Synthesis of norbornene block copolymers containing polyhedral oligomeric silsesquioxane by sequential ring-opening metathesis polymerization

Abstract

The synthesis of a series of poly(POSS-NBE-b-MTD) copolymers was successfully accomplished, taking advantage of sequential, ring-opening, metathesis block copolymerization using RuCl 2 (=CHPh)(PCy 3 ) 2 catalyst. By using cyclopentyl-POSS-norbornene (POSS-NBE) monomer as the first block in the block copolymer, living poly(POSS-NBE) with controlled molecular weight and narrow molecular weight distribution was produced. Then, poly(POSS-NBE-b-MTD) copolymers were successfully prepared, in which sequential monomer addition of methyltetracyclododecene (MTD) to the living poly(POSS-NBE) chain ends was utilized to achieve quantitative crossover efficiency. Characterization by 1 H NMR spectroscopy and GPC confirmed the high definition and structural integrity of the poly(POSS-NBE-b-MTD) copolymers. Thermal properties and morphologies of the POSS-containing block copolymer nanocomposites were also investigated by using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and wide-angle X-ray scattering (WAXS).

Synthesis and properties of polysiloxanes containing polyhedral oligomeric silsesquioxane (POSS) and oligo (ethylene oxide) groups in the side chains

“…Numerous classes of hybrid nanocomposite materials have recently been developed, such as threedimensional sol-gel materials, 1-3 inorganic/organic polymer blends, 4,5 and polymeric nanocomposites having polyhedral oligomeric silsesquioxane (POSS) groups. [6][7][8][9][10][11] In particular, polymers having POSS groups covalently bonded to the polymer chains have been studied extensively since POSS groups can increase and improve decomposition temperature and oxidation stability. [12][13][14] Poly(ethylene oxide) (PEO) has been studied as a solid polymer electrolyte in lithium ion batteries due to its ability to solvate lithium ions.…”

Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

“…Kim and Kwon have shown that ring-opening metathesis copolymerization of norbornenylethyl-POSS with methyltetracyclododecene in the presence of first generation Grubbs catalyst ( Ru-1 ) is a practical route to the synthesis of block copolymers containing POSS nanoparticles (Scheme 26) [50]. ROMP of norbornenylethyl-POSS produced the corresponding homopolymer in relatively controlled molecular weights ( M n = 17,900–26,300 Da) and narrow molecular weight distributions (in the range M n / M w = 1.19–1.29).…”

Amphiphilic norbornene-based diblock copolymers containing polyhedral oligomeric silsesquioxane prepared by living ring opening metathesis polymerization

“…However, only a few block copolymers containing POSS nanoparticles have been reported so far. [19][20][21][22] In this study, synthesis and characterization of amphiphilic organic/inorganic block copolymers containing hydrophobic POSS segments have been explored to provide key model block copolymer nanocomposites. For constructing hydrophilic segment in block copolymers, 2-endo-3-exo-5-norbornene dicarboxylic acid (NBECOOH) is considered, due to the highly polar carboxylic acid groups.…”