Article pubs.acs.org/Macromolecules
A Novel, Highly Gas-Permeable Polymer Representing a New Class of Silicon-Containing Polynorbornens As Efficient Membrane Materials Pavel P. Chapala,† Maxim V. Bermeshev,*,†,∥ Ludmila E. Starannikova,† Nikolay A. Belov,† Victoria E. Ryzhikh,† Victor P. Shantarovich,§ Valentin G. Lakhtin,‡ Natalia N. Gavrilova,⊥ Yuri P. Yampolskii,*,†,∥ and Eugene Sh. Finkelshtein*,†,∥ †
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy pr., 119991, Moscow, Russia N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygina ul., 119334, Moscow, Russia ‡ State Scientific Center of the Russian Federation “State Research Institute for Chemistry and Technology of Organoelement Compounds”, 38 Shosse Entuziastov, 111123 Moscow, Russia ⊥ D.I. Mendeleyev University of Chemical Technology of Russia, 9 Miusskaya sq., 125047 Moscow, Russia §
S Supporting Information *
ABSTRACT: The synthesis and gas permeation properties of additiontype poly(3,3-bis(trimethylsilyl)tricyclononene-7) (PTCNSi2g) are first reported. High molecular weight PTCNSi2g was obtained via addition polymerization of 3,3-bis(trimethylsilyl)tricylononene-7 on a Pd-containing catalyst. It possessed a BET surface area as high as 790 m2/g. This new polymer is distinguished by extra high gas permeability and solubility controlled permeation of hydrocarbons. Positron annihilation lifetime spectroscopy revealed extremely large size of free volume elements (8.3 Å). PTCNSi2g is a promising membrane material for separation of natural gas.
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INTRODUCTION Development of new polymer membrane materials for gas and vapor separations is an urgent problem attracting much attention of researchers.1 There are several approaches for creation of such new type of materials. One of them is a design of a new polymer having appropriate side groups or a backbone. This approach is extensively used in the membrane community. There are several examples of highly permeable glassy polymers: disubstituted polyacetylenes (and poly(trimethylsilylpropyne) in particular),2 polymers of intrinsic microporosity (e.g., PIM-1), 3 polynorbornenes (e.g., PTCNSi1),4 thermally rearranged polymers (TR-1),5 perfluorinated polymers6 (AF 2400) (Figure 1). In this work, we report the preparation of a new additionty pe po ly (3,3-bis(tr im et hy lsily l)t ricy clo no nene-7) (PTCNSi2g) with extremely high gas permeation parameters
which are close to those of PTMSP. This polymer is the most permeable member of a novel class of membrane materials: Sisubstituted addition polynorbornenes. The most important property of these polymers is their solubility controlled selectivity for hydrocarbons, thus making these membrane materials capable for separation of components of natural gases. © 2015 American Chemical Society
EXPERIMENTAL SECTION
Chemicals. All chemicals were purchased from Sigma-Aldrich unless is mentioned otherwise. Toluene was distilled over sodium under argon and it was kept in inert atmosphere (dried argon) with sodium/potassium alloy. THF was distilled three times, first over NaOH, for the second time over sodium, and for the third time over sodium with benzophenone when persisted violet color was observed. Hexane was distilled over sodium metal under argon, and it was kept under inert atmosphere with sodium/potassium alloy. Quadricyclane was synthesized as reported previously.7 Physicochemical Measurements. NMR spectra were recorded on a Varian Inova-500 spectrometer operating at 499.83 MHz for 1H, at 125.69 MHz for 13C, and at 99.30 MHz for 29Si. Each sample was dissolved in a solvent (CDCl3 or C6D6) up to a concentration of 10%. Gel-permeation chromatography (GPC) analysis of the polymers was performed on a Waters system with a differential refractometer (Chromatopack Microgel-5, toluene as the eluent, flow rate 1 mL/ min). Molecular mass and polydispersity were calculated by standard procedure relative to monodispersed polystyrene standards. Differential scanning calorimetry (DSC) was performed on a Mettler TA4000 system at a heating rate 20 °C/min. Thermal gravimetric measurements (TGA) were carried out using a PerkinElmer TGA-7 instrument. X-ray diffraction (XRD) experiments were carried out using two-coordinate AXS detector (Bruker) with the Cu Kα line (wavelength of 0.154 nm). The adsorption/desorption analysis were carried out at liquid nitrogen temperature (−196 °C) for N2 and at 0 °C for CO2 on a Micromeritics Gemini VI surface area analyzer. All Received: September 22, 2015 Revised: October 28, 2015 Published: November 10, 2015 8055
