Poly 1 - -1 -propyne

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... 

PtOEP is widely used as a PSP probe among the metalloporphyrins. The absorption and emission maximum of PtOEP are 381 and 535, and 646 nm, respectively. For examples of PSPs based on the OEP metal complexes in silicone polymer films, PSPs based on the platinum or palladium OEP immobilized in poly(TMSP) film have been reported. Oxygen permeability of poly(l-trimethylsily-l-propyne) (poly(TMSP)) film is about ten times larger than that of poly(dimethylsiloxane) (poly(DMS)) film, and provides a tough and thin film [14,15]. The poly(TMSP) film is a porous polymer matrix with a high oxygen permeability and diffusion, indicating that the probe... 

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). 

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). 

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. 

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... 

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. 

All of the syntheses shown in Table 19 were achieved by us for the first time. These polymers are all new polymers, though high-molecular-weight poly(terf-butylace-tylene) 9) and poly(l-phenyl- 1-propyne)55) were also prepared at similar periods with catalysts 3 and 7, respectively. 

Membranes for gas separation have recently attracted much attention since membrane separation is one of promising energy-saving operations 104). For example, membranes for the oxygen enrichment of air, the isolation of helium, and the removal of C02 and S02 from natural gas are being intensively studied. The high gas permeability of substituted polyacetylenes, especially of poly[l-(triinethylsilyl)-l-propyne], is described below. 

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... 

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