Skip to main content
SpringerLink
Log in

Gas Chromatography Columns Based on Functionalized Polymer for the Analysis of Catalytic Reaction Products

  • Original
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

For the first time in this work, two methods of modification of poly(1-trimethylsilyl-1-propyne) (PTMSP) and the possibilities of its application for the determination of catalytic reaction products are described. Aging of PTMSP is determined by three mechanisms: physical, chemical and mechanical effects. Free volume decreases, texture characteristics change, and partial oxidation of the polymer takes place in the structure of PTMSP. The chromatographic behavior of PTMSP, which was used for 18 months, differs significantly from the properties of the freshly prepared polymer. Thermal stability and chemical inertness are the main requirements for chromatographic materials. Therefore, two methods were used to stabilize the aging process. The first method consisted of preparing a mixed phase by adding disubstituted polyacetylene poly(1-phenyl-1-propyne) (PPP) to PTMSP. The resulting sorbent Chromosorb Р NAW + 10 wt% (97% PTMSP + 3% PPP) is efficient for solving a wide range of chromatographic tasks such as simultaneous analysis of hydrocarbons and sulfur-containing inorganic gases, analysis of chlorine-substituted methanes in CCl4 and thiophene in benzene, separation of hydrocarbons and aromatic compounds. It should be noted, the low selectivity of separation of oxygen-containing components on this sorbent. A second method of PTMSP modification, namely the oxidation treatment with nitrous oxide, is proposed. It was shown that the polymer is oxidized by means of its C=C double bond with the formation of ketone, carbonyl and hydroxyl groups. The increase in number of those groups in the polymer changed the polarity of PTMSP. The change in polarity of polymer led to the selectivity of separations, including oxygen-containing substances. Examples of separations of aliphatic and aromatic hydrocarbons, oxygen- and halogen-containing substances are presented. Chromatographic characteristics of the sorbent Chromosorb P NAW + 10 wt% (97% PTMSP + 3% PPP) and PTMSP oxidized by nitrous oxide are stable in the temperature range from 30 to 220 °C for at least 1.5 years of continuous operation.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Masuda T, Isobe E, Higashimura T (1985) Polymerization of 1-(trimethylsilyl)-1-propyne by halides of niobium(V) and tantalum(V) and polymer properties. Macromolecules 18:841–845

    Article  CAS  Google Scholar 

  2. Masuda T, Takahashi T, Higashimura T (1985) Polymerization of 1-phenyl-1-alkynes by halides of niobium and tantalum. Macromolecules 18:311–317

    Article  CAS  Google Scholar 

  3. Shantarovich VP, Azamatova ZK, Novikov YA, Yampolskii YP (1998) Free-volume distribution of high permeability membrane materials probed by positron annihilation. Macromolecules 31:3963–3966

    Article  CAS  Google Scholar 

  4. Raharjo RD, Freeman BD, Paul DR, Sanders ES (2007) Pure and mixed gas CH4 and n-C4H10 permeability and diffusivity in poly(1-trimethylsilyl-1-propyne). Polymer 48:7329–7344

    Article  CAS  Google Scholar 

  5. Consolati G, Genco I, Pegoraro M, Zanderighi L (1996) Positron annihilation lifetime (PAL) in poly[1-(trimethyl-silyl)propine] (PTMSP): free volume determination and time dependence of permeability. J Polym Sci Part B Polym Phys 34:357–367

    Article  CAS  Google Scholar 

  6. Rutherford SW (2001) Mechanism of sorption and diffusion in a high free-volume polymer. Ind Eng Chem Res 40:1370–1376

    Article  CAS  Google Scholar 

  7. Borisevich OB, Syrtsova DA, Teplyakov VV, Khotimskii VS, Roizard D (2004) Study of permeability process of organic substance vapors through poly(1-trimethylsilylpropyne). Desalination 163:267–272

    Article  CAS  Google Scholar 

  8. Gomes D, Nunes SP, Peinemann KV (2005) Membranes for gas separation based on poly(1-trimethylsilyl-1-propyne)—silica nanocomposites. J Membr Sci 246:13–25

    Article  CAS  Google Scholar 

  9. Syrtsova D, Shkrebko O, Teplyakov V, Khotimslii V, Roizard D, Grinshpan D (2006) Removing of light hydrocarbons from gas mixtures using polymeric composite membranes based on poly(1-trimethylsilylpropyne). Desalination 200:253–255