DOI: 10.1021/acs.macromol.5b02087 Macromolecules 2015, 48, 8055−8061
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Figure 1. Highly permeable glassy polymers. the samples were degassed at 100 °C at 25−50 mTorr for 10 h before measurements. Film Casting. The films of the polymers studied were cast from the 1.5−2 wt % solution in toluene. The solution was poured into a steel cylinder with a stretched cellophane bottom. The solvent was allowed to evaporate slowly to yield the desired polymer films. After the films formation, cellophane was detached from the films. Before testing, the films were kept under vacuum until the constant weight is achieved. The thickness of the films was in the range of 100−200 μm. Gas Permeation and Sorption Measurements. Permeability coefficients were determined using the gas chromatographic method. The steady state stream of penetrant gases under atmospheric pressure flew around upstream part of the film, while the downstream part of it was swept by the gas-carrier (helium or nitrogen, the latter was used in measurement of permeation rate of H2 and He). The choice of the sweep gas (He or N2) did not affect the measured permeability coefficients. The permeability coefficients were determined by measuring the penetrant concentration in the gas-carrier and the total flow of this mixture. Partial pressure of the penetrants was 1 atm in upstream part of the cell and close to zero in the downstream part. Temperature in the cell was 20−22 °C. Solubility coefficients and sorption isotherms were determined using a novel method of isothermal desorption with chromatographic ending.8 Its brief description is given in the Supporting Information. For calculations the volume of a polymer sample density of the polymer was estimated to be ca. 0.853 g/cm3 measured from the geometry (the same value for EtOH-treated film was ca. 0.824 g/cm3). PALS Measurements. The positron annihilation lifetime decay curves were measured at room temperature using an EG@GOrtec “fast−fast” lifetime spectrometer. A nickel-foil-supported [44Ti] radioactive positron source was used. Two stacks of film samples, each with a total thickness of about 1 mm, were placed on either side of the source. All the measurements were performed in inert (nitrogen) atmosphere. The time resolution was 230 ps (full width at the halfmaximum (fwhm) of the prompt coincidence curve). The contribution from annihilation in the source material, a background, and instrumental resolution were taken into account in the PATFIT program for treating the experimental lifetime data. The resulting data were determined as an average value from the several spectra collected for the same sample, having an integral number of counts of at least 106 in each spectrum. PALS is based on the measurements of positron lifetime spectra in polymers−lifetimes τi (ns) and corresponding intensities Ii (%). Longer lifetimes τ3 and τ4 can be related to the mean size of free volume elements (FVE) in polymers according to Tao - Eldrup formula.9
⎧ ⎫−1 ⎡ ⎛ 2πR i ⎞⎤⎪ ⎪ Ri 1 T ⎢ ⎥ ⎨ τi = ⎪λ 0 + 2 1 − + sin⎜ ⎟ ⎬ ⎢⎣ R i + ΔR 2π ⎝ R i + ΔR ⎠⎥⎦⎪ ⎩ ⎭ where τi = τ3 or τ4 are o-Ps lifetimes and Ri = R3 or R4 are the radii of FVE expressed in nanoseconds and angstroms respectively; λT0 stands for the intrinsic o-Ps annihilation rate (0.7 × 109 s−1); ΔR = 1.66 Å is the fitted empirical parameter. The PALS results are presented in Table S3 together with the results of the study of time dependence (aging) of the PALS parameters and the effects of alcohol treatment on these parameters.
