Functional Phthalaldehyde Polymers by Copolymerization with Substituted Benzaldehydes

Kaitz, Joshua A.; Moore, Jeffrey S.

doi:10.1021/ma302575s

Cited by 56 publications

(73 citation statements)

References 37 publications

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“…Rapid depolymerization of PPA likely is the consequence of the low ceiling temperature ( T c ) of the polymer: without a stabilizing reaction‐based detection unit, the ceiling temperature of the polymer is −40°C, whereas when functionalized with a reaction‐based detection unit, the polymer remains stable up to ∼150°C . This rapid rate of depolymerization is balanced, however, with stability issues when the polymer is exposed to mild acid or base . This polymer highlights the orthogonal challenges associated with designing polymers for stability, but also for rapid depolymerization …”

Section: Current Classes Of Cdr Polymersmentioning

confidence: 99%

Amplified responses in materials using linear polymers that depolymerize from end‐to‐end when exposed to specific stimuli

Phillips

Robbins

DiLauro

et al. 2014

J of Applied Polymer Sci

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This review describes new types of smart materials that have the dual capabilities of responding to selective signals and providing an amplified response. Amplification arises from a signal-induced depolymerization reaction, where a single signaling event causes an entire polymer to convert to small molecules. When incorporated into a material, depolymerization of these polymers causes a change in shape, internal structure, or surfaces properties of the material. Moreover, the small molecules arising from depolymerization can play a role in the amplified response, particularly when they provide a secondary function (e.g., production of color or fluorescence). A brief overview of the current examples of linear depolymerizable polymers is provided, as are representative proof-of-concept applications of these polymers in the context of diagnostics and materials that remodel themselves and/or their surroundings. Together, these examples highlight the potential of this new class of polymers to provide unique and dramatic function to stimuli-responsive materials.

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Section: Current Classes Of Cdr Polymersmentioning

confidence: 99%

Amplified responses in materials using linear polymers that depolymerize from end‐to‐end when exposed to specific stimuli

Phillips

Robbins

DiLauro

et al. 2014

J of Applied Polymer Sci

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“…Copolymers with PHA have been previously synthesized, but the equilibrium thermodynamic data has not been reported. 23,24 The contribution of each type of aldehyde to the forming polymer was determined by in situ NMR. The interaction of BA with BF 3 -OEt 2 has previously been studied.…”

Section: Also Of Note Inmentioning

confidence: 99%

Determination of ceiling temperature and thermodynamic properties of low ceiling temperature polyaldehydes

Schwartz

Engler

Phillips

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Knowledge of the ceiling temperature and thermodynamic variables for low ceiling temperature polymers is critical to understanding the material's synthesis and use. Synthesis of the polymer below its ceiling temperature is the routine polymerization route. In situ 1H NMR of the equilibrium polymerization reaction can provide critical information for determining the enthalpy and entropy of polymer formation. Three polyaldehydes were synthesized with in situ 1H NMR, and their energies of formation were determined for the linear region of ceiling temperature. Insights into the mechanism of polymerization were also found using this method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 221–228

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“…16,17 The polymer also is sensitive to acid and base, which limits the number of techniques that can be used to fabricate microcapsules using PPHA. 19 ■ RESULTS AND DISCUSSION Preparing End-Capped Poly(phthalaldehydes). To investigate the effect of membrane polymer molecular weight on the release kinetics, we prepared several lengths of the fluoride-responsive PPHA polymer using the anionic polymerization procedure shown in Figure 2.…”

Section: ■ Introductionmentioning

confidence: 99%

Stimuli-Responsive Core–Shell Microcapsules with Tunable Rates of Release by Using a Depolymerizable Poly(phthalaldehyde) Membrane

et al. 2013

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Flow-focusing microfluidic techniques were used to provide access to core−shell microcapsules in which the shell is composed of end-capped poly(phthalaldehydes) that depolymerize completely from head-to-tail in response to fluoride. Microcapsules made from these depolymerizable polymers provide an amplified response to the applied chemical signal, where the rate of the response can be tuned both by varying the length of the polymer and the thickness of the shell wall. ■ INTRODUCTIONStimuli-responsive polymeric core−shell microcapsules are promising materials for controlled release applications. 1−8 Capsules of this type typically release their contents either through induced chemical changes in the polymers that compose the shell or via bulk structural changes to the shell wall. 1 These traditional triggered-release strategies provide responses that are nonamplified: i.e., a single membrane−signal interaction produces one small structural change in the shell wall, whereas release occurs only after many signals have reacted with and altered the shell wall. In contrast, a new release strategy has emerged where shell walls are formed from polymers that depolymerize continuously and completely from head-to-tail when an appropriate signal is detected by the polymer. 1,9 This depolymerization reaction provides an amplified response that, in theory, increases the sensitivity of the capsules as well as their rate of response once the appropriate signal is detected. Despite these favorable attributes, however, only one example of a stimuli-responsive core−shell polymeric microcapsule made from a head-to-tail depolymerizable polymer has been demonstrated to date, 10 with additional related examples demonstrated in responsive nanocapsules and micelles. 11,12 Further development of this depolymerizable shell wall concept has been hindered by the limited number of polymers that are capable of depolymerizing from head-to-tail in response to a specific signal, as well as by substantial challenges in fabricating core−shell microcapsules using polymers that are primed to depolymerize.In this article, we describe the use of flow-focusing microfluidic strategies for fabricating these types of depolymerizable core−shell microcapsules. 13−15 This technique is highly reproducible, readily forms capsules that contain aqueous interiors, is capable of generating capsules that can be suspended in an aqueous solution that differs from the solution within the capsule, and does not require synthetic manipulation of the polymer for incorporation into the shell wall. Moreover, the fabrication technique is exceptionally mild and thus enables the formation of core−shell microcapsules using sensitive depolymerizable polymers such as poly(phthalaldehyde) (PPHA) (Figure 1). 16,17 Herein we demonstrate these concepts by fabricating model stimuli-responsive core−shell microcapsules using PPHA that contains a fluoride-responsive endcap. The end-cap controls the stability and reactivity of the PPHA polymer and thus enables release of the ...

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Functional Phthalaldehyde Polymers by Copolymerization with Substituted Benzaldehydes

Cited by 56 publications

References 37 publications

Amplified responses in materials using linear polymers that depolymerize from end‐to‐end when exposed to specific stimuli

Amplified responses in materials using linear polymers that depolymerize from end‐to‐end when exposed to specific stimuli

Determination of ceiling temperature and thermodynamic properties of low ceiling temperature polyaldehydes

Stimuli-Responsive Core–Shell Microcapsules with Tunable Rates of Release by Using a Depolymerizable Poly(phthalaldehyde) Membrane

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