Multiarm hyperbranched polyester‐b‐Poly(ε‐caprolactone):Plasticization effect and migration resistance for PVC

Abstract

A series of multiarm structure hyperbranched polyester‐b‐poly(ε‐caprolactone) (HEPCLs) with different lengths of poly(ε‐caprolactone) (PCL) segments (s = 3, 6, 7, 8) were synthesized. Hyperbranched polyester (HE) was synthesized from glycidol and succinic anhydride and used as a macromolecular polymerization initiator for ε‐caprolactone. The HEPCLs were used as polyvinyl chloride (PVC) plasticizers and the mechanical properties, thermal properties, morphology, and migration stabilities of PVC films were explored. The plasticizing efficiency increased with the increase in PCL segments, and the plasticizing efficiency of HEPCL8 exceeded that of dioctyl phthalate. Scanning electron microscopy and solid‐state 1H NMR showed that the HEPCLs possess better compatibility with PVC than HE. Moreover, HEPCLs exhibited excellent migration stability even at very harsh condition, indicating that HEPCLs can be used as no‐migration PVC plasticizers in medical products, children's toys, and food packaging. J. VINYL ADDIT. TECHNOL., 26:35–42, 2020. © 2019 Society of Plastics Engineers

Recent Attempts in the Design of Efficient PVC Plasticizers with Reduced Migration

“…Similar studies were carried out by Li et al [ 50 ] The new plasticizer was synthesized through a reaction of glycidyl and succinic anhydride. In the second step, the obtained hyperbranched polyester acted as an initiator in reactions with ɛ-caprolactone via ring-opening polymerization.…”

“…In comparison to their linear counterparts, hyperbranched plasticizers exhibit high terminal functional group concentrations and, therefore, are able to increase free volume in polymer matrices. On the other hand, a high molecular weight plasticizer is usually difficult to process, especially because of its higher viscosity [ 48 , 49 , 50 , 51 ].…”

Effects of hetero‐armed star‐shaped PCL‐PLA polymers with POSS core on thermal, mechanical, and morphological properties of PLA

“…The addition of SPLA polymers caused an increase as expected due to the four flexible PCL arms in its structure, a slight increase is observed with the increase in arm length of the star polymer. Three‐dimensional molecular architecture has a significant influence on mechanical properties, and it was reported in the literature that branched PCL polymers gives better plasticizing effect than linear PCL and the increase of PCL segment in the material cause increments in mechanical properties 13,34,48,50 . Li et al investigated the effect of different CL segment lengths by synthesizing multiarmed hyperbranched polyester‐ b ‐PCL and found that it significantly improved the compatibility and plasticization efficiency of PVC 50 .…”

“…Threedimensional molecular architecture has a significant influence on mechanical properties, and it was reported in the literature that branched PCL polymers gives better plasticizing effect than linear PCL and the increase of PCL segment in the material cause increments in mechanical properties. 13,34,48,50 Li et al investigated the effect of different CL segment lengths by synthesizing multiarmed hyperbranched polyester-b-PCL and found that it significantly improved the compatibility and plasticization efficiency of PVC. 50 As seen in Figure 4(b), a tremendous increase was observed when PDI was added to PLA/SPLA20 system especially in 90/10 blends, showing that the stronger interaction occurs between PLA and SPLA20 polymer in the presence of PDI.…”

“…13,34,48,50 Li et al investigated the effect of different CL segment lengths by synthesizing multiarmed hyperbranched polyester-b-PCL and found that it significantly improved the compatibility and plasticization efficiency of PVC. 50 As seen in Figure 4(b), a tremendous increase was observed when PDI was added to PLA/SPLA20 system especially in 90/10 blends, showing that the stronger interaction occurs between PLA and SPLA20 polymer in the presence of PDI. This is the prove that SPLA20 has the most appropriate arm length for chain extension reactions of PDI.…”