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RESULTS AND DISCUSSION Synthesis. Details of synthesis of PTCNSi2g and the monomer are presented in the Supporting Information Scheme 1. Monomer Synthesis
Scheme 2. Addition Polymerization of TCNSi2g
together with NMR and IR spectra. The target monomer 3,3bis(trimethylsilyl)tricyclononene-7) (TCNSi2g) was prepared according to the developed scheme based on [2σ + 2σ + 2π]cycloaddition reaction of quadricyclane with 1-trimethylsilyl-1trichlorosilylethene as is shown below (Scheme 1). This reaction is stereo- and regioselective, which allowed us to synthesize the only norbornene isomerexo-tricyclononene10 having the most preferable structure for polymerization.4a,11 The consequent methylation of the cycloadduct resulted in the formation of the desired monomer3,3bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7 (TCNSi2g) with a good yield. Addition polymerization of 3,3-bis(trimethylsilyl)tricyclononene-7 was successfully carried out in the presence of Pd-based catalytic systems (Scheme 2). 8056
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Macromolecules Table 1. Addition Polymerization of TCNSi2g catalytic system Pd(OAc)2/B(C6F5)3
Pd(OAc)2/MAO Pd(OAc)2/B(C6F5)3/MAO Pd(AcAc)2/B(C6F5)3 Pd(OAc)2/[Ph3C]+ [B(C6F5)4]−
[M]/[Pd]/[B]
Mw × 10−3
Mw/Mn
yield, %
3200/1/150 3200/1/200 4000/1/300 5000/1/200 5000/1/300 3200/1/500 3200/1/150/800 3200/1/200 3200/1/1 3200/1/5 3200/1/8 3000/1/3 2000/1/3 1000/1/3 500/1/3 250/1/3 100/1/3 50/1/3 25/1/3
173 218 165 200 170 46 147 167 225 330 230 317 248 201 162 83 64 36 22
1.7 2.6 1.7 2.1 1.9 3.6 2.1 2.6 2.9 2.5 2.3 2.5 2.2 2.1 2.3 2.0 2.7 2.6 2.3
64 65 60 28 48 13 58 49 34 50 62 67 94 87 87 87 70 63 71
Figure 4. Micropore distribution of PTCNSi2g.
It should be noted that only the use of Pd(OAc)2/ [Ph3C]+[B(C6F5)4]− as a catalyst allowed us to perform efficiently the addition polymerization of 3,3-bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7 with formation of high molecular weight polymer, possessing necessary film-forming properties, while the use of some other Ni- and Pd-salts activated with B(C6F5)3 and/or methylalumoxane (MAO) resulted in low molecular weight products (Table 1). The structure of the obtained monomer and the polymer was confirmed by NMR and IR-spectroscopy (Figures S1−S16) as well as elemental analysis. It is interesting that an analogous norbornene derivative with geminal position of two SiMe3groups (i.e., 5,5-bis(trimethylsilyl)norbornene-2) or a norbor-
Figure 2. WAXD pattern of PTCNSi2g.
