A novel soluble, reactive ladder-like polysilsesquioxane (L) with lateral bromophenyl groups was synthesized successfully by stepwise coupling polymerization (SCP) method including preaminolysis, hydrolysis and polycondensation steps. The monomer 3-trichlorosilylpropoxy-4-bromobenzene (M) was first prepared via hydrosilylation reaction catalyzed by dicyclopentadienylplatinum dichloride (Cp2PtCl2). The title polymer (L) was characterized by 1H-NMR, 29Si-NMR, FTIR, X-ray diffraction (XRD), DSC and vapor pressure osmometry (VPO). The experimental results indicate that the polymer (L) possesses a typical ladder-like structure.
A novel ordered reactive oligomeric ladderlike copolymethyl-aminopropylsilsesquioxane(Me-AP-T),was successfully synthesized by an efficient hydrosilylation graft reaction of 1,1,1-trimethyl-N-2-propenyl-silanamine with a reactive oligomeric ladderlike copolymethyl-hydrosilsesquioxane(Me-H-T),which was prepared by“supramolecular chemistry-dictated stepwise coupling polymerization”process.FT-IR,~1H-and ^(29)Si-NMR spectra show that hydrosilylation reaction proceeds completely.Moreover,~1H-NMR spectra also indicate that both the molar ratios of≡SiMe group to Si—H and≡SiMe group to≡SiPrNH_2 are approximately 1:1 respectively based on the ratio of integrated resonance areas of the different groups.XRD analysis and ^(29)Si-NMR spectra are used for investigating the ladderlike structure of the polymers.A high T_g(128.38℃)of Me-AP-T shown in DSC measurement implies that the ordered reactive Me-AP-T macromolecules have much stiff chains.
