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The transparent and flexible photocatalytic films composed of titanium oxide, organophosphonate-modified polysilsesquioxane, and poly(bisphenol A-co-epichlorohydrin) were prepared. The effects of hydroxy group ratio and organic substituent on phosphorus atoms in these films were evaluated by appearance and photocatalytic ability. Film using anchoring layer with APPS-low was formed large cracks, while films with other anchoring layers were formed no cracks. However, all films were formed small cracks after a 10-day durability test. All films showed photodegradation ability of methylene blue, photoinduced hydrophilicity, and photocatalytic bactericidal effects on Escherichia coli.

In this work, POSS with an acetylacetonato group (POSS-acac) and metal–coordination polymers comprising POSS-acac (CP(Metal)s) were synthesized. The possible structure of CP(Metal)s was estimated from the UV–Vis spectrum and the residual mass after burning off and the surface morphologies of the CP(Metal)s were observed using scanning electron microscopy.

Organic–inorganic hybrid thin films containing [Ti₄(μ₃-O)(OiPr)₅(μ-OiPr)₃(O₃PPh)₃]·THF (TiOPPh) as element blocks were prepared via hybridization with the hydroxyl-substituted organic polymers (PVP, PSA, or PBE) by spin-coating. The hybrid thin films were characterized by AFM, DSC, and pencil hardness. The pencil hardness values of the PVP hybrid thin films were in the order 20 > 40 > 0 wt% and were dependent on the surface smoothness. When TiOPPh was reacted with excess ethanol, the core was retained. Therefore, the core of TiOPPh will be retained in the hybrid polymers.

We synthesized poly(bisphenol A-co-ephichlorohydrin)–titanium phosphonate clusters (Ti₄P₃: [Ti₄(μ₃-O)(OiPr)₅(μ-OiPr)₃(O₃PPh)₃]·thf; Ti₄P₄: [Ti(OiPr)(acac)(O₃PPh)]₄; Ti₇P₆: Ti₇(μ₃-O)₂ (OiPr)₆(μ-OiPr)₆(O₃PBnBr)₆). From the result of swelling test using tetrahydrofuran, Ti₇P₆ cluster showed highest cross-linking efficiency.

Titanium phosphonate (TiOPPh: [Ti₄(μ₃-O)(OⁱPr)₅(μ-OⁱPr)₃(PhPO₃)₃]·thf) was synthesized. TiOPPh was mixed with poly(methyl methacrylate) (PMMA) or poly(vinyl alcohol) (PVA) to prepare organic–inorganic hybrid polymer films. The film using PMMA was formed by the interaction between organic and inorganic components. The temperatures of 10% weight loss of TiOPPh–PMMA were 30 °C higher than that of PMMA only. The film using PVA was formed by the alcohol exchange reaction between TiOPPh and PVA. The transparency of TiOPPh-PVA in the visible region was higher than that of PVA only.

Organic–inorganic hybrids containing [Ti₄(μ₃-O)(OiPr)₅(μ-OiPr)₃(O₃PPh)₃]·thf (TiOPPh) as element-blocks were prepared by hybridization with silicone polymers (poly(dimethylsiloxane) (PDMS), poly(methylsilsesquioxane) (PMS) or poly(ethoxysilsesquioxane) (PEOS)), the hydroxyl groups substituted organic polymers (poly(vinyl alcohol) (PVA), poly(4-vinylphenol), poly(styrene-co-allyl alcohol) or poly(bisphenol A-co-epichlorohydrin) (PBE)) or poly(methyl methacrylate) (PMMA). The concentration of TiOPPh was increased to 40 wt% to form free-standing hybrid films with PDMS, PMS, PVA and PBE polymers. The tensile strengths and elongations of PMMA and PVA films were higher improved than only polymers because TiOPPh acted good crosslinkers.