherms for native XG, PLLA-grafted native XG and PLLAgrafted enzymatically modified XG.
3.3. Moisture uptake
DVS analysis was carried out to see if the grafting of hydrophobic PLLA chains leads to a decrease in the water uptake of XG. Fig. 9 shows the moisture sorption isotherms for native XG as well as for PLLA-grafted XG and PLLA-grafted modified XG.No differences were observed between native XG and grafted XG in terms of moisture uptake. On the other hand, grafting of PLLA chains to modified XG (with lesser number of galactose side groups)resulted in a relative decrease in moisture content of around 30% (in the practically useful RH of 30–80%) as compared to the native XG.It was demonstrated in a previous study that enzymatic treatment and the removal of around 30% of galactose side groups did not change water sorption properties of XG (Kochumalayil et al., 2010).
The difference that can be observed here is then exclusively due to the grafting of hydrophobic PLLA chains from the surface of XG.The grafting appeared to be more efficient (higher grafting density and chain length) for the modified XG, causing decreased moisture uptake.
4. Conclusions
The chemical modification of high molar mass xyloglucan (XG) with poly(l-lactic acid) was investigated in this study. PLLA chains were successfully grafted from XG via ring-opening polymerization of l-lactide. The presence of moisture in the reaction system, the nature of the substrate and the ratio of substrate/monomer are key parameters in accomplishing good grafting efficiency; minimization of residual water, enzymatic removal of galactose residues from XG, and increase in the substrate/monomer ratio improve the efficiency of the grafting, i.e., increase the length of the grafted
chains (on the assumption that the grafted chains follow the same trend as the free benzyl alcohol-initiated chains). Grafting with PLLA decreased the glass transition temperature of XG from 252 ◦C to 216 ◦C. Finally, the grafting of hydrophobic chains on the surface of the hydrophilic XG led to changed interaction with water: the water uptake of PLLA-grafted XG was at best reduced about 30% (in the region of RH from 30% to 80%) compared to native XG, and the water solubility was also significantly decreased.
PLLA-grafted XG is a new high molar mass compatibilizer for potential use in cellulose fiber-reinforced PLLA composite applications. XG has strong affinity for cellulose and the grafted PLLA may form physical entanglements with the PLLA matrix. The concept