Table 2. WAXD Data for Some Highly Permeable Glassy Polymers polymer
(2θ)1
d1-spacing, Å
(2θ)2
d2-spacing, Å
PTCNSi2g PTCNSi2v4a PTCNSi14a PTMSP13
5.6 5.6 6.0 9.8
15.8 15.8 14.8 9.3
13 13 15 19
6.8 6.8 5.9 3.2
Figure 3. Nitrogen adsorption/desorption isotherms of PTCNSi2g at 77K. 8057
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Macromolecules Table 3. Permeability Coefficients of Permanent Gases in PTCNSi2g and Other Polymers (in the Latter Cases “As Cast” State) polymer PTCNSi2g PTCNSi2v4a PTCNSi14a PMP18 PTMSP19 PIM-1
history
He
H2
O2
N2
CO2
as cast after EtOH
3670 5350 1890 930 2630 6500 760 −
8600 12250 4090 2060 5800 16700 1630 −
4750 6570 2380 990 2700 9700 580 1610
2650 4000 1240 390 1330 6300 180 500
19900 25900 11280 5300 10700 34200 4390 12600
−
2774
747
156
4045
as cast after MeOH3
TR-15
Table 4. Ideal Separation Factors for Some Gas Pairs for PTCNSi2g in Comparison with Some Other Highly Permeable Glassy Polymers α(Pi/Pj) polymer
history
O2/N2
CO2/N2
H2/N2
C4/C1
PTCNSi2g
as cast EtOH as cast EtOH as cast MeOH
1.8 1.6 1.9 1.7 1.5 3.2
7.5 6.5 9.0 7.2 5.4 25.5
3.2 3.1 3.3 3.0 2.7 5.4
6.3 5.7 8.2 7.7 5.1 58.4
PTCNSi2v4a PTMSP22 PIM-13,20
nene derivative with vicinal position of these groups (i.e., 5,6bis(trimethylsilyl)norbornene-2) did not undergo addition polymerization at all due to high steric hindrance of bulky SiMe3-substituents located close to the double bond.4c,12 It was presumed that the reason for 3,3-bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7 activity was the exo-configuration of cyclobutane ring as well as shifting of bulky groups away from the double bond leading to the elimination of the steric hindrance on the polymerization process. Despite the presence of a strained cyclobutane ring in the monomer unit of the synthesized addition type polymer, it showed high thermal stability up to 300 °C in air and up to 340 °C in argon (Figure S18). Glass transition temperature was not observed until the onset of thermal decomposition as DSC indicated. The metathesis polymerization of TCNSi2g as well as the properties of the obtained polymer was studied earlier.4d Wide Angle X-ray Diffraction. WAXD data of PTCNSi2g (Figure 2) showed two broad peaks indicating that the obtained polymer was completely amorphous. The maxima of the peaks of PTCNSi2g indicate relatively large d-spacing as is seen from Table 2. The interchain distance (d-spacing) in PTCNSi2g is the same as in its structural analogue PTCNSi2v. On the other
Figure 5. Sorption isotherms of permanent gases (a) and hydrocarbons C1−C4 (b) in PTCNSi2g at 22 ± 2 °C.
Table 6. Dual Mode Sorption Model Parameters of Light Hydrocarbons C2−C4 in PTCNSi2g and Other Polymers polymer
gas
PTCNSi2g
C2H6 C3H8 n-C4H10 n-C4H10 n-C4H10
PMP18 PTMSPa
kD, cm3(STP)· cm3−(polymer)· atm−1 4.7 12 33 21 31
± ± ± ± ±
0.8 2 1 1 6
CH′ , cm3(STP)/ 3 cm (polymer) 31 31 33 37 52
± ± ± ± ±
4 5 1 1 6
b, atm−1 0.8 4 28 16 13
± ± ± ± ±
0.1 2 4 1 4
a
Calculated on the basis of the experimental data reported by Morisato et al.27
hand, d-spacings in PTCNSi2g are markedly higher than those in the polymer with one SiMe3 group PTCNSi1 and in PTMSP. Surface Area. The low temperature nitrogen adsorption/ desorption isotherms of PTCNSi2g were measured by low
Table 5. Permeability Coefficients of Hydrocarbons C1−C4 in PTCNSi2g and Other Polymers (Pure Gas Experiments) polymer PTCNSi2g PTCNSi2v4a PTCNSi14a PMP18 PTMSP19 PIM-1 (MeOH treated)20
as cast after EtOH
CH4
C2H6
C3H8
n-C4H10
P(C4H10)/P(CH4)
6900 10900 3320 1010 2900 15400 430
14500 20750 6040 1360 3700 26000 1500
14900 22300 7530 1470 4700 30300 5500
43700 62450 26910 13030 40300 78000 25100
