Temperature dependences of gas transport parameters of ladder-like polyphenylsilsesquioxane

The temperature dependences of the diffusion, solubility, and permeability coefficients for ladder-like polyphenylsilsesquioxane (L-PPSQ) samples with molecular weights of 400, 600, and 1000 kDa were analyzed. A comparison, in terms of the gas transport parameters and temperature coefficients, with other silicon-containing polymers revealed that L-PPSQ is most similar to glassy polyvinyltrimethylsilane (PVTMS) rather than to polydimethylsiloxane (PDMS), which is structurally related to it. The heat of sorption values obtained for the studied samples using the temperature dependences are consistent with those from the literature for polytrimethylsilylpropyne (PTMSP), while their diffusion activation energies are more in agreement with PDMS and PVTMS, which may indicate the presence of enclosed free volume elements in L-PPSQ, comparable in size to the ones in PTMSP. The observed tendency of the permeability coefficient to increase with temperature confirms the dominant contribution of the diffusion component of permeability in L-PPSQ. The molecular weight of L-PPSQ was found to have no influence on its gas transport properties in the range of 400–1000 kDa. Therefore, the production of asymmetric and composite membranes is limited solely by the mechanical properties and solubility of L-PPSQ with different molecular weights. 

1. Robb W.L. Thin silicone membranes-their permeation properties and some applications. Ann. N. Y. Acad. Sci., 1968, vol. 146, no. 1, pp. 119–137. https://doi.org/10.1111/j.1749-6632.1968.tb20277.x.

2. Gringolts M.L., Bermeshev M.V., Starannikova L.E., Rogan Yu.V., Yampol’skii Yu.P., Finkel’shtein E.Sh. Synthesis and gas separation properties of metathesis polynorbornenes with different positions of one or two SiMe3 groups in a monomer unit. Polym. Sci., Ser. A, 2009, vol. 51, nos. 11–12, art. 1233–1240. https://doi.org/10.1134/S0965545X0911008X.

3. Bermeshev M.V., Syromolotov A.V., Gringolts M.L., Starannikova L.E., Yampolskii Y.P., Finkelshtein E.Sh. Synthesis of high molecular weight poly[3-{tris(trimethylsiloxy)silyl} tricyclononenes-7] and their gas permeation properties. Macromolecules, 2011, vol. 44, no. 17, pp. 6637–6640. https://doi.org/10.1021/ma201486d.

4. Chapala P., Bermeshev M., Starannikova L., Borisov I., Shantarovich V., Lakhtin V., Volkov V., Finkelshtein E. Synthesis and gas-transport properties of metathesis polytricyclononenes bearing three Me 3Si groups per monomer unit. Macromol. Chem. Phys., 2016, vol. 217, no. 17, pp. 1966–1976. https://doi.org/10.1002/macp.201600232.

5. Masuda T., Iguchi Y., Tang B.-Z., Higashimura T. Diffusion and solution of gases in substituted polyacetylene membranes. Polymer, 1988, vol. 29, no. 11, pp. 2041–2049. https://doi.org/10.1016/0032-3861(88)90178-4.

6. Sakaguchi T., Takeda A., Hashimoto T. Highly gas-permeable silanol-functionalized poly(diphenylacetylene)s: Synthesis, characterization, and gas permeation property. Macromolecules, 2011, vol. 44, no. 17, pp. 6810–6817. https://doi.org/10.1021/ma201280s.

7. Platé N.A., Bokarev A.K., Kaliuzhnyi N.E., Litvinova E.G., Khotimskii V.S., Volkov V.V., Yampol’skii Yu.P. Gas and vapor permeation and sorption in poly (trimetylsilylpropyne). J. Membr. Sci., 1991, vol. 60, no. 1, pp. 13–24. https://doi.org/10.1016/S0376-7388(00)80321-X.

8. Starannikova L.E., Teplyakov V.V. Gas permeability of poly[1-(trimethylsilyl)-1-propyne]: Evaluation of experimental data and calculation methods. Polym. Sci. Ser., A, 1997, vol. 39, no. 10, pp. 1142–1147.

9. Teplyakov V.V., Durgar’yan S.G. Temperature parameters of the gas permeability of polymers. Polym. Sci. U.S.S.R., 1984, vol. 26, no. 10, pp. 2415–2421. https://doi.org/10.1016/0032-3950(84)90155-2.

