A parametric study of the terminal maleation of polypropylene through an Alder Ene reaction

A study of the parameters that affect the Alder Ene reaction with respect to the synthesis of a terminally anhydride-functionalized polypropylene was carried out over a temperature range of 220–250°C using maleic anhydride concentrations of 2–12 mol equivalence with respect to the vinylidene group. As previously observed, a Lewis acid (i.e., SnCl₂ · 2H₂O) had a catalytic effect on the reaction at these temperatures, thereby improving anhydride content in the polymer for short reaction times. Increased temperature and maleic anhydride concentration had a positive effect on improving the incorporation of the succinyl anhydride moiety at the terminal site in polypropylene. Lower SnCl₂ · 2H₂O concentrations, likewise, improve the functionality of the product. The application of a second-order kinetic model to the measured succinyl anhydride results was not valid over the entire temperature range studied due to side reactions, particularly vinylidene isomerization, and homopolymerization of maleic anhydride. Ruthenium chloride has been examined as another possible catalyst candidate in the reaction and has been found to improve the level of anhydride incorporation in polypropylene compared to stannous chloride. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2371–2380, 1998     

Study on Direct Grafting Maleic Anhydride onto Poly(D,L-lactide-co-glycolide) Chains

Direct graft copolymerization of maleic anhydride (MAH) onto poly(D,L-lactide-co-glycolide) (PLGA) was performed by use of benzoyl peroxide (BPO) as initiator. Fourier transform infrared spectra, nuclear magnetic resonance, titration analysis of maleation extent and water contact angle were employed to characterize the obtained MPLGA. The effects of monomer concentration, initiator concentration and reaction temperature on the degree of maleation were investigated. The MPLGA scaffold was obtained by using NaCl as the porogen. The results showed that maleic anhydride was successfully grafted onto the PLGA chains. The monomer and initiator concentrations played an important role in the graft copolymerization; the extent of maleation first increased with increasing content of MAH and BPO and then declined. The extent of maleation continuously increased with increasing temperature to 100°C, and then the rate of increase decreased. The extent of maleation could be controlled in the range from 0.15 to 0.71% by adjusting the graft copolymerization conditions. The introduction of anhydride enhanced the water contact angle of PLGA. The MPLGA scaffold showed a network of interconnected pores ranging from 50 to 300 μm.