6.3 5.7 8.1 12.9 13.9 5.1 58.4
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Macromolecules Table 7. Solubility Coefficients S of Gases and Vapors in PTCNSi2g in Comparison with Other Highly Permeable Glassy Polymers
type polytricyclononenes (e.g., PTCNSi1, 610 m2/g;16 PTCNSi2v, 650 m2/g;17 Figure 1). This value of BET surface area is an agreement with large free volume of this polymer. On the basis of this result the inner surface area 280 m2/g was found and the rest was attributed to external surface area. Micropore distribution was estimated using Horvath−Kawazoe method. For the calculations, the model of slit-shape pores was used. The dominant pores’ diameter is about 7 Å (Figure 4). Structural reasons for intrinsic microporosity of PTCNSi2g are based on combination of two bulky side SiMe3-groups, rigidity of main chains and lack of conformational freedom leading to inability to pack space efficiently. Permeability. PTCNSi2g is extremely permeable polymer as Table 3 shows where its permeability coefficients for a number of gases are compared with those of other highly permeable glassy polymers. One can see that PTCNSi2g belongs to the group of extra highly permeable glassy polymers. Permeability coefficients of PTCNSi2g are significantly higher than the corresponding values, e.g., for PIMs3 and for PMP.18 Recently, we have shown that the number of SiMe3 groups in the repeat units substantially affects the observed permeability (using PTCNSi1 and PTCNSi2v as examples).4 The present work indicates that also the relative location of side groups influences gas transport properties of polymers. Thus, gas permeability of the PTCNSi2g is markedly higher than that of its isomer PTCNSi2v. The possible reason for this interesting phenomenon is a difference in conformations of the corresponding polymer chains. Probably, two geminal SiMe3-groups located asymmetrically in respect to the monomer unit of PTCNSi2g, lead to a more rigid polymer chains and their looser packaging. This provides higher size of free volume elements (FVEs) in PTCNSi2g (see below). The final explanation of this effect would be obtained as soon as the results of modeling of these polymers are ready which are now in progress. As in the case of other high free volume polymers, ethanol treatment of PTCNSi2g films resulted in an additional increase in permeability coefficients (Table 3). The reason for this is the swelling of polymers in alcohols capable to increase free volume.3,21 As it can be expected, ultra high gas permeable polymers exhibit comparatively moderate or even low selectivities in comparison with conventional low permeable glassy polymers (Table 4). A traditional trade-off effect holds between permeability and permselectivity as an analysis of Tables 3 and 4 shows: more permeable states of polymers (EtOHtreated) demonstrate lower selectivity. Permeability−permselectivity diagram for gas pair CO2/N2 with the data points for PTCNSi2g and other polymers is given in the Supporting Information (Figure S19).
S (cm3(STP) cm−3 atm−1) gas
PTCNSi2g
PTCNSi2v28
PTMSP29
PIM-13
O2 N2 CO2 CH4 C2H6 C3H8 C4H10
1.75 1.55 9.10 4.24 18.7 36.9 65.1
1.27 1.0 7.0 3.2 − − −
1.29 1.10 6.05 3.45 18.10 36.73 −
3.9 3.7 70 16.3 − − −
Table 8. Diffusion Coefficients D of Gases and Vapors in PTCNSi2g in Comparison with Other Highly Permeable Glassy Polymers D × 105 (cm2 s−1) gas
PTCNSi2g
PTCNSi2v28
PTMSP29
PIM-13
O2 N2 CO2 CH4 C2H6 C3H8 C4H10
2.10 1.30 1.66 1.24 0.58 0.31 0.51
1.40 0.92 1.00 0.76 0.23 0.08 −
5.2 4.4 3.3 3.6 1.7 1.4 −
0.3900 0.1600 0.1600 0.0710 − − −
Figure 6. Changes of permeability coefficients of PTCNSi2g for oxygen and nitrogen in time.
