Supramolecular engineering polyesters: endgroup functionalization of glycol modified PET with ureidopyrimidinone

Houston, Katelyn R.; Jackson, Anne-Martine S.; Yost, R.; Carman, Howard S.; Ashby, Valerie Sheares

doi:10.1039/c6py01421f

Cited by 18 publications

(15 citation statements)

References 30 publications

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“…The progress of self‐healing was monitored at room temperature for approximately 1 h, whereupon no change was observed. The resins were heated to 80 °C in order to induce disassembly of UPy/UPy associations and observed at room temperature after 15 and 45 min. No visible changes were observed in the notch of the control resin B .…”

Section: Resultsmentioning

confidence: 99%

Self Assembly–Assisted Additive Manufacturing: Direct Ink Write 3D Printing of Epoxy–Amine Thermosets

Manning

Wyatt

Hughes

et al. 2018

Macro Materials & Eng

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The use of self‐assembling, pre‐polymer materials in 3D printing is rare, due to difficulties of facilitating printing with low molecular weight species and preserving their reactivity and/or functions on the macroscale. Akin to 3D printing of small molecules, examples of extrusion‐based printing of pre‐polymer thermosets are uncommon, arising from their limited rheological tuneability and slow reactions kinetics. The direct ink write (DIW) 3D printing of a two‐part resin, Epon 828 and Jeffamine D230, using a self‐assembly approach is reported. Through the addition of self‐assembling, ureidopyrimidinone‐modified Jeffamine D230 and nanoclay filler, suitable viscoelastic properties are obtained, enabling 3D printing of the epoxy–amine pre‐polymer resin. A significant increase in viscosity is observed, with an infinite shear rate viscosity of approximately two orders of magnitude higher than control resins, in addition to, an increase in yield strength and thixotropic behavior. Printing of simple geometries is demonstrated with parts showing excellent interlayer adhesion, unachievable using control resins.

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Section: Resultsmentioning

confidence: 99%

Self Assembly–Assisted Additive Manufacturing: Direct Ink Write 3D Printing of Epoxy–Amine Thermosets

Manning

Wyatt

Hughes

et al. 2018

Macro Materials & Eng

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“…96,34 Therefore, a plethora of studies reported the contribution of UPy stacking on polymer dynamics as an inevitable part of this sticker. 97,98 This is indeed a big disadvantage when comparing with theories, although in some studies this effect has not been truly addressed. 99,100 For instance, in one study by Binder et al on PnBA end-capped with THY and/or DAT the absence of a plateau in the frequency sweeps was related to the absence of phase separation.…”

Section: Sticker Positionmentioning

confidence: 99%

A Critical Approach to Polymer Dynamics in Supramolecular Polymers

Golkaram

Loos

2019

Macromolecules

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Over the past few years, the concurrent (1) development of polymer synthesis and (2) introduction of new mathematical models for polymer dynamics have evolved the classical framework for polymer dynamics once established by Doi–Edwards/de Gennes. Although the analysis of supramolecular polymer dynamics based on linear rheology has improved a lot recently, there are a large number of insecurities behind the conclusions, which originate from the complexity of these novel systems. The interdependent effect of supramolecular entities (stickers) and chain dynamics can be overwhelming depending on the type and location of stickers as well as the architecture and chemistry of polymers. This Perspective illustrates these parameters and strives to determine what is still missing and has to be improved in the future works.

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“…Moreover, it was proposed that an additional stacking of the UPy groups is supported by hydrogen bonding of the urethane/urea groups next to the UPy moieties ( Van Beek et al, 2007 ; Bobade et al, 2014 ). An important additional contribution to the improved printability of such supramolecular “chain-extended” polymers is induced by avoiding phase segregation effects, as the UPy groups present in linear polymers ( Kan et al, 2019 ; Houston et al, 2016 ) can induce phase separation, in turn changing the relaxation behavior, then behaving more like shorter chains rather than long segregated systems ( Boothroyd et al, 2019 ; Golkaram et al, 2019 ). A third principle important in many supramolecular polymers is the formation of transient networks, formed by hydrogen bonds inside a thermoplastic polymer, which leads to supramolecular transient crosslinking between the chains ( Figure 3C ), in turn increasing melt viscosity and elasticity, able to facilitate 3D printing of such polymers ( Reppel et al, 2013 ; Döhler et al, 2020 ).…”

Section: Rheology Of Supramolecular Materialsmentioning

confidence: 99%

3D Printing of Solvent-Free Supramolecular Polymers

Rupp

Binder

2021

Front. Chem.

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Additive manufacturing has significantly changed polymer science and technology by engineering complex material shapes and compositions. With the advent of dynamic properties in polymeric materials as a fundamental principle to achieve, e.g., self-healing properties, the use of supramolecular chemistry as a tool for molecular ordering has become important. By adjusting molecular nanoscopic (supramolecular) bonds in polymers, rheological properties, immanent for 3D printing, can be adjusted, resulting in shape persistence and improved printing. We here review recent progress in the 3D printing of supramolecular polymers, with a focus on fused deposition modelling (FDM) to overcome some of its limitations still being present up to date and open perspectives for their application.

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Supramolecular engineering polyesters: endgroup functionalization of glycol modified PET with ureidopyrimidinone

Abstract: We report the first supramolecular engineering polymer with melt viscosity suitable for non-degradative processing plus enhanced thermal and mechanical properties.

Cited by 18 publications

References 30 publications

Self Assembly–Assisted Additive Manufacturing: Direct Ink Write 3D Printing of Epoxy–Amine Thermosets

Self Assembly–Assisted Additive Manufacturing: Direct Ink Write 3D Printing of Epoxy–Amine Thermosets

A Critical Approach to Polymer Dynamics in Supramolecular Polymers

3D Printing of Solvent-Free Supramolecular Polymers

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