    Article  CAS  Google Scholar 

  10. Syrtsova D, Borisevich O, Shkrebko O, Teplyakov V, Grinshpan D, Khotimskii V, Roizard D (2007) The permeability of gases and light hydrocarbons through new polymeric composite membranes based on poly(1-trimethylsilylpropyne). Sep Purif Technol 57:435–439

    Article  CAS  Google Scholar 

  11. Baschetti MG, Ghisellini M, Quinzi M, Doghieri F, Stagnaro P, Costa G, Sarti GC (2005) Effects on sorption and diffusion in PTMSP and TMSP/TMSE copolymers of free volume changes due to polymer ageing. J Mol Struct 739:75–86

    Article  CAS  Google Scholar 

  12. Strannikova L, Khodzhaeva V, Yampolskii Y (2004) Mechanism of aging of poly[1-(trimethylsilyl)-1-propyne] and its effect on gas permeability. J Membr Sci 244:183–191

    Article  CAS  Google Scholar 

  13. Morlière N, Vallières C, Perrin L, Roizard D (2006) Impact of thermal ageing on sorption and diffusion properties of PTMSP. J Membr Sci 270:123–131

    Article  CAS  Google Scholar 

  14. Nagai K, Higuchi A, Nakagawa T (1995) Gas permeability and stability of poly(1-trimethylsilyl-1-propyne-co-1-phenyl-1-propyne) membranes. J Polym Sci Part B Polym Phys 33:289–298

    Article  CAS  Google Scholar 

  15. Jia J, Baker GL (1998) Cross-linking of poly[1-(trimethylsilyl)-1-propyne] membranes using bis(aryl azides). J Polym Sci Part B Polym Phys 36:959–968

    Article  CAS  Google Scholar 

  16. Pinnau I, Casillas CG, Morisato A, Freeman BD (1996) Hydrocarbon/hydrogen mixed gas permeation in poly(1-trimethylsilyl-1-propyne) (PTMSP), poly(1-phenyl-1-propyne) (PPP), and PTMSP/PPP blends. J Polym Sci Part B Polym Phys 34:2613–2621

    Article  CAS  Google Scholar 

  17. Toy LG, Nagai K, Freeman BD, Pinnau I, He Z, Masuda T, Teraguchi M, Yampolskii YP (2000) Pure-gas and vapor permeation and sorption properties of poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA). Macromolecules 33:2516–2524

    Article  CAS  Google Scholar 

  18. Masuda T, Isobe E, Higashimura T, Takada K (1983) Poly[1-(trimethylsilyl)-1-propyne]: a new high polymer synthesized with transition-metal catalysts and characterized by extremely high gas permeability. J Am Chem Soc 105:7473–7474

    Article  CAS  Google Scholar 

  19. Olivieri L, Ligi S, De Angelis MG, Cucca G, Pettinau A (2015) Effect of graphene and graphene oxide nanoplatelets on the gas permselectivity and aging behavior of poly(trimethylsilyl propyne) (PTMSP). Ind Eng Chem Res 54:11199–11211

    Article  CAS  Google Scholar 

  20. Volkov AV, Bakhtin DS, Kulikov LA, Terenina MV, Golubev GS, Bondarenko GN et al (2016) Stabilization of gas transport properties of PTMSP with porous aromatic framework: effect of annealing. J Membr Sci 517:80–90

    Article  CAS  Google Scholar 

  21. Berezkin VG, Korolev AA, Malyukova IV, Popova TP, Shiryaeva VE, Khotimskii VS (2002) P oly[1-(trimethylsilyl)-1-propine] as chromatographic adsorbent and prospects of its application in packed and capillary columns. J Chromatogr A 960:151–158

    Article  CAS  PubMed  Google Scholar 

  22. Dorkenoo KD, Pfromm PH (2000) Accelerated physical aging of thin poly[1-(trimethylsilyl)-1-propyne] films. Macromolecules 33:3747–3751

    Article  CAS  Google Scholar 

  23. Berezkin VG, Popova TP, Shiryaeva VE, Korolev AA, Malyukova IV (2002) Equilibrium chromatographic characteristics of capillary column coated with polytrimethylpropyne for separating polar and non-polar organic compounds by gas capillary chromatography. Russ Chem Bull 51:828–832

