Internal plasticization of poly(vinyl) chloride using glutamic acid as a branched linker to incorporate four plasticizers per anchor point

Abstract

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) by grafting acrylate copolymers via copper‐mediated atom transfer radical polymerization

“…Info (Table S1), all showing values higher than 70%. Plasticization efficiency increases with increasing percentage of P2EEA ratio, attesting to the efficiency of the polyether functionality as PVC plasticizer 13,14,26,27 …”

“…Polyethers have been utilized by a number of researchers as highly effective internal plasticizers for PVC. 13,14,26,27 Polyether chains tend to be more effective compared to analogous materials with straight-chain or branched alkyl groups. Multiple groups have demonstrated good compatibility between PVC and PBA segments in graft copolymers.…”

“…This is referred to as “internal plasticization.” The flexibility of a polymer is indicated by its glass transition temperature ( T g ), with lower T g values observed for more flexible materials. Different nucleophilic substitution methods have been explored for chemically attaching plasticizers to PVC, including sulfide linkages, 10–14 amine linkages, 15–17 and triazole linkages 18–27 . All of these methods require three or more synthetic steps.…”

“…Different nucleophilic substitution methods have been explored for chemically attaching plasticizers to PVC, including sulfide linkages, [10][11][12][13][14] amine linkages, [15][16][17] and triazole linkages. [18][19][20][21][22][23][24][25][26][27] All of these methods require three or more synthetic steps. The lowest Tg of -42 °C reported to date was achieved in three steps using 84 wt % of an attached plasticizer by the Braslau group.…”

Advances in Internal Plasticization of PVC: Copper-Mediated Atom-Transfer Radical Polymerization from PVC Defect Sites To Form Acrylate Graft Copolymers

“…Studies using the nucleophilic-substitution approach have focused on sulfides, 3,4 amines, 5 and azides (to form triazole linkages). [6][7][8][9][10][11][12][13][14][15][16] Previous work in this laboratory highlighted the use of thermal azide/alkyne Huisgen cycloadditions to attach plasticizers to PVC. 6,12,14,15 However, the nucleophilic-substitution approach to attaching plasticizers requires at least three synthetic steps from PVC, which is impractical on an industrial scale.…”