Molecular Design of Side-Group Liquid Crystalline Polymers: Understanding Their Interactions with Small Molecule Liquid Crystal Solvent

Liquid crystal (LC) gels – the combination of macromolecules with small molecule LCs – couple the elasticity and mechanical strength of polymers to the order inherent to LCs and are attractive to many researchers hoping to marry liquid crystals' optical and electro-optical responsiveness with polymers' mechanical strength and ease of processing. In particular, side-group liquid crystal polymers (SGLCPs) are flexible-chain polymers that are functionalized with LC side-groups. Here we introduce the concept of polymer dopants: homogenously dissolved LC-containing SGLCP homopolymers that are molecularly designed for solubility in and coupling to small molecule LC solvents. Using polymer analogous chemistry (changing the molecular makeup of the side groups and their linkers, while keeping backbone molecular weight, polydispersity index, and degree of polymerization constant), we’ve targeted the effect of side-group orientation, dipole position and strength, spacer length and linking-group type on polymer solubility and bulk material properties. We've shown that, at low concentration, these dopants can have significant effects on the bulk material properties of two types of LCs: ferroelectric and vertically aligned nematic LCs

Model photo-responsive elastomers based on the self-assembly of side group liquid crystal triblock copolymers (Presentation Recording)

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

Thermoreversible networks for moldable photo-responsive elastomers (Presentation Recording)

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

pH-responsive aqueous/LC interfaces using SGLCP-b-polyacrylic acid block copolymers

Block copolymers that combine a side-group liquid crystalline polymer (SGLCP) block and a pH-responsivehydrophilic block, poly(acrylic acid) (PAA), are shown to confer pH-dependent anchoring of the director orientation at the aqueous/LC interface. The SGLCP block, poly(4-cyanobiphenyl-4-oxyundecylacrylate), was chosen based on its ability to influence the director field of the 5CB (4-cyano-4'-pentylbiphenyl). At low pH the PAA block collapses and the inherent, planar alignment tendency of 5CB at a water interface prevails. As pH increases, the polyelectrolyte block becomes increasingly charged and expands, producing a change to homeotropic anchoring. The change in anchoring occurs as quickly as the buffer can be changed (within ~2 s) and is reversible, with a response that is repeatable over as many cycles as were tested (approximately 20 cycles). The polymer-mediated anchoring persists for 6 days, indicating that the SGLCP block secures the self-assembled layer on the 5CB, even under conditions that cause repulsive interactions among the PAA blocks. Thus, SGLCP blocks can translate conformational changes of a responsive hydrophilic block into rapid, reversible changes in the director fiel

Photo-responsive and thermoreversible networks from the self-assembly of azobenzene-containing liquid crystal triblock copolymers

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