10. Stern S.A., Vaidyanathan R., Pratt J.R. Structure/permeability relationships of siliconcontaining polyimides. J. Membr. Sci., 1990, vol. 49, no. 1, pp. 1–14. https://doi.org/10.1016/s0376-7388(00)80774-7.

11. Nakagawa T., Nishimura T., Higuchi A. Morphology and gas permeability in copolyimides containing polydimethylsiloxane block. J. Membr. Sci., 2002, vol. 206, nos. 1–2, pp. 149–163. https://doi.org/10.1016/S0376-7388(01)00775-X.

12. Brown J.F., Jr., Vogt L.H., Jr., Katchman A., Eustance J.W., Kiser K.M., Krantz K.W. Double chain polymers of phenylsilsesquioxane. J. Am. Chem. Soc., 1960, vol. 82, no. 23, pp. 6194–6195. https://doi.org/10.1021/ja01508a054.

13. Andrianov K.A., Zhdanov A.A., Levin V.Y. Some physical properties of organosilicon ladder polymers. Annu. Rev. Mater. Res., 1978, vol. 8, pp. 313–326. https://doi.org/10.1146/annurev.ms.08.080178.001525.

14. Yang X-f., Cao C., Chen Z.-h., Liu J., Luo M.-x., Lai G.-q. Synthesis of ladder-like polyphenylsilsesquioxanes with fairly high regularity using 1,2-ethylenediamine as endo-template. Chin. J. Polym. Sci., 2015, vol. 33, no. 9, pp. 1305–1312. https://doi.org/10.1007/s10118-015-1678-z.

15. Yang X., Cao C., Chen Z., Liu J., Bassindale A.R., Lai G. Preparation and characterization of a type of ladder-like poly(phenyl silsesquioxane) based hybrid star-shaped copolymer of ε-caprolactone. J. Appl. Polym. Sci., 2015, vol. 132, no. 31, art. 42335. https://doi.org/10.1002/app.42335.

16. Choi S.-S., Lee A.S., Hwang S.S., Baek K.-Y. Structural control of fully condensed polysilsesquioxanes: Ladderlike vs cage structured polyphenylsilsesquioxanes. Macromolecules, 2015, vol. 48, no. 17, pp. 6063–6070. https://doi.org/10.1021/acs.macromol.5b01539.

17. Mi Y., Stern S.A. Gas permeability of a new silicone ring polymer: Isotactic poly(phenyl silsesquioxane). J. Polym. Sci., Part B: Polym. Phys., 1991, vol. 29, no. 4, pp. 389–393. https://doi.org/10.1002/polb.1991.090290401.

18. Anokhina T.S., Ershova T.O., Anisimov A.A., Temnikov M.N., Grushevenko E.A., Borisov I.L., Volkov A.V., Muzafarov A.M. Pervaporation and gas separation properties of highmolecular ladder-like polyphenylsilsesquioxanes. Polymers, 2023, vol. 15, no. 15, art. 3277. https://doi.org/10.3390/polym15153277.

19. Gordon A.J., Ford R.A. The Chemist’s Companion: A Handbook of Practical Data, Techniques, and References. New York, NY, Wiley VCH, 1972. 537 p.

20. Shchegolikhina O.I., Pozdnyakova Y.A., Molodtsova Y.A., Korkin S.D., Bukalov S.S., Leites L.A., Lyssenko K.A., Peregudov A.S., Auner N., Katsoulis D.E. Synthesis and properties of stereoregular cyclic polysilanols: cis-[PhSi(O)OH]4, cis-[PhSi(O)OH]6, and tris-cis-tris-trans-[PhSi(O)OH]12. Inorg. Chem., 2002, vol. 41, no. 25, pp. 6892–6904. https://doi.org/10.3390/10.1021/ic020546h.

21. Raharjo R.D., Freeman B.D., Paul D.R., Sarti G.C., Sanders E.S. Pure and mixed gas CH4 and n-C4H10 permeability and diffusivity in poly(dimethylsiloxane). J. Membr. Sci., 2007, vol. 306, nos. 1–2, pp. 75–92. https://doi.org/10.1016/j.memsci.2007.08.014.