temperature adsorption of nitrogen. They were irreversible type I with hysteresis (Figure 3). The found BET surface area of 790 m2/g is comparable with those of such polymers as PIM-1 (760−830 m2/g)14 or PTMSP (780 m2/g)15 and it is higher than the corresponding values of other early studied addition-
Table 9. Free Volume Parameters of PTCNSi2g in Comparison with Those of Other Highly Permeable Glassy polymers polymer
history
τ3, ns
I3, %
τ4,ns
I4, %
R3 , Å
R4 , Å
PTCNSi2g
as cast aged 1 week aged 1 month EtOH-treated aged 1 month as cast MeOH-treated
3.8 3.5 2.6 2.9 2.7 2.7 1.8
11.0 10.4 7.9 7.3 7.1 4.4 5.8
11.7 11.6 10.9 15.3 14.9 10.9 7.1
35.6 35.7 35.6 33.9 27.8 33.8 17.3
4.2 4.0 3.4 3.6 3.4 3.4 2.7
7.3 7.3 7.0 8.3 8.2 6.8 5.6
PTMSP32 PIM-13
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with vicinal position of SiMe3 groups. The absolute values of D in PTCNSi2g are very high as compared with those of other glassy polymers from our database.30 For example, they are higher by 1−2 orders than those of PIM-1. However, as has been noted earlier,3 the solubility coefficients of PIM-1 still remained the highest among all the polymers studied. The observed high P values of PTCNSi2g can be explained by great diffusion and solubility coefficients in this polymer. It will be interesting to check eventually whether the diffusion coefficients estimated as the ratio P/S will be in agreement with the values found via time-lag method. Highly permeable glassy polymers (especially PTMSP) are prone to fast aging. So, an investigation of aging of PTCNSi2g films was performed. Figure 6 presents the data for O2 and N2. The results for other gases are given in Supporting Information. A general conclusion that can be made is that the rate of aging of PTCNSi2g is relatively slow than can be expected for a polymer with such level of permeability. For example, it is slower that the rate of aging of PTMSP.31 It seems that the high permeability of PTCNSi2g can be caused by its microporous nature and large free volume. Hence, free volume of PTCNSi2g was studied by means of positron annihilation lifetime spectroscopy (PALS). The measurements were performed for “as cast” film, for the film treated with EtOH and also the process of aging was studied. As in other highly permeable glassy polymers, the size distribution of free volume in PTCNSi2g is bimodal. This polymer demonstrates extremely large size of FVE (Table 9). The larger radius of FVE in PTCNSi2g (R4 = 7.3 Å) is unexpectedly greater than those in PTMSP and PIM-1. Treatment of PTCNSi2g with EtOH results in further increase in free volume: R4 becomes equal to 8.3 Å. Highly permeable glassy polymers usually reduce in time their sizes of FVE. The same is true for PTCNSi2g, however, the pace of this process is relatively slow: after one month of storage of “as cast” film of PTCNSi2g the value of R4 is 7.0 Å and in EtOH treated sample 8.2 Å. These results are in agreement with low rate of decreasing permeability coefficients of PTCNSi2g. Detailed molecular modeling as well as investigations of polymers chain rigidity of SiMe3-substututed polynorbornenes and polytricyclonones is in progress now.