    Article  CAS  Google Scholar 

  24. Krylov VA, Berezkin VG, Chernova OY, Salganskii YM, Korolev AA (2003) Gas–adsorption chromatography of reactive compounds on open-tubular columns with poly(trimethylsilylpropyne). J Anal Chem 58:372–374

    Article  CAS  Google Scholar 

  25. Berezkin VG, Mukhina VP, Korolev AA, Fatkullina AF, Seroshtan VA (2004) Poly(1-trimethylsilyl)-1-propin (PTMSP)—a new porous polymeric sorbent for light hydrocarbonics capillary gas chromatography. Zavodskaya laboratoriya Diagnostika materialov 70:9–13 (in Russian)

    CAS  Google Scholar 

  26. Belotserkovskaya VY, Yakovleva EY (2010) Study of poly(1-trimethylsilyl-1-propyne) aging by gas chromatography. J Struct Chem 51:159–163

    Article  CAS  Google Scholar 

  27. Morisato A, Shen HC, Sankar SS, Freeman BD, Pinnau I, Casillas CG (1996) Polymer characterization and gas permeability of poly(1-trimethylsilyl-1-propyne) [PTMSP], poly(1-phenyl-1-propyne) [PPP], and PTMSP/PPP blends. J Polym Sci Part B Polym Phys 34:2209–2222

    Article  CAS  Google Scholar 

  28. Yakovleva EY, Belotserkovskaya VY (2011) Chromatographic and adsorption properties of the mixed stationary phase poly(1-trimethylsilyl-1-propyne)/poly(1-phenyl-1-propyne). J Anal Chem 66:629–633

    Article  CAS  Google Scholar 

  29. Berezkin VG, Korolev AA, Khotimsky VS (2003) Polychromatic(trimethylsilylpropyne) modified with volatile organic solids as an adsorbent for capillary gas adsorption chromatography of hydrocarbon gases. Pet Chem 43:202–204

    Google Scholar 

  30. Berezkin VG, Korolev AA, Khotimskii VS (2002) Modification of the polytrimethylsilylpropyne adsorption layer in open capillary columns. Russ Chem Bull 51:625–627

    Article  CAS  Google Scholar 

  31. Malakhov AO, Berezkin VG, Sorokina EY, Volkov AV, Volkov VV (2004) Poly(1-trimethylsilyl-1-propyne) as a stationary phase in capillary gas-solid chromatography of alcohols: effect of carrier-gas humidity. Polym Sci Ser B 46:23–30

    Google Scholar 

  32. Dubkov KA, Semikolenov SV, Ivanov DP, Babushkin DE, Matsko MA, Panov GI (2009) Synthesis of functionalized liquid rubbers from polyisoprene. J Appl Polym Sci 114:1241–1249

    Article  CAS  Google Scholar 

  33. Dubkov KA, Panov GI, Parmon VN (2017) Nitrous oxide as a selective oxidant for ketonization of C=C double bonds in organic compounds. Russ Chem Rev 86:510–529

    Article  CAS  Google Scholar 

  34. Patrushev YV, Yakovleva EY, Shundrina IK, Ivanov DP, Glazneva TS (2015) The properties of capillary columns with sorbents based on poly-(1-trimethylsilyl-1-propyne) modified with nitrous oxide. J Chromatogr A 1406:291–298

    Article  CAS  PubMed  Google Scholar 

  35. Belotserkovskaya VY, Yakovleva EY (2011) Chromatographic properties of poly(1-trimethylsilyl-1-propyne). Russ J Phys Chem A 85:851–856

    Article  CAS  Google Scholar 

  36. Belotserkovskaya VY, Yakovleva EY (2010) Chromatographic properties of poly(1-phenyl-1-propyne). Russ J Phys Chem A 84:307–311

    Article  CAS  Google Scholar 

  37. Nagai K, Mori M, Watanabe T, Nakagawa T (1997) Gas permeation properties of blend and copolymer membranes composed of 1-trimethylsilyl-1-propyne and 1-phenyl-1-propyne structures. J Polym Sci Part B Polym Phys 35:119–131

