Poly trimethylsilyl-1-propyne

The diffusion of gases through a polymer matrix is determined by the mobility of gas molecules through the matrix. The diffusion coefficient is therefore, at least partially determined by the free volume size of the polymer. It has been shown, for example, that there is a correlation between the free volume measured by PAL and the diffusivity of carbon dioxide in a seriers of polycarbonates [58], In a study of poly (trimethylsilyl propyne) (PTMSP), which has an extremely high gas permeability and diffusion coefficients, it was found that the lifetime data could be resolved into four components [59]. The longest lifetime component (T4) had a lifetime of... 

Yu. P. Yampolskii, V. P. Shantarovich, F. P. Chemyakovskii, A. 1. Kornilov, N. A. Plate, Estimation of free volume in poly(trimethylsilyl propyne) by positron annihilation and electrochromism methods, J. Appl. Polym. Set, 47, 85-92 (1993). 

GS, gas separation OSN, organic solvent nanofiltration RO, reverse osmosis BTB, Bromothymol Blue PTMSP, poly(trimethylsilyl propyne) PMP, Polym hylpentene PIMA, polymer of intrinsic microporosity. 

Another possible approach to indirectly characterize the membrane morphology is based on the investigation of the free volume within the matrix. Density measurements [119,120] and positron annihilation lifetime spectroscopy evaluation [47] are common methods. Typically, the comparison between the theoretical density or free volume (calculated by simple additivity rules) and the experimental one can reveal the presence of a good interfacial morphology or the presence of interface voids or clustering formation. Fig. 7.13 shows the influence of filler content on the morphology of poly(trimethylsilyl propyne) (PTMSP)/Ti02 NCMs in terms of the volumetric fraction of interface voids as calculated from a comparison of the expected and measured membrane density [119],... 

Figure 7.13 Void volume fraction as a function of the Ti02 content in a poly(trimethylsilyl propyne)/Ti02 composite membrane as calculated from a comparison of the theoretical and experimental density.

As a typical representative of the first type of behavior one can mention glassy poly(vinyltrhnethyl silane), of die second one it is rubbery poly(di-methylsiloxane), and, of the third one is poly(trimethylsilyl propyne) [2] ... 

M. Langsam, M. Anand and E.J. Karwacki, Substituted Propyne Polymers I. Chemical Surface Modification of Poly [ 1 -(trimethylsilyl)propyne] for Gas Separation Membranes, Gas Sep. Purif. 2, 162 (1988). 

Pinnau I, Casillas CG, Morisato A, and Freeman BD. Long-term permeation properties of poly(l-trimethylsilyl-propyne) membranes in hydrocarbon-vaport environment. J. Polym. Sci. PartB Polym. Phys. 1997 35 1483-1490. 

Sitter, K.D., Andersson, A., D Haen, J., Leysen, R., Mullens, S., Maurer, F.H.J., and Vankelecom, I.F.). (2008) Silica filled poly(4-methyl-2-pentyne) nanocomposite membranes similarities and differences with poly(1 -trimethylsilyl-1 -propyne)-silica systems./. Membr. Sd., 321 (2), 284-292. 

In 1975, it was discovered that WCk, which is a typical metathesis catalyst, is capable to catalyze the polymerization of phenylacetyl-ene. Subsequently, various substituted acetylenes have been polymerized by this type of catalyst. In 1983, poly(l-(trimethylsilyl)-l-propyne)) was synthesized in the presence of Tads and NbCls (35). The alkyne polymerization has many similarities with ROMP. 

K. Nagai, T. Masuda, T. Nakagawa, B.D. Freeman, and I. Pinnau, Poly[l-(trimethylsilyl)-l-propyne] and related polymers Synthesis, properties and functions, Prog. Polym. Sci., 26(5) 721-798, June 2001. 

Glucose sensors II and HI were prepared from the semipermeable membrane of PMSP, poly(1-trimethylsilyl-l-propyne), which has 4 times the oxygen permeability compared with that of FEP membrane. The response properties of sensor H, using a PMSP membrane with 25 Um diameter pinhole, were almost similer to that of the sensor I, so that their calibration curves were not presented in this paper. 

FEP Teflon FEP membrane PMSP Poly(1-trimethylsilyl-l-propyne) membrane Nz Enzyme immobilized Nylon filter... 

A. Morisato, B.D. Freeman, I. Pinnau and C.G. Casillas, Pure Hydrocarbon Sorption Properties of Poly(l-trimethylsilyl-l-propyne) [PTMSP] and Poly(l-phenyl-l-propyne) [PPP] and PTMSP/PPP Blends, J. Polym. Sci., Polym. Phys. Ed. 34, 1925 (1996). 

H. Nishide, H. Kawakami, S.Y. Sasame, K. Ishiwata and E. Tsuchida, Facilitated Transport of Molecular Oxygen in Cobaltporphyrin/Poly(l-trimethylsilyl-l-propyne) Membrane, J. Polym. Sci., Part A Polym. Chem. 30, 77 (1992). 

In contrast, organophilic PV membranes are used for removal of (volatile) organic compounds from aqueous solutions. They are typically made of rubbery polymers (elastomers). Cross-linked silicone rubber (PDMS) is the state-of-the-art for the selective barrier [1, 43, 44]. Nevertheless, glassy polymers (e.g., substituted polyacetylene or poly(l-(trimethylsilyl)-l-propyne, PTMSP) were also observed to be preferentially permeable for organics from water. Polyether-polyamide block-copolymers, combining permeable hydrophilic and stabilizing hydrophobic domains within one material, are also successfully used as a selective barrier. 

As shown in Fig. 2, the polymerization of l-(trimethylsilyl)-l-propyne by TaCl5 is accelerated, and the MW of polymer is increased by use of Ph3Bi as cocatalyst61). To our knowledge, the Mw of 4 x 106 for poly[l-(trimethylsilyl)-l-propyne] obtained with TaCl5—Ph3Bi is the highest of those of any polyacetylenes reported to date. 

The Pq2 and Po2/Pn2 values of substituted polyacetylenes so far determined are given in Table 30. Poly[l-(trimethylsilyl)-l-propyne] shows the highest P0z value... 

A few other characteristics for the gas permeation of poly[l-(trimethylsilyl)-l-propyne] are as follows ... 

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