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Internal plasticization of polyvinyl chloride (PVC) using thermal azide‐alkyne Huisgen dipolar cycloaddition between azidized PVC and electron‐poor acetylenediamides incorporating a branched glutamic acid linker resulted in incorporation of four plasticizing moieties per attachment point on the polymer chain. A systematic study incorporating either alkyl or polyethylene glycol esters provided materials with varying degrees of plasticization, with depressed Tg values ranging from −1 °C to 62 °C. Three interesting trends were observed. First, Tg values of PVC bearing various internal plasticizers were shown to decrease with increasing chain length of the plasticizing ester. Second, branched internal plasticizers bearing triethylene glycol chains had lower Tg values compared to those with similar length long‐chain alkyl groups. Finally, thermogravimetric analysis of these internally plasticized PVC samples revealed that these branched internal plasticizers bearing alkyl chains are more thermally stable than similarity branched plasticizers bearing triethylene glycol units. These internal tetra‐plasticizers were synthesized and attached to PVC‐azide in three simple synthetic steps. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1821–1835

Internal plasticization of poly(vinyl chloride) (PVC) was achieved in one‐step using copper‐mediated atom transfer radical polymerization to graft different ratios of random n‐butyl acrylate and 2–2‐(2‐ethoxyethoxy)ethyl acrylate copolymers from defect sites on the PVC chain. Five graft polymers were made with different ratios of poly(butyl acrylate) (PBA) and poly(2–2‐(2‐ethoxyethoxy)ethyl acrylate) (P2EEA); the glass transition temperatures (Tg) of functionalized PVC polymers range from − 25 to − 50°C. Single Tg values were observed for all polymers, indicating good compatibility between PVC and grafted chains, with no evidence of microphase separation. Plasticization efficiency is higher for polyether P2EEA moieties compared with PBA components. The resultant PVC graft copolymers are thermally more stable compared to unmodified PVC. Increasing the reaction scale from 2 to 14 g produces consistent and reproducible results, suggesting this method could be applicable on an industrial scale.