Marvin D. Alim

Mechanistic Kinetic Modeling of Thiol–Michael Addition Photopolymerizations via Photocaged “Superbase” Generators: An Analytical Approach

A kinetic mechanism and the accompanying mathematical framework are presented for base-mediated thiol-Michael photopolymerization kinetics involving a photobase generator. Here, model kinetic predictions demonstrate excellent agreement with a representative experimental system composed of 2-(2-nitrophenyl)propyloxycarbonyl-1,1,3,3-tetramethylguanidine (NPPOC-TMG) as a photobase generator that is used to initiate thiol-vinyl sulfone Michael addition reactions and polymerizations. Modeling equations derived from a basic mechanistic scheme indicate overall polymerization rates that follow a pseudo-first-order kinetic process in the base and coreactant concentrations, controlled by the ratio of the propagation to chain-transfer kinetic parameters (kp/kCT) which is dictated by the rate-limiting step and controls the time necessary to reach gelation. Gelation occurs earlier as the kp/kCT ratio reaches a critical value, wherefrom gel times become nearly independent of kp/kCT. The theoretical approach allowed determining the effect of induction time on the reaction kinetics due to initial acid-base neutralization for the photogenerated base caused by the presence of protic contaminants. Such inhibition kinetics may be challenging for reaction systems that require high curing rates but are relevant for chemical systems that need to remain kinetically dormant until activated although at the ultimate cost of lower polymerization rates. The pure step-growth character of this living polymerization and the exhibited kinetics provide unique potential for extended dark-cure reactions and uniform material properties. The general kinetic model is applicable to photobase initiators where photolysis follows a unimolecular cleavage process releasing a strong base catalyst without cogeneration of intermediate radical species.

High Dynamic Range (Δn) Two-Stage Photopolymers via Enhanced Solubility of a High Refractive Index Acrylate Writing Monomer

Holographic photopolymers capable of high refractive index modulation (Δn) on the order of 10-2 are integral for the fabrication of functional holographic optical elements that are useful in a myriad of optical applications. In particular, to address the deficiency of suitable high refractive index writing monomers for use in two-stage holographic formulations, here we report a novel high refractive index writing monomer, 1,3-bis(phenylthio)-2-propyl acrylate (BPTPA), simultaneously possessing enhanced solubility in a low refractive index (n = 1.47) urethane matrix. When examined in comparison to a widely used high refractive index monomer, 2,4,6-tribromophenyl acrylate, BPTPA exhibited superior solubility in a stage 1 urethane matrix of approximately 50% with a 20% higher refractive index increase per unit amount of the writing monomer for stage 2 polymerizations. Formulations with 60 wt % loading of BPTPA exhibit a peak-to-mean holographic Δn ≈ 0.029 without obvious deficiencies in transparency, color, or scatter. To the best of our knowledge, this value is the highest reported in the peer-reviewed literature for a transmission hologram. The capabilities and versatility of BPTPA-based formulations are demonstrated at varying length scales via demonstrative refractive index gradient structure examples including direct laser write, projection mask lithography of a 1″ diameter Fresnel lens, and ∼100% diffraction efficiency volume transmission holograms with a 1 μm fringe spacing in 11 μm thick samples.

Transport-of-intensity-based phase imaging to quantify the refractive index response of 3D direct-write lithography

Precise direct-write lithography of 3D waveguides or diffractive structures within the volume of a photosensitive material is hindered by the lack of metrology that can yield predictive models for the micron-scale refractive index profile in response to a range of exposure conditions. We apply the transport of intensity equation in conjunction with confocal reflection microscopy to capture the complete spatial frequency spectrum of isolated 10 μm-scale gradient-refractive index structures written by single-photon direct-write laser lithography. The model material, a high-performance two-component photopolymer, is found to be linear, integrating, and described by a single master dose response function. The sharp saturation of this function is used to demonstrate nearly binary, flat-topped waveguide profiles in response to a Gaussian focus.

A readily programmable, fully reversible shape-switching material

Liquid crystalline elastomers programmed with light-activated bond exchange allowing controlled shape change. Liquid crystalline (LC) elastomers (LCEs) enable large-scale reversible shape changes in polymeric materials; however, they require intensive, irreversible programming approaches in order to facilitate controllable actuation. We have implemented photoinduced dynamic covalent chemistry (DCC) that chemically anneals the LCE toward an applied equilibrium only when and where the light-activated DCC is on. By using light as the stimulus that enables programming, the dynamic bond exchange is orthogonal to LC phase behavior, enabling the LCE to be annealed in any LC phase or in the isotropic phase with various manifestations of this capability explored here. In a photopolymerizable LCE network, we report the synthesis, characterization, and exploitation of readily shape-programmable DCC-functional LCEs to create predictable, complex, and fully reversible shape changes, thus enabling the literal square peg to fit into a round hole.

