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. 2021 Feb 25;11(15):8782-8792.
doi: 10.1039/d0ra09630j. eCollection 2021 Feb 23.

Fabrication and characterization of the ternary composite catalyst system of ZnGA/RET/DMC for the terpolymerization of CO2, propylene oxide and trimellitic anhydride

Ningzhang Liu  1   2   3 , Chuanhai Gu  1   2   3 , Qinghe Wang  4 , Linhua Zhu  1   2   3 , Huiqiong Yan  1   2   3 , Qiang Lin  1   2   3   5
Affiliations

Fabrication and characterization of the ternary composite catalyst system of ZnGA/RET/DMC for the terpolymerization of CO2, propylene oxide and trimellitic anhydride

Ningzhang Liu et al. RSC Adv. .

Abstract

To achieve the poly(propylene carbonate trimellitic anhydride) (PPCTMA) with excellent performance, high molecular weight, enhanced yield and good thermal stability, the ternary composite catalyst system of zinc glutarate/rare earth ternary complex/double metal cyanide (ZnGA/RET/DMC) was proposed to perform the terpolymerization of CO2, propylene oxide and trimellitic anhydride. Since the crystallinity and surface activity point of Zn-Co DMC could significantly influence the catalytic ability, mechanical ball milling was applied to increase the surface area of the Zn-Co DMC catalyst with better surface activity point. Moreover, the ZnGA/RET/DMC composite catalytic system and polycarbonate products were comparatively evaluated by XRD, SEM, FT-IR, TGA, NMR, XPS and TEM. Experimental results showed that the ZnGA/RET/DMC composite catalyst system displayed outstanding synergistic effect on the terpolymerization of CO2, PO and TMA with better selectivity, activity, and higher molecular weight (M w) tercopolymer than those of the individual catalyst. According to optimum reaction conditions, the M w of PPCTMA could be up to 8.29 × 104 g mol-1, and the yield could be up to 66 gpolym/gcat. The alternating tercopolymer, PPCTMA, showed wonderful thermal stability and high decomposition temperature (TGA10% = 313 °C). A possible synergistic catalytic mechanism of the ZnGA/RET/DMC ternary composite catalyst system was also conjectured.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Reaction of CO2 with PO and TMA.
Fig. 1
Fig. 1. XRD patterns of the synthesized Zn–Co DMC with different ways.
Fig. 2
Fig. 2. SEM images of the Zn–Co DMC catalyst samples.
Fig. 3
Fig. 3. Comparisons of the FTIR spectra of the Zn–Co DMC samples synthesized for the specified time.
Fig. 4
Fig. 4. XRD patterns of the pure DMC, RET, ZnGA and ZnGA/RET/DMC composite catalyst.
Fig. 5
Fig. 5. SEM images of the DMC, RET, ZnGA and ZnGA/RET/DMC composite catalyst samples.
Fig. 6
Fig. 6. TEM images of the DMC, RET, ZnGA and ZnGA/RET/DMC composite catalyst samples.
Fig. 7
Fig. 7. XPS spectra of various DMC, RET, ZnGA and ZnGA/RET/DMC composite catalysts.
Fig. 8
Fig. 8. 1H and 13C NMR spectra of the tercopolymer PPCTMA synthesized by using ZnGA/RET/DMC as the catalyst.
Fig. 9
Fig. 9. FTIR spectra of PPCTMA.
Fig. 10
Fig. 10. TGA and DTA curves of the tercopolymer PPCTMA synthesized by the ZnGA/RET/DMC composite catalyst.
Scheme 2
Scheme 2. Proposed mechanism of the CO2/PO/TMA terpolymerization over the ZnGA/RET/DMC composite catalyst system.
See this image and copyright information in PMC

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