3D printable non-isocyanate polyurethanes with tunable material properties
(2019) In Polymer Chemistry 10(34). p.4665-4674- Abstract
Green chemistry-based non-isocyanate polyurethanes (NIPU) are synthesized and 3D-printed via rapid, projection photopolymerization into compliant mechanisms of 3D structure with spatially-localized material properties. Trimethylolpropane allyl ether-cyclic carbonate is used to couple the unique properties of two types of reaction chemistry: (1) primary diamine-cyclic carbonate ring-opening conjugation for supplanting conventional isocyanate-polyol reactions in creating urethane groups, with the additional advantage of enabling modular segment interchangeability within the diurethane prepolymers; and (2) thiol-ene (click) conjugation for non-telechelic, low monodispersity, quasi-crystalline-capable, and alternating step-growth... (More)
Green chemistry-based non-isocyanate polyurethanes (NIPU) are synthesized and 3D-printed via rapid, projection photopolymerization into compliant mechanisms of 3D structure with spatially-localized material properties. Trimethylolpropane allyl ether-cyclic carbonate is used to couple the unique properties of two types of reaction chemistry: (1) primary diamine-cyclic carbonate ring-opening conjugation for supplanting conventional isocyanate-polyol reactions in creating urethane groups, with the additional advantage of enabling modular segment interchangeability within the diurethane prepolymers; and (2) thiol-ene (click) conjugation for non-telechelic, low monodispersity, quasi-crystalline-capable, and alternating step-growth co-photopolymerization. Fourier transform infrared spectroscopy is used to monitor the functional group transformation in reactions, and to confirm these process-associated molecular products. The extent of how these processes utilize molecular tunability to affect material properties were investigated through measurement-based comparison of the various polymer compositions: frequency-related dynamic mechanical analysis, tension-related elastic-deformation mechanical analysis, and material swelling analysis. Stained murine myoblasts cultured on NIPU slabs were evaluated via fluorescent microscopy for "green-chemistry" affects on cytocompatibility and cell adhesion to assess potential biofouling resistance. 3D multi-material structures with micro-features were printed, thus demonstrating the capability to spatially pattern different NIPU materials in a controlled manner and build compliant mechanisms.
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- author
- Warner, John J. ; Wang, Pengrui ; Mellor, William M. ; Hwang, Henry H. ; Park, Ji Hoon ; Pyo, Sang Hyun LU and Chen, Shaochen
- organization
- publishing date
- 2019
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Polymer Chemistry
- volume
- 10
- issue
- 34
- pages
- 10 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- pmid:33093876
- scopus:85071553363
- ISSN
- 1759-9954
- DOI
- 10.1039/c9py00999j
- language
- English
- LU publication?
- yes
- id
- e50b1be9-3258-4056-8723-550bd4349afc
- date added to LUP
- 2019-09-16 14:08:41
- date last changed
- 2024-08-21 07:21:43
@article{e50b1be9-3258-4056-8723-550bd4349afc,
abstract = {{<p>Green chemistry-based non-isocyanate polyurethanes (NIPU) are synthesized and 3D-printed via rapid, projection photopolymerization into compliant mechanisms of 3D structure with spatially-localized material properties. Trimethylolpropane allyl ether-cyclic carbonate is used to couple the unique properties of two types of reaction chemistry: (1) primary diamine-cyclic carbonate ring-opening conjugation for supplanting conventional isocyanate-polyol reactions in creating urethane groups, with the additional advantage of enabling modular segment interchangeability within the diurethane prepolymers; and (2) thiol-ene (click) conjugation for non-telechelic, low monodispersity, quasi-crystalline-capable, and alternating step-growth co-photopolymerization. Fourier transform infrared spectroscopy is used to monitor the functional group transformation in reactions, and to confirm these process-associated molecular products. The extent of how these processes utilize molecular tunability to affect material properties were investigated through measurement-based comparison of the various polymer compositions: frequency-related dynamic mechanical analysis, tension-related elastic-deformation mechanical analysis, and material swelling analysis. Stained murine myoblasts cultured on NIPU slabs were evaluated via fluorescent microscopy for "green-chemistry" affects on cytocompatibility and cell adhesion to assess potential biofouling resistance. 3D multi-material structures with micro-features were printed, thus demonstrating the capability to spatially pattern different NIPU materials in a controlled manner and build compliant mechanisms.</p>}},
author = {{Warner, John J. and Wang, Pengrui and Mellor, William M. and Hwang, Henry H. and Park, Ji Hoon and Pyo, Sang Hyun and Chen, Shaochen}},
issn = {{1759-9954}},
language = {{eng}},
number = {{34}},
pages = {{4665--4674}},
publisher = {{Royal Society of Chemistry}},
series = {{Polymer Chemistry}},
title = {{3D printable non-isocyanate polyurethanes with tunable material properties}},
url = {{http://dx.doi.org/10.1039/c9py00999j}},
doi = {{10.1039/c9py00999j}},
volume = {{10}},
year = {{2019}},
}