Polymeric phthalates: Potential nonmigratory macromolecular plasticizers

Abstract

The synthesis of 4-vinyl-1,2-phthalate esters via Suzuki coupling is described, followed by nitroxide-mediated polymerization to prepare short homopolymers (degree of polymerization [DP] ¼ 10-40, polydispersity index [PDI] ¼ 1.1-1.3). Random copolymers with n-butyl acrylate (NBA) were prepared. Copolymers rich in phthalate ester residues of medium lengths (DP ¼ 16-48, PDI ¼ 1.2-1.8) and of shorter lengths (DP ¼ 8-17, PDI ¼ 1.2-1.3) were prepared. Copolymers rich in NBA residues were also prepared (DP ¼ 13-19, PDI ¼ 1.2-1.3). All polymers were oily liquids, with glass transitions temperatures undetected between 75 and À40 C, indicating these polymeric phthalates hold promise as potential nonmigratory phthalate plasticizers.

Evaluating effects of biobased 2,5‐furandicarboxylate esters as plasticizers on the thermal and mechanical properties of poly (vinyl chloride)

“…To reduce or prevent the release of PAE plasticizers from products, reactive phthalates, crosslinking phthalates, and polymeric phthalates have been synthesized and investigated. However, the accelerated thermal degradation of the crosslinking products and the poor miscibility of reactive and polymeric products have limited their applications .…”

“…1,2 Therefore, PAEs have been banned from use in commodity applications by a variety of U.S. and European agencies on the basis of evidence that PAE plasticizers can trigger kidney lesions, 3 hepatic tumorigenesis, 4 reproductive malformations, 5 and other diseases. 6,7 To reduce or prevent the release of PAE plasticizers from products, reactive phthalates, 8 crosslinking phthalates, 9 and polymeric phthalates 10 have been synthesized and investigated. However, the accelerated thermal degradation of the crosslinking products and the poor miscibility of reactive and polymeric products have limited their applications.…”

Plasticiser loss from plastic or rubber products through diffusion and evaporation

“…To avoid the deterioration of polymer materials caused by plasticiser loss, several approaches have been used to hinder plasticiser migration. The most common way is to increase the molecular size of the plasticiser, which can be achieved by using polymeric plasticisers and oligomers, 64,65 and branched and starshape plasticisers. [66][67][68] The diffusivity of these plasticisers in polymers is low due to their large size, leading to slow plasticiser losses.…”

Covalently Linked Plasticizers: Triazole Analogues of Phthalate Plasticizers Prepared by Mild Copper‐Free “Click” Reactions with Azide‐Functionalized PVC

“…Recently, our group has investigated polymerized 4‐vinyl‐phthalates as an alternative to traditional phthalate plasticizers. These polymeric phthalates in PVC blends are expected to minimize plasticizer migration and are unlikely to be metabolized into endocrine disrupting chemicals . However a significant drawback to this approach is the multistep synthesis required to prepare the vinyl phthalate monomers.…”