Novel ternary block copolymerization of carbon dioxide with cyclohexene oxide and propylene oxide using zinc complex catalyst

Abstract

Block copolymers of poly (propylene carbonatecyclohexyl carbonate) (PPC-PCHC) were successfully synthesized by a one-pot method with the zinc complex catalyst (Zn2G). The IR and 1 H-NMR and 13 C-NMR spectra verified the introducing of PCHC segments in the copolymers. The GPC curves of the copolymers appeared only one peak and the DSC results showed three glass transition temperatures at 40°C, 66°C and 115°C, indicating the three-block copolymer structure. TGA tests revealed that the thermal decomposition temperature of the synthesized block copolymers increased up to about 300°C. The mechanical properties proved to be also enhanced greatly as evidenced by static and dynamic mechanical tests. The thermal and mechanical properties of the resultant block copolymers lay between those of PPC and PCHC, demonstrating the desired properties of a polymer can be achieved via block copolymerization.

Study on Thermal Decomposition Behaviors of Terpolymers of Carbon Dioxide, Propylene Oxide, and Cyclohexene Oxide

“…The synthesized copolymers containing polycarbonates and polyesters are terpolymers as Scheme 1. These have proven by our previous paper [15]. 1 H NMR spectrum of the purified terpolymer shown in Figures S1–S4 demonstrates the formation of ester and carbonate linkages.…”

“…The di-block PPC-PCHC copolymerization was carried out using ‘one pot, two steps’ method in a 500 mL stainless steel autoclave equipped with a mechanical stirrer [15]. A multi-component catalyst (Zn2G) was introduced into the autoclave and the autoclave with the catalyst inside was dried for 24 h under vacuum at 80 °C and then cooled down to room temperature.…”

“…Similarly, the tri-block polymer PCHC-PPC-PCHC was synthesized by using the ‘one pot, three steps’ method. The first step was the copolymerization of CO 2 with CHO, which is followed by the copolymerization of CO 2 with PO, and then the copolymerization of CO 2 with CHO again [15]. The random copolymer poly (propylene cyclohexene carbonate) (PPCHC) was prepared by terpolymerization of CO 2 , PO, and CHO [14].…”

“…It has also been found that PPC is easily decomposed to cyclic carbonate by the unzipping reaction, which is initiated by the free hydroxyl terminal groups [12,13]. In order to enhance the thermal properties of PPC, a third monomer cyclohexene oxide (CHO) copolymerizing with CO 2 and PO is considered as a profitable mean [14,15]. However, the thermal degradation kinetics of the terpolymer has not been investigated until now.…”

Inhibitory effect of hydrogen bonding on thermal decomposition of the nanocrystalline cellulose/poly(propylene carbonate) nanocomposite

“…By introducing the third monomers, including lactide (LA), cyclohexene oxide (CHO), caprolactone (CL) and γ‐butyrolactone (BL) into the PO‐CO 2 copolymerization system, the thermal properties of the resultant terpolymers could be clearly improved. However, this method is considered to be high cost because introduction of the third monomer into the PO‐CO 2 copolymerization system requires effective catalyst systems for keeping high monomers' conversion and complex post‐treatment method for purifying the product.…”