Another interesting and potentially important feature of PTCNSi2g is the observed solubility controlled permeation of hydrocarbons (Table 5). For conventional glassy polymers an increase in penetrant size results in a decrease in the permeability coefficients (size sieving effect). For PTCNSi2g an increase in penetrant (n-alkane) size results in the growth of permeability coefficients (the same trend as that of the solubility coefficients) (Table 5). It can be explained by relatively low energy barriers for diffusion in microporous PTCNSi2g. Since the permeability coefficient can be represented as P = D × S, where D is the diffusion coefficient and S is the solubility coefficient, great permeability can be caused by large values of D or S (or both). Because of this, measurement of gas sorption isotherms of PTCNSi2g was conducted. A novel method for the determination of the solubility coefficients and sorption isotherms was used.8 Sorption isotherms are shown in Figure 5. It is seen that sorption isotherms of light gases are linear in the given pressure range so they obey Henry’s law. On the other hand, the sorption isotherms of hydrocarbons C2−C4 are concave to the pressure axis, i.e., are in agreement with the dual mode sorption (DMS) model characteristic for glassy polymers. The curved isotherms were fitted according to the equation23,24 c = kDp +
CH′ bp 1 + bp
where c is solute concentration [cm3(STP)·cm−3(polymer)], kD is the Henry law coefficient [cm3(STP)·cm−3(polymer)· atm−1)], b is the Langmuir affinity parameter [atm−1], CH′ is the Langmuir capacity parameter [cm3(STP)·cm−3(polymer)], and p is penetrant pressure [atm]. The solubility coefficient of the solutes dissolved in the equilibrium regions of the polymer matrix is characterized by kD. The values of kD for hydrocarbons (Table 6) increase as the size of the solutes increases, i.e., are larger for the solutes with higher boiling point or critical temperature. The same is true for the affinity constant b. Consideration of the DMS parameters of n-butane in various highly permeable glassy polymers (Table 6) shows that the Henry’s law coefficient kD in PTCNSi2g is quite high and comparable with that in PTMSP. The parameter b of n-butane in PTCNSi2g is higher than those in other highly permeable glassy polymers. However, this discrepancy can be also explained by the range of pressure in which the sorption was measured.25 The CH′ parameter is a measure of the maximum sorption capacity in the Langmuir domains. Often CH′ value in glassy polymers is related to the nonequilibrium excess free volume.26 For all hydrocarbons in Table 6, the Langmuir capacity is similar to each other and CH′ of n-butane is significantly lower than that in PTMSP. So, it can indicate indirectly that PTCNSi2g have smaller free volume than PTMSP. This is in contrast, however, with the results of PALS studies of this polymer and PTMSP. This circumstance requires further elucidation. Since the permeability coefficients of gases and vapors in PTCNSi2g (Tables 3 and 5) were measured at 1 atm, the solubility coefficient S was estimated as c1/p, where c1 is the concentration of sorbed penetrant at 1 atm. The corresponding values are given in Table 7. Then, using the found S values the diffusion coefficients were calculated as D = P/S. They are given in Table 8. These tables show that PTCNSi2g has higher diffusion and solubility coefficients as compared with its isomer PTCNSi2v
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CONCLUSIONS The synthesis of addition-type poly(3,3-bis(trimethylsilyl)tricyclononene-7) resulted in obtaining a new ultra high permeable microporous polymer with large free volume and properties stable in time. It reveals the solubility controlled permeation of hydrocarbons. Therefore, PTCNSi2g and its structural analogues form a new class of highly permeable glassy polymers that can find applications as membrane materials for separation of natural and associated petroleum gases.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.5b02087. Synthesis and polymerization of PTCNSi2g and precursors including NMR and IR spectra and TGA plots, a brief description of the method for determination solubility coefficients, gas-transport data plots, and aging data (PDF) 8060
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AUTHOR INFORMATION
Corresponding Authors
*(M.V.B.) E-mail:
[email protected]. *(E.S.F.) E-mail: fi
[email protected]. *(Y.P.Y.) E-mail:
[email protected]. Author Contributions ∥
M.V.B. and E.S.F., macromolecular design and synthesis of polymers; Y.P.Y., study of gas permeation properties. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The authors gratefully acknowledge the support of the Russian Science Foundation (Grant No. 14-19-01362).
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REFERENCES
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DOI: 10.1021/acs.macromol.5b02087 Macromolecules 2015, 48, 8055−8061
