Multihydroxy-Functional Polysilanes via an Acetal Protecting Group Strategy

Abstract

A new acetal-protected monomer for Wurtz-type coupling to polysilanes, dichloro(3-(2,2dimethyl-1,3-dioxolane-4-yloxy)propyl)methylsilane, referred to as dichloro(isopropylidene glyceryl propyl ether)methylsilane (DCIMS), has been introduced to synthesize a series of protected linear polysilane copolymers, poly[di-n-hexylsilane-co-(isopropylidene glyceryl propyl ether)methylsilane] (P(DHS-co-IMS)) via alkali-mediated reductive Wurtz-type coupling. The acetal protecting group proved stable under the harsh polymerization conditions. Differential scanning calorimetry combined with 1 H, 13 C, and 29 Si NMR measurements confirmed composition and random structure of the obtained copolymers. After separation of the cylic fraction, this route yielded defined linear polysilane copolymers with monomodal molecular weight distributions (2000-98700 g mol -1 (SEC)) and polydispersities in the range 1.61-2.60. Subsequent cleavage of the acetal protecting groups under acidic conditions resulted in the multihydroxy-functional polysilanes poly[di-n-hexylsilane-co-(glyceryl propyl ether)methylsilane] (P(DHS-co-GMS)).

A facile method to prepare a polyethylene glycol modified polysilane as a waterborne photoinitiator

“…Meanwhile, a crystallization peak at À29 C and a melting peak at 14 C were also observed in the DSC curve of polymer 6. All these changes could be ascribed to the introduction of poly(polyether acrylate) unit [36]. The thermal stability of 4 and 6 was investigated by thermogravimetric analysis (TGA).…”

“…The watersoluble or waterborne photoinitiators could be obtained by introducing ionic groups such as quaternary ammonium salts, carboxylic acids, sulfonates [22][23][24][25][26], or hydrophilic groups such as ethoxyethers and carbohydrates into oil-soluble photoiniatiators [27,28], or through inclusion chemistry such as the inclusion complex of 2-hydroxy-2-methyl-1-phenylpropan-1-one and methylated b-cyclodextrin [21]. Conventionally, water-soluble polysilanes such as 1-3 in Chart 1, were prepared by attaching quaternary ammonium salts [29][30][31][32], ethoxyethers [33][34][35] and multihydroxy groups [36] with polysilanes. Some water-soluble polysilanes such as 1 can also be used as a photoinitiator to photoinitiate a series of vinyl monomers in water solution [31].…”

Infrared emissivity property study and conformational analysis of helical polysilane

“…Linear polysilane is a kind of polymer constructed by one‐dimensional silicon backbone with functional sidechain groups . To be more specific, poly(di‐ n ‐hexylsilane) (PDHS) possesses a random distributed 7/3 helical backbone with the dihedral angle around 150° which ascribes to the noncovalent interaction between hexyl side groups and 115.4° bond angle of ∠SiSiSi .…”

Synthesis and Characterization of Multifunctional Chiral and Photoactive Organic-Inorganic Block Copolymers of Poly(methylphenylsilane) with (R)-N-(1-phenylethyl)methacrylamide, Disperse Red 1 Methacrylate and Their optical and Photophysical Properties

“…Hydrosilylation reaction verified as an important approach for obtaining functional polysiloxane and the synthesis of functional polysilane [12]. Multihydroxy functional polysilane copolymer synthesized via acetal protecting group strategy [19]. The multifunctional polysilane synthesized by formation of Si-Cl intermediate and the substitution of Cl with hydroxy containing functional NLO chromophore [20].…”