    Article  CAS  Google Scholar 

  38. Toy LG, Freeman BD, Spontak RJ, Morisato A, Pinnau I (1997) Gas permeability and phase porphology of poly(1-(trimethylsilyl)-1-propyne)/Poly(1-phenyl-1-propyne) plends. Macromolecules 30:4766–4769

    Article  CAS  Google Scholar 

  39. Yakovleva EY, Belotserkovskaya VY (2010) Chromatographic properties and polarity evaluation of poly(1-trimethylsilyl-1-propyne) and poly(1-phenyl-1-propyne). J Anal Chem 65:1014–1020

    Article  CAS  Google Scholar 

  40. Belotserkovskaya V, Yakovleva E (2013) Chromatographic and adsorption properties of poly(1-trimethylsilyl-1-propyne) and their stabilization by adding poly(1-phenyl-1-propyne). J Chromatogr A 1298:109–117

    Article  CAS  PubMed  Google Scholar 

  41. Ettre LS (1993) Nomenclature for chromatography (IUPAC Recommendations 1993). Pure Appl Chem 65:819–872

    Article  CAS  Google Scholar 

  42. Sakodinskiy KI, Panina LI (1977) Polymer sorbents for molecular chromatography. Nauka, Moscow

    Google Scholar 

  43. Yakovleva EY, Belotserkovskaya VY (2013) Separation of hydrocarbon and sulfur-containing gases on a new poly-(1-trimethylsilyl-1-propyne)/poly-(1-phenyl-1-propyne) mixed stationary phase in the presence of water. J Anal Chem 68:646–651

    Article  CAS  Google Scholar 

  44. Yakovleva EY, Patrushev YV, Belotserkovskaya VY (2015) Products of catalytic hydrofluorination of perchloroethylene to pentafluoroethane as determined by gas chromatography with a mixed stationary phase poly-(1-trimethylsilyl-1-propyne/poly-(1-phenyl-1-propyne). Catal Ind 2:15–19.

    Google Scholar 

  45. Drugov YS, Zenkevich IG, Rodin AA (2014) Gas-chromatographic identification of contaminants in air, water, soil and biological environments. Binom, Moscow

    Google Scholar 

  46. Mazepa EA, Arystanbekova SA, Volynsky AB (2013) Express-determination of sulfur -containing compositions in hydrocarbon liquid samples, being under high pressure, by means of gas chromatography method. Equip Technol Oil Gas Complex 1:35–42

    Google Scholar 

  47. ASTM D 5504-08. Standard test methods for determination of sulfur compounds in natural gas and gaseous fuels by gas chromatography and chemiluminescence

  48. Yakovleva EY, Patrushev YV, Pai ZP (2017) Analysis of isobutane dehydrogenation products by gas chromatographic method. Katal v promyshlennosti 17:460–464

    Article  Google Scholar 

  49. Yakovleva EY, Patrushev YV, Pai ZP (2017) Capillary column based on modified poly(1-trimethylsilyl-1-propyne) for analysis of natural gas. Russ J Phys Chem A 92 (in press)

  50. Supelco (1998) Bulletin 876A Monitor sulfur compounds in petroleum chemical, environmental, and other samples, using a special-purpose capillary GC column

Download references

Acknowledgements

This work was conducted within the framework of the budget project 17-117041710081-1 for Boreskov Institute of Catalysis. The authors are grateful to Prof. A. S. Kharitonov for the idea to modify poly(1-trimethylsilyl-1-propyne) with nitrous oxide.

Author information

Authors and Affiliations

  1. Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia

    E. Yu. Yakovleva, Y. V. Patrushev, D. P. Ivanov & I. P. Prosvirin

  2. Novosibirsk State University, Pirogova Str., 2, Novosibirsk, 630090, Russia

    E. Yu. Yakovleva & Y. V. Patrushev

Authors
  1. E. Yu. Yakovleva
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Y. V. Patrushev
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. D. P. Ivanov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. I. P. Prosvirin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to E. Yu. Yakovleva.

Ethics declarations

Conflict of interest

The authors declare that have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 14 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yakovleva, E.Y., Patrushev, Y.V., Ivanov, D.P. et al. Gas Chromatography Columns Based on Functionalized Polymer for the Analysis of Catalytic Reaction Products. Chromatographia 81, 1305–1315 (2018). https://doi.org/10.1007/s10337-018-3567-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-018-3567-4

Keywords

Search

Navigation