High dynamic range two-stage photopolymer materials through enhanced solubility high refractive index writing monomers

Holographic photopolymers capable of high refractive index modulations (Δn) on the order of 10-2 are integral for the fabrication of functional holographic optical elements (HOEs) for use in a range of optical applications. A novel high refractive index liquid writing monomer suitable for two-stage photopolymer systems was designed and synthesized. This monomer exhibits facile synthetic procedure, low viscosity, high refractive index as well as excellent solubility in a low refractive index urethane matrix. The solubility limit, refractive index change and reaction kinetics/conversion were studied against a commercial reference high refractive index monomer, 2,4,6-tribromophenyl acrylate (TBPA). Superior performance in solubility to TBPA is shown with similar reaction kinetics and final conversion as confirmed by realtime Fourier transform infrared spectroscopy (FTIR) and real-time monitoring of diffraction grating growth. We demonstrate the ability to load substantial amounts of these writing monomers enabling a straightforward path to higher achievable Δn values (peak-to-mean Δn ~ 0.03) without sacrificing optical properties (transparency, color or scatter) as validated through recording ~100% efficiency volume transmission holograms in sub-15 μm thick films.

Recyclable and repolymerizable thiol–X photopolymers

We demonstrate a class of rapidly photopolymerizable step-growth cross-linked networks that incorporate thioesters into the backbone. The thioester functional groups enable complete degradation of the network into oligomers that can subsequently be recycled into a nearly indistinguishable material with no change in material behavior.

Predictive modeling of two-component holographic photopolymers

We present a general strategy for characterizing the reaction and diffusion kinetics of polymeric holographic recording media by which key processes are decoupled and independently measured. The separate processes are combined into a predictive model that is shown to make accurate quantitative predictions of index response over three orders of exposure dose (~1 to ~103 mJ/cm2) and feature size (0.35 to 500 microns) for a model material similar to commercial media. Several critical performance concepts also emerge from the model, including a prediction of a formulation’s maximum potential index response, insight into why a particular material may not achieve this maximum and the process that limits the recording resolution.

Mechanical response of holographic photopolymers

Two-chemistry polymer systems are attractive platforms for a wide range of optical and mechanical applications due to the orthogonal chemistries of the initial thermoset matrix and the subsequent photo-initiated polymerization. This scheme allows the mechanical and optical properties of the materials to be individually addressed. However, the mechanical properties of both the initial matrix and the photopolymer system affect the performance of these materials in many applications from holography to optically-actuated folding. We present a mechanical model along with experimental demonstrations of a two-chemistry holographic photopolymer system. A three-dimensional finite element model is used to simulate the mechanical and chemical responses in time. The model uses standard material measurements to predict both large-scale deformation and more localized stress and strain. To demonstrate the magnitude of mechanical stresses possible in these materials, we show bending of thin strips with UV light activation using an optical absorber to create an intensity gradient in depth. The resulting non-uniform polymerization causes shrinkage and bending toward the light followed by swelling and bending away from the light caused by monomer diffusion. In addition to this large-scale bending, we demonstrate that the model can be used to qualitatively predict surface deformations that can be used for surface relief optical elements. The mechanical model enables understanding of shrinkage and swelling properties of a material system that affect the performance of that system over a wide range of illumination conditions.

Holographic analysis of photopolymers

Two-beam holographic exposure and subsequent monitoring of the time-dependent first-order Bragg diffraction is a common method for investigating the refractive index response of holographic photopolymers for a range of input writing conditions. The experimental set up is straightforward, and Kogelnik’s well-known coupled wave theory (CWT)[1] can be used to separate measurements of the change in index of refraction (Δn) and the thickness of transmission and reflection holograms. However, CWT assumes that the hologram is written and read out with a plane wave and that the hologram is uniform in both the transverse and depth dimensions, assumptions that are rarely valid in practical holographic testing. The effect of deviations from these assumptions on the measured thickness and Δn become more pronounced for over-modulated exposures. As commercial and research polymers reach refractive index modulations on the order of 10-2, even relatively thin (< 20 μm thick) transmission volume holograms become overmodulated. Peak Δn measurements for material analysis must be carefully evaluated in this regime. We present a study of the effects of the finite Gaussian write and read beams on the CWT analysis of photopolymer materials and discuss what intuition this can give us about the effect other non-uniformities, such as mechanical stresses and significant absorption of the write beam, will have on the analysis of the maximum attainable refractive index in a material system. We use this analysis to study a model high Δn two-stage photopolymer holographic material using both transmission and reflection holograms.

Analysis of holographic photopolymers for integrated optical systems via quantitative phase microscopy

Optically-driven diffusion of high refractive index molecules within a transparent thermoset polymer matrix is a promising platform for hybrid optics that combines a wide range of optical structures from large scale holograms to micron-scale gradient index waveguides in a single integrated optical system. Design of such a system requires characterization of the optical response of the material at a wide range of spatial scales and intensities. While holographic analysis of the photopolymers is appropriate to probe the smaller spatial scales and lower intensity optical response, quantitative phase mapping of isolated structures is needed to probe the response to the higher intensities and lower spatial frequencies used in direct write lithography of waveguides. We apply the transport of intensity equation (TIE) to demonstrate quantitative refractive index measurements of 10 μm-scale localized gradient index structures written into diffusive photopolymer materials using both single- and two-photon polymerization. These quantitative measurements allow us to study the effect of different exposure conditions and material parameters such as writing beam power, exposure time, and wt% loading of the writing monomer on the overall profile of the refractive index structure. We use these measurements to probe the time scales over which diffusion is significant, and take advantage of the diffusion of monomer with a multiple-write scheme that achieves a peak refractive index contrast of 0.025.