Supported organometallic complexes. XXI - Novel D- and T-functionalized polysiloxane matrices for reactions in interphases

New hydrocarbon bridged co-condensation agents of the type RSi(OMe)(2)(CH2) (z)C6H4(CH2)(z)(OMe)(2)SiR {3[Ph(1,4-C3D0)(2)], z=3, R=Me; 3[Ph(1,4-C3T0)(2 )], z=3, R=OMe; 4[Ph(1,4-C3D0)(2)], z=4, R=Me} were synthesized by hydrosil ylation of the corresponding alpha,omega-dienes CH2=CH-(CH2)(z-2)C6H4-(CH2) (z-2)-CH=CH2 [z=3 (1), 4 (2)] with HSiR(OMe)(2) (R=Me, OMe). These silane m onomers were sol-gel processed, partially with MeSi(OMe)(3) (TO) to give th e polysiloxanes 3 a, 3b, 4c, 3d, 3e, 4f and 3 ab (Table 1, Schemes 2 and 3) ; D=D type silicon atom (two oxygen neighbors), T=T type of silicon atom (t hree oxygen neighbors). The relative amounts of T and D silyl species and t he degrees of condensation were determined by Si-29 and C-13 CP/MAS NMR spe ctroscopic investigations. Si-29 and C-13 CP/MAS NMR relaxation time studie s (T-SiH, T-CH, T-1 rho H), and 2D WISE NMR experiments were applied to get knowledge about the polymer dynamics. For the first time protons of such p olysiloxane systems were detected by H-1 SPE/MAS NMR measurements in suspen sion. Mobility studies were carried out in different solvents. Furthermore the swelling capacities of the polymers 3a, 3b, and 4c in different solvent s and the BET surface areas of all materials were investigated. SEM microgr aphs show the morphology of 3a and 3b.