## 4 Precursors to Materials
### Miscellaneous  
In addition to the plethora of chemical transformations presented in the previous sections in which glycerol carbonate is involved, the versatility of this glycerol derivative has allowed it to be employed in singular polymerization reactions, leading to diversified products with significant potential for application in various materials. In this line, the synthesis of new fluorinated terpolymers bearing cyclocarbonate pendant groups to ensure the crosslinking of the polymer chains was reported [205]. The new cyclocarbonate- and triazole-functionalized fluorinated terpolymer **176** was obtained in three steps from chlorotrifluoroethylene **76**, as shown in Scheme 83. The glycerol carbonate vinyl ether monomer **11** was obtained with 45% yield via a transesterification reaction between GC **1a** and ethoxyethylene **177** under palladium catalysis. The key co-polymerization step involving **11**, **76**, and 2-chloroethyl vinyl ether **178** was catalyzed by \"butylperoxypivalate and proceeded in a HFP solution at 74 \({}^{\circ}\)C, leading to the terpolymer **179**. After two more steps, the triazolyl-modified terpolymer **176** was obtained as a membrane, which was removable from the glassy substrate via immersion in 1M aqueous hydrochloric acid. After the final conditioning process, it was verified that the developed semi-interpenetrating polymer network (semi-IPN) blended membranes presented lower water uptake and better mechanical properties compared to non-crosslinked membranes. In the same year, [PERSON] and co-workers [206] described the preparation of polyester resins derived from rosin acids for application as a xerographic toner. Rosin acids obtained from pulp byproduct (tall oil), gum, or wood rosims are more sustainable monomers than those from food biomass. Reacting renewable dehydrodiabetic acid **180** with GC **1a** (3.3 equivalent) in the presence of catalytic tetraethylammonium iodide at 150 \({}^{\circ}\)C provided a mixture of dehydrodiabetes **11e**, **181**, and **182**. After adding more **180**, the reaction was continued for 8 h at the same temperature to deliver a mixture of the monoesters **12e** and **181** (61.9% yield) and **182** (12.5%), together with the isomeric diesters  
**183** (12.4%) and **184** (5.3%). This mixture of **182**, **183**, **184**, and **12e** rosin adducts was reacted with various organic diacids to provide novel polyester resins with a glass transition of 35-53.9 \({}^{\circ}\)C, which is the suitable temperature range for toner applications (Scheme 84). **Scheme 84. Preparation of polyester resins. Conditions for _i_: **180** (0.330 mol), Et\({}_{4}\)NI (0.005 mol) and **1a** (1.1 mol) were reacted in a 1 L Parr 4020 reactor at 150 \({}^{\circ}\)C under N\({}_{2}\) atmosphere for 2 h; then, more acid **180** (0.670 mol) was added and the reaction was maintained at 150 \({}^{\circ}\)C for 8 h (>99% conversion). A promising approach in green and sustainable chemistry is the direct use of CO\({}_{2}\) by combining the coupling reaction and free-radical polymerization to efficiently produce polyacrylates bearing cyclic carbonate groups. In 2016, [PERSON], [PERSON] and co-workers [207] described the use of a new nano-lamellar double-metal cyanide complex, Zn-Co(III) DMCC/CTAB, a catalyst that allows the preparation of highly transparent polyacrylates with specific UV absorption. The reaction of CO\({}_{2}\) with glycidyl methacrylate **185** followed by free radical polymerization (FRP) of the resulting alkenyl carbonate ester DOMA **1s** provided new polyacrylates, known as PDOMAs (Scheme 85).