Siloxanes cationic

Radiation-Induced Polymerization. In 1956 it was discovered that D can be polymerized in the soHd state by y-irradiation (145). Since that time a number of papers have reported radiation-induced polymerization of D and D in the soHd state (146,147). The first successhil polymerization of cychc siloxanes in the Hquid state (148) and later work (149) showed that the polymerization of cycHc siloxanes induced by y-irradiation has a cationic nature. The polymerization is initiated by a cleavage of Si—C bond and formation of silylenium cation. 

FIGURE 9.33 Analysis of cationic poly(amino siloxane). Columns PSS PFG 100 + 1000. Eluent HFIP + O.l A1 KtFat. Temp 25°C. Detection UV 230 nm, Rl. Calibration PSS PDMS siloxane standards. 

An interesting feature of the ring opening polymerization of siloxanes is their ability to proceed via either anionic or cationic mechanisms depending on the type of the catalyst employed. In the anionic polymerization alkali metal hydroxides, quaternary ammonium (I NOH) and phosphonium (R POH) bases and siloxanolates (Si—Oe M ) are the most widely used catalysts 1,2-4). They are usually employed at a level of 10 2 to KT4 weight percent depending on their activities and the reaction conditions. The activity of alkali metal hydroxides and siloxanolates decrease in the following order 76 79,126). 

Detailed procedures for the synthesis ofa,o>-organofunctionally terminated siloxane oligomers with well defined structures have been given 50,66-67). Tables 6 and 7 provide the data on the synthesis and characteristics of aminopropyl and hydroxybutyl terminated polydimethylsiloxane oligomers prepared via anionic and cationic ringopening polymerization of octamethylcyclotetrasiloxane (D in the presence of appropriate disiloxanes, respectively. 

These spacings correspond to cationized fragments with the general composition [SixOyHz]+. The results of the peak analysis prove that the uppermost monolayer of the surface film consists of totally hydrolyzed polymeric siloxanes. There is evidence that these fragments appear as ring- and cage-like silsesquioxane cations (Fig. 2) ... 

L-ascorbic acid and, 25 751 catalytic esterification of, 10 482 in cationic polymerization of cyclic siloxanes, 22 560 cellulose as, 11 266 a-chiral and homologated, 13 669 control methods for, 26 687-690 derived from halogen fluorides,... 

Cationic polyelectrolytes, 20 469—472 Cationic polymerization, 19 835 20 409 living, 14 271-272 of cyclic siloxanes, 22 560 of higher olefin polymers, 20 425 Cationic polymers, 11 632 Cationic products, 9 193-194 Cationic PVA, 25 602... 

Protic acids, in cationic polymerization of cyclic siloxanes, 22 560 PROTO (-)-Protoemetine, 2 84, 85 Protonated ozone, 7 7 774-775 Protonated pyridines, 27 100-101 Protonation, 75 653-654... 

Cypryk, M. Chojnowski, J. Kurjata, J. Tertiary Trisilyloxonium Ion and Silylenium Cation in Cationic Ring-opening Polymerization of Cyclic Siloxanes. In Organosilicon Chemistry VI From Molecules to Materials Auner, N., Weis, J., Eds. Wiley-VCH Weinheim, 2005 pp 85-92. 

Chojnowski, J. Kazmierski, K. Cypryk, M. Fortuniak, W. Cationic Ring Opening Polymerization of Cyclotrisiloxanes with Mixed Siloxane Units. In Silicones and Silicone-Modified Materials-, Clarson, S. J., Fitzgerald, J. J., Owen, M. J., Smith, S. D., Eds. ACS Symposium Series 729 American Chemical Society Washington, DC, 2000 pp 20-37. 

Surface complexes between metal cations and siloxane ditrigonal cavities on 2 1 phyllosilicates, shown in exploded view. 

A special case of coagulation is the "quasi crystal" formation by unit layers of mont-morillonite bearing exchangeable Ca2+ cations (cf. Fig. 3.10). As Sposito (1989) points out, "one can imagine that the competition between the repulsive electrostatic forces and the attractive van der Waals force will, along with random thermal motions, largely determine the behavior of two siloxane surfaces approaching each other to a distance of separation >10 nm. However, at a separation distance of... 

In this paper we will discuss the synthesis of a, urhydroxybutyl terminated polydimethylsiloxane oligomers by cationic routes and a,u-aminopropyl terminated poly(dimethy1-diphenyl)siloxane oligomers by anionic methods respectively. Detailed procedures for the synthesis of aminopropyl, carhoxypropyl and glycidoxypropyl terminated polydimethylsiloxane oligomers have already been described elsewhere(1 1). ... 

The configuration of near sohd phase water can be altered in close proximity to the phyUosilicate. The siloxane surface influences the character of the water due to the nature of their charge distribution and the complexes formed between the cation and the surface functional groups. Both the type of charge and degree of charge localization, as well the valence and size of the complexed cations, confiol the characteristics of the water molecules near the surface. 

The commercial importance of polysiloxanes (silicone polymers) was discussed in Sec. 2-12f. The higher-MW polysiloxanes are synthesized by anionic or cationic polymerizations of cyclic siloxanes [Bostick, 1969 Kendrick et al., 1989 Noll, 1968 Saam, 1989 Wright, 1984]. The most commonly encountered polymerizations are those of the cyclic trimers and tetra-... 

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