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84929103128
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Most CDr polymers depolymerize only in polar media, where the transition states that facilitate depolymerization are presumably well solvated.
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Most CDr polymers depolymerize only in polar media, where the transition states that facilitate depolymerization are presumably well solvated.
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84929103129
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Poly(phthalaladehyde)(PPA) that is end-capped with specific detection units is the only other existing CDr polymer that has been demonstrated to depolymerize in the context of macroscopic solid-state materials in response to specific applied molecular signals
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Poly(phthalaladehyde)(PPA) that is end-capped with specific detection units is the only other existing CDr polymer that has been demonstrated to depolymerize in the context of macroscopic solid-state materials in response to specific applied molecular signals. PPA, however, is thermally unstable, and highly sensitive to mild acids and bases, and thus decomposes readily, even when stored as a solid at room temperature. Therefore, PPA is not suitable for selective laser sintering or other thermal additive manufacturing processes that could be used to create macroscopic, multi-stimuli-responsive materials. PPA derivatives that contain unresponsive end caps, however, have been used in thermal probe nanolithography to pattern 3D, nanoscale structures in thin films by a thermal ablation process, where the thermal instability of PPA is used as an advantage.[10] The fabrication portion herein, in contrast, uses additive processes to create stable, yet multi-stimuli-responsive macroscopic plastics that display response properties that are inspired by biological materials in plants.
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84929103130
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(University of Texas System), US 4863538A.
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C. R. Deckard, (University of Texas System), US 4863538A, 1989.
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Deckard, C.R.1
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84929103131
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We previously reported a crude demonstration of a macroscopic plastic that provided an amplified response to an applied signal.[14] This example used poly(phthalaldehyde)(PPA) that contained an end cap that responded to fluoride. We cast a millimeter-thick piece of PPA that contained an unreactive end cap, then used a lancet to punch a hole in the piece. This hole was filled with PPA, which responded to fluoride. This seminal demonstration provided the motivation for this current work, since a piece of plastic with a hole was the best plastic that we could prepare (with substantial difficulty) because of the general instability of PPA.
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We previously reported a crude demonstration of a macroscopic plastic that provided an amplified response to an applied signal.[14] This example used poly(phthalaldehyde)(PPA) that contained an end cap that responded to fluoride. We cast a millimeter-thick piece of PPA that contained an unreactive end cap, then used a lancet to punch a hole in the piece. This hole was filled with PPA, which responded to fluoride. This seminal demonstration provided the motivation for this current work, since a piece of plastic with a hole was the best plastic that we could prepare (with substantial difficulty) because of the general instability of PPA.
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84929103132
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Electron-withdrawing groups at positions para to benzylic acetals in small molecules decreases the reactivity of the acetals to acid-catalyzed deprotection (Ref. [16]).
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Electron-withdrawing groups at positions para to benzylic acetals in small molecules decreases the reactivity of the acetals to acid-catalyzed deprotection (Ref. [16]).
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130 days was the length of the study.
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- 130 days was the length of the study.
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84929103134
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No glass transition temperature (Tg) was found for Alloc-PCl2PA-OiPr (4) using differential scanning calorimetry (DSC, Figure S12), which is consistent with similar observations for PPA.[24] Additional TGA experiments on Ac-PCl2A-OiPr and Ac-PPA-OiPr, which contain ester rather than carbonate end caps (Alloc-PCl2A-OiPr and Alloc-PPA-OiPr contain carbonate end caps), reveal a similar 40 C increase in the stability of the PCl2PA derivative over the PPA derivative, as well as 8-14 C increases in stability for the Ac-end-capped derivatives relative to the Alloc-end-capped variants (i.e. Ac-PPA-OiPr is 14 C more stable than Alloc-PPA-OiPr, and Ac-PCl2A-OiPr is 8 C more stable than Alloc-PCl2A-OiPr)
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No glass transition temperature (Tg) was found for Alloc-PCl2PA-OiPr (4) using differential scanning calorimetry (DSC, Figure S12), which is consistent with similar observations for PPA.[24] Additional TGA experiments on Ac-PCl2A-OiPr and Ac-PPA-OiPr, which contain ester rather than carbonate end caps (Alloc-PCl2A-OiPr and Alloc-PPA-OiPr contain carbonate end caps), reveal a similar 40 C increase in the stability of the PCl2PA derivative over the PPA derivative, as well as 8-14 C increases in stability for the Ac-end-capped derivatives relative to the Alloc-end-capped variants (i.e. Ac-PPA-OiPr is 14 C more stable than Alloc-PPA-OiPr, and Ac-PCl2A-OiPr is 8 C more stable than Alloc-PCl2A-OiPr). This consistent trend in stability between PCl2PA and PPA, as well as Ac versus Alloc suggests that the TGA measurements reflect the thermal stability of the polymers, rather than differences in the boiling points of the thermal decomposition products.
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84929103135
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Powder bed selective laser sintering machines are used for the manufacture of 3D objects.
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Powder bed selective laser sintering machines are used for the manufacture of 3D objects.
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36
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84929103136
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The granules were formulated with 30 % w/w dibutyl phthalate as a plasticizer.
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The granules were formulated with 30 % w/w dibutyl phthalate as a plasticizer.
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We measured 39 particles to determine the average length and the standard deviation.
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We measured 39 particles to determine the average length and the standard deviation.
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38
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84929103138
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The granular polymers and sintered objects were redissolved in THF for the GPC analysis.
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The granular polymers and sintered objects were redissolved in THF for the GPC analysis.
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39
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84908431217
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Other chemical species in solution (such as the stimulus and plasticizers) limited the yield of recovered 3 by recrystallization or sublimation.
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Other chemical species in solution (such as the stimulus and plasticizers) limited the yield of recovered 3 by recrystallization or sublimation.
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