Cargando…
Controlling Healing and Toughness in Polyurethanes by Branch-Mediated Tube Dilation
[Image: see text] In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of alip...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2019
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6854654/ https://www.ncbi.nlm.nih.gov/pubmed/31736512 http://dx.doi.org/10.1021/acs.macromol.9b01554 |
_version_ | 1783470253629505536 |
---|---|
author | Montano, Vincenzo Wempe, Max M. B. Does, Sam M. H. Bijleveld, Johan C. van der Zwaag, Sybrand Garcia, Santiago J. |
author_facet | Montano, Vincenzo Wempe, Max M. B. Does, Sam M. H. Bijleveld, Johan C. van der Zwaag, Sybrand Garcia, Santiago J. |
author_sort | Montano, Vincenzo |
collection | PubMed |
description | [Image: see text] In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of aliphatic propane diol derivatives with alkyl branches ranging from butyl (C4) to octadecanyl (C18). The series of brush polyurethanes was synthesized by polyaddition of the diols and hexamethylene diisocyanate. Polyurethanes with very short (C < 4) and very long (C = 18) brush lengths did not lead to any significant healing due to crystallization. An intermediate amorphous regime appears for polymers with middle branch lengths (C = 4 to 8) showing a fine control of material toughness. For these systems, the side chain length regulates tube dilation, and significant macroscopic healing of cut samples was observed and studied in detail using melt rheology and tensile testing. Despite the high healing degrees observed immediately after repair, it was found that samples with medium to long length brushes lost their interfacial strength at the healed site after being heated to the healing temperature for some time after the optimal time to reach full healing. Dedicated testing suggests that annealed samples, while keeping initial tackiness, are not able to completely heal the cut interface. We attribute such behavior to annealing-induced interfacial crystallization promoted by the aliphatic branches. Interestingly, no such loss of healing due to annealing was observed for samples synthesized with C4 and C7 diols, which is identified as the optimal healing regime. These results point at the positive effect of branching on healing, provided that a critical chain length is not surpassed, as well as the need to study healing behavior long after the optimal healing times. |
format | Online Article Text |
id | pubmed-6854654 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-68546542019-11-15 Controlling Healing and Toughness in Polyurethanes by Branch-Mediated Tube Dilation Montano, Vincenzo Wempe, Max M. B. Does, Sam M. H. Bijleveld, Johan C. van der Zwaag, Sybrand Garcia, Santiago J. Macromolecules [Image: see text] In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of aliphatic propane diol derivatives with alkyl branches ranging from butyl (C4) to octadecanyl (C18). The series of brush polyurethanes was synthesized by polyaddition of the diols and hexamethylene diisocyanate. Polyurethanes with very short (C < 4) and very long (C = 18) brush lengths did not lead to any significant healing due to crystallization. An intermediate amorphous regime appears for polymers with middle branch lengths (C = 4 to 8) showing a fine control of material toughness. For these systems, the side chain length regulates tube dilation, and significant macroscopic healing of cut samples was observed and studied in detail using melt rheology and tensile testing. Despite the high healing degrees observed immediately after repair, it was found that samples with medium to long length brushes lost their interfacial strength at the healed site after being heated to the healing temperature for some time after the optimal time to reach full healing. Dedicated testing suggests that annealed samples, while keeping initial tackiness, are not able to completely heal the cut interface. We attribute such behavior to annealing-induced interfacial crystallization promoted by the aliphatic branches. Interestingly, no such loss of healing due to annealing was observed for samples synthesized with C4 and C7 diols, which is identified as the optimal healing regime. These results point at the positive effect of branching on healing, provided that a critical chain length is not surpassed, as well as the need to study healing behavior long after the optimal healing times. American Chemical Society 2019-10-17 2019-11-12 /pmc/articles/PMC6854654/ /pubmed/31736512 http://dx.doi.org/10.1021/acs.macromol.9b01554 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Montano, Vincenzo Wempe, Max M. B. Does, Sam M. H. Bijleveld, Johan C. van der Zwaag, Sybrand Garcia, Santiago J. Controlling Healing and Toughness in Polyurethanes by Branch-Mediated Tube Dilation |
title | Controlling Healing and Toughness in Polyurethanes
by Branch-Mediated Tube Dilation |
title_full | Controlling Healing and Toughness in Polyurethanes
by Branch-Mediated Tube Dilation |
title_fullStr | Controlling Healing and Toughness in Polyurethanes
by Branch-Mediated Tube Dilation |
title_full_unstemmed | Controlling Healing and Toughness in Polyurethanes
by Branch-Mediated Tube Dilation |
title_short | Controlling Healing and Toughness in Polyurethanes
by Branch-Mediated Tube Dilation |
title_sort | controlling healing and toughness in polyurethanes
by branch-mediated tube dilation |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6854654/ https://www.ncbi.nlm.nih.gov/pubmed/31736512 http://dx.doi.org/10.1021/acs.macromol.9b01554 |
work_keys_str_mv | AT montanovincenzo controllinghealingandtoughnessinpolyurethanesbybranchmediatedtubedilation AT wempemaxmb controllinghealingandtoughnessinpolyurethanesbybranchmediatedtubedilation AT doessammh controllinghealingandtoughnessinpolyurethanesbybranchmediatedtubedilation AT bijleveldjohanc controllinghealingandtoughnessinpolyurethanesbybranchmediatedtubedilation AT vanderzwaagsybrand controllinghealingandtoughnessinpolyurethanesbybranchmediatedtubedilation AT garciasantiagoj controllinghealingandtoughnessinpolyurethanesbybranchmediatedtubedilation |