We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that can serve as mechano-optic actuators for applications that include non-invasively steering fiber optics. The coil (polystyrene) end-blocks phase segregate from the liquid crystal midblock forming of uniform and uniformly-spaced physical crosslinks, resulting in highly reproducible and thermoreversible networks by self-assembly. These polymers are elastic in the melt (at room temperature) and can be easily spun, coated or molded. Mechanical stretching results in a temporary monodomain alignment. Starting from identical triblock prepolymers (with polystyerene end blocks and 1,2-polybutadiene midblocks), a matched pair (azobenzene-containing, and non-azobenzene-containing) of liquid crystal triblock copolymers was synthesized. These triblocks were then be blended to prepare a series of elastomers with 0 to 5% azobenzene groups, while matching in nearly all other physical properties (cross-link density, modulus, birefringence, etc.), allowing the effect of concentration of photo-responsive groups to be unambiguously determined. Results will be presented that demonstrate this approach to independent control of optical density and photo-mechanical sensitivity.
We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that form uniform and highly reproducible elastomers by self-assembly. To serve as actuators to (non-invasively) steer a fiber optic, for example in deep brain stimulation, the polymers are designed to become monodomain “single liquid crystal” elastomers during the fiber-draw process and to have a large stress/strain response to stimulation with either light or heat. A fundamental scientific question that we seek to answer is how the interplay between the concentration of photoresponsive mesogens and the proximity to the nematic-isotropic transition governs the sensitivity of the material to stimuli. Specifically, a matched pair of polymers, one with ~5% azobenzene-containing side groups (~95% cyanobiphenyl side groups) and the other with 100% cyanobiphenyl side groups were synthesized from identical triblock pre-polymers (with polystyerene end blocks and 1,2-polybutadiene midblocks). These can be blended in various ratios to prepare a series of elastomers that are precisely matched in terms of the backbone length between physical crosslinks (because each polymer is derived from the same pre-polymer), while differing in % azobenzene side groups, allowing the effect of concentration of photoresponsive groups to be unambiguously determined.
Soft-solids that retain the responsive optical anisotropy of liquid crystals (LC) can be used as mechano-optical, electro-optical and electro-mechanical elements. We use self-assembly of block copolymers to create reversible LC gels and elastomers that flow at elevated temperatures and physically cross link upon cooling. In the melt, they can be spun, coated or molded. Segregation of the end-blocks forms uniform and uniformly spaced crosslinks. Matched sets of block copolymers are synthesized from a single "prepolymer." Specifically, we begin with polymers having polystyrene (PS) end blocks and a poly(1,2-butadiene) midblock. The pendant vinyl groups along the backbone of the midblock are used to graft mesogens, converting it to a side-group LC polymer (SGLCP). In the present case, cyanobiphenyl groups are used as the nonphotoresponsive mesogens and azobenzene groups are used as photoresponsive mesogens. Here we show that matched pairs of block copolymers, with and without photo-responsive mesogens, provide model systems in which the optical density can be adjusted while holding other properties fixed (cross-link density, modulus, birefringence, isotropic-nematic transition temperature). For example, a triblock in which the SGLCP block has 95% cyanobiphenyl and 5% azo side groups is miscible with one having 100% cyanobiphenyl side groups. Simply blending the two gives a series of LC elastomers that have from 0 to 5% azo, while having all other physical properties matched. Results will be presented that show the outcomesof this approach to systematic and largely independent control of optical density and photo-mechanical sensitivity.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.