Two‐Stage Reactive Polymer Network Forming Systems
Abstract
There are distinct advantages to designing polymer systems that afford two distinct sets of material properties– an intermediate polymer that would enable optimum handling and processing of the material, while maintaining the ability to tune in different, final polymer properties that enable the optimal functioning of the material. In this study, by designing a series of non‐stoichiometric thiol‐acrylate systems, a polymer network is initially formed via a base catalyzed Michael addition reaction that proceeds stoichiometrically via the thiol‐acrylate “click” reaction. This self‐limiting reaction results in a polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. These two stage reactive thiol‐acrylate networks that have intermediate stage rubbery moduli and glass transition temperatures that range from 0.5 MPa and ‐10 °C to 22 MPa and 22 °C, respectively, are formulated and characterized. The same polymer networks can then attain glass transition temperatures that range from 5 °C to 195 °C and rubbery moduli of up to 200 MPa after the subsequent photocuring stage. The two stage reactive networks formed by varying the stoichiometric ratios of the thiol and acrylate monomers were shown to perform as substrates for three specific applications: shape memory polymers, impression materials, and as optical materials for writing refractive index patterns.
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Two-stage polymerization typically leads to higher crosslinking densities, without significant other changes.
“two-stage polymerization typically leads to higher crosslinking densities, without significant other changes.”
From On demand shape memory polymer via light regulated topological defects in a dynamic covalent network (2020) · cites this paper as [41]
After shape recovery, a second stage reaction can photo-polymerize remaining acrylate functional groups to form a more stable chemical cross-linking system, allowing the SMP to keep its mechanical strength even at high temperature.
“After shape recovery, a second stage reaction can photo-polymerize remaining acrylate functional groups to form a more stable chemical cross-linking system.In this way, even at a high temperature, the SMP can keep its mechanical strength.”
From A review of stimuli-responsive shape memory polymer composites (2013) · cites this paper as Nair et al. [536]
A two-stage reactive nonstoichiometric thiol-acrylate SMP system can photo-polymerize remaining acrylate functional groups after shape recovery to form a more stable chemical cross-linking system, allowing the SMP to keep its mechanical strength even at high temperature.
“After shape recovery, a second stage reaction can photo-polymerize remaining acrylate functional groups to form a more stable chemical cross-linking system.In this way, even at a high temperature, the SMP can keep its mechanical strength.”
From A review of stimuli-responsive shape memory polymer composites (2013) · cites this paper as [536]
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- Authors
- Nair, D. P., Cramer, N. B., Gaipa, J. C., McBride, M. K., Matherly, E. M., McLeod, R. R., Shandas, R., & Bowman, C. N.
- Affiliations
- University of Colorado Boulder (US)
- Corresponding author
- Bowman, Christopher N.
- Venue
- Advanced Functional Materials
- Publisher
- Wiley
- Published
- 2012-01-26
- Volume
- 22
- Issue
- 7
- Pages
- 1502-1510
- ISSN
- 1616-301X (ISSN-L)
- 1616-3028
- OpenAlex
- W2151162168
- Cited by
- 166
- References
- 42
- Citations by year
- 2026: 6 · 2025: 10 · 2024: 19 · 2023: 6 · 2022: 13 · 2021: 8 · 2020: 13 · 2019: 13 · 2018: 17 · 2017: 8 · 2016: 17 · 2015: 11 · 2014: 11 · 2013: 10 · 2012: 4
- FWCI
- 5.30
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Advanced Functional Materials (publishedVersion)
- Funders
- National Science Foundation
- Foundation for the National Institutes of Health
- Division of Chemical, Bioengineering, Environmental, and Transport Systems
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer composites and self-healing
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Keywords
- Michael addition, radical photopolymerization, glass transition temperature, rubbery modulus, polymer networks, shape memory polymers, impression materials, optical materials
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