Amanda S. Fawcett

Simple Strategies to Manipulate Hydrophilic Domains in Silicones

Hydrophilic silicone polymers offer advantageous properties in a variety of applications. However, it is not always straightforward to control the placement of hydrophilic domains in a hydrophobic silicone elastomer. A facile method for the preparation of poly(ethylene oxide)(PEO)-modified PDMS elastomers is described. Hydrosilane rich elastomers are fabricated by adding poly(hydromethylsiloxane) to a standard addition cure elastomer formula. After curing the elastomer, the silicones can be modified using hydrosilylation with mono- and di-allyl pol(ethylene oxide) of varying molecular weights to give PEO-rich silicone surfaces. The efficiency of the grafting process, as measured by PEO on the surface, depends both on molecular weight and functionality of the PEO. By contrast, when the allyl functional PEO is added directly to the elastomer preparation (co-cure), silicone elastomers with internal PEO domains are formed: SiH rich polymers present preferentially at the external interface.

Surface-active copolymer formation stabilizes PEG droplets and bubbles in silicone foams.

Large increases in viscosity are not normally observed when insoluble liquid polymers are mixed in the absence of a compatibilizing agent: the liquids separate into bulk phases. Mixing propyl- or allyl-modified oligo(ethylene glycol)(PEG), but not the parent hydroxy-terminated oligo(ethylene glycol), with silicone pre-elastomers led a sharp increase in viscosity that preceded the onset of cure. Only in the case of allyl-modified PEG, however, did a low density, closed cell silicone foam form that, in addition to trapped bubbles, contained dispersed PEG droplets. Rheological studies demonstrate that the origins of the viscosity build lie in the formation, shortly after mixing, of organo-PEG stabilized droplets that act as fillers within the silicone pre-elastomers. Similar viscosity builds were not observed with hydroxy-terminated oligo(ethylene glycol). Although the propyl-modified PEG led initially to large viscosity increases, its ability to stabilize bubbles was comparably limited. The surface activity of the propyl- and allyl-PEG compounds themselves facilitates the formation of a colloidal dispersion within the silicone. However, the key to the observed foamed product is the in situ platinum-catalyzed hydrosilylation of the allyl group, prior to or concomitant with silicone cure, leading to PEG-silicone copolymers that are able to stabilize both dispersed PEG droplets and bubbles.

Silicone foams stabilized by surfactants generated in situ from allyl-functionalized PEG

Silicone foams normally require the use of agents or chemical reactions that blow gases, and a surfactant for bubble stabilization. We have discovered that the presence of monoallyl-functionalized poly(ethylene glycol) (PEG) leads to large increases in the viscosity of silicone pre-elastomers such that stable foams form with bubbles mostly being generated by coalescence of dissolved gases during the normal degassing process. Although silicone elastomer cure may take up to 24 h for completion, the foams remain stable during this time when appropriate concentrations of allyl-PEG and curing catalyst are used. No traditional surfactant is required, but PEG-modified silicone surfactants are formed in situ by covalent grafting of the PEG to the silicone matrix, leading to the increase in viscosity. The presence of allyl-PEG decreases elastomer cure efficiency, but this is readily overcome, if necessary, to generate more rigid foams by the use of additional platinum catalyst, in which case foaming occurs both due to loss of dissolved gases and to hydrogen evolution. Foam stabilization with appropriate allyl-PEG compounds is a consequence of an initial viscosity increase.