Research ArticleMATERIALS SCIENCE

Claisen thermally rearranged (CTR) polymers

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Science Advances  29 Jul 2016:
Vol. 2, no. 7, e1501859
DOI: 10.1126/sciadv.1501859
  • Fig. 1 General schemes of TR polymers, first description of the Claisen rearrangement, and aromatic Claisen rearrangement.
  • Fig. 2 Mass loss and absorbance spectra of CO2 as a function of temperature for the pristine and allyl-functionalized 6FDA-HAB polymers.
  • Fig. 3 Proposed mechanism.

    Claisen rearrangement is just the first step of the process.

  • Fig. 4 Physical appearance and mechanical robustness for the CTR polymers.
  • Fig. 5 Evaluation of the CO2/CH4 separation properties as a function of the degree of conversion.

    Continuous lines represent the evolution of the CO2 permeability and dashed lines represent CO2/CH4 selectivity. Vertical dotted lines denote the results at the same treatment temperature for the CTR polymer (squares) and the classical TR polymer (circles).

  • Fig. 6 Robeson’s trade-off for the CO2/CH4 gas pair.

    Samples are represented by symbols as follows: circles for 6FDA-HAB; squares for 6FDA-HAB-allyl; and diamonds (17), triangles pointing down (29), and triangles pointing up (28) for literature data on the polymer 6FDA-HAB synthesized under the same conditions. The largest symbols are for samples thermally treated at 350°C, and small symbols are for the samples thermally treated at 450°C.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/2/7/e1501859/DC1

    fig. S1. IR spectra during the TGA as a function of the time (rate was 5°C/min) for pristine 6FDA-HAB polymer and allyl-functionalized 6FDA-HAB polymer.

    fig. S2. FTIR for the allyl-functionalized 6FDA-HAB polymer at different temperatures of thermal treatment.

    fig. S3. FTIR for the pristine and functionalized polymers derived from 6FDA-HAB before and after thermal rearrangement.

    fig. S4. 1H NMR for the polymer 6FDA-HAB.

    fig. S5. 1H NMR for the polymer 6FDA-HAB-allyl.

    fig. S6. Solid-state 13C NMR for the polymer 6FDA-HAB-allyl after different thermal treatments.

    fig. S7. Dynamic TGA for the pristine and functionalized polymers derived from 6FDA-BisAPAF, BTDA-BisAPAF, and PMDA-BisAPAF.

    fig. S8. CO2 solubility and diffusivity for the polymers studied in this work.

    fig. S9. Robeson’s trade-off for the separation CO2/N2 and O2/N2 gas pairs.

    fig. S10. High feed pressure experiments for 6FDA-HAB-allyl thermally treated at 350°C.

    table S1. Characteristic thermal points for the rearrangement and degradation temperature for the pristine and functionalized polymers derived from 6FDA-HAB.

    table S2. Mechanical properties of the polymers under study.

    table S3. Rearrangement properties for all the polymers synthesized in this work.

    table S4. Results for the permeability of different pure gases and selectivity of different pairs of gases at 1 bar feed pressure and 30°C.

    table S5. Physical properties of precursor allyl-functionalized polyimide (6FDA-HAB-allyl)– and allyl-TR-PBO–derived membranes.

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. IR spectra during the TGA as a function of the time (rate was 5°C/min) for pristine 6FDA-HAB polymer and allyl-functionalized 6FDA-HAB polymer.
    • fig. S2. FTIR for the allyl-functionalized 6FDA-HAB polymer at different temperatures of thermal treatment.
    • fig. S3. FTIR for the pristine and functionalized polymers derived from 6FDA-HAB before and after thermal rearrangement.
    • fig. S4. 1H NMR for the polymer 6FDA-HAB.
    • fig. S5. 1H NMR for the polymer 6FDA-HAB-allyl.
    • fig. S6. Solid-state 13C NMR for the polymer 6FDA-HAB-allyl after different thermal treatments.
    • fig. S7. Dynamic TGA for the pristine and functionalized polymers derived from 6FDA-BisAPAF, BTDA-BisAPAF, and PMDA-BisAPAF.
    • fig. S8. CO2 solubility and diffusivity for the polymers studied in this work.
    • fig. S9. Robeson’s trade-off for the separation CO2/N2 and O2/N2 gas pairs.
    • fig. S10. High feed pressure experiments for 6FDA-HAB-allyl thermally treated at 350°C.
    • table S1. Characteristic thermal points for the rearrangement and degradation temperature for the pristine and functionalized polymers derived from 6FDA-HAB.
    • table S2. Mechanical properties of the polymers under study.
    • table S3. Rearrangement properties for all the polymers synthesized in this work.
    • table S4. Results for the permeability of different pure gases and selectivity of different pairs of gases at 1 bar feed pressure and 30°C.
    • table S5. Physical properties of precursor allyl-functionalized polyimide (6FDA-HAB-allyl– and allyl-TR-PBO–derived membranes.

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