Dataset Information

Stress Reduction and T(g) Enhancement in Ternary Thiol-Yne-Methacrylate Systems via Addition-fragmentation Chain Transfer.

ABSTRACT: Since polymerization-induced shrinkage stress is detrimental in many applications, addition-fragmentation chain transfer (AFCT) was employed to induce network relaxation and adaptation that mitigate the shrinkage stress. Here, to form high glass transition temperature, high modulus polymers while still minimizing stress, multifunctional methacrylate monomers were incorporated into allyl sulfide-containing thiol-yne resins to provide simultaneously high glass transition temperatures and a facile mechanism for AFCT throughout the network. As a negative control, in an attempt to isolate just the effects of AFCT in the polymerization, a propyl sulfide-based diyne, which has a nearly identical chemical structure though absent any AFCT-capable functional group, was synthesized and implemented in place of the allyl sulfide-based diyne. The glass transition temperature of the ternary systems increased from 39°C to 79°C as the methacrylate content increased while the shrinkage stress of the optimal ternary resin was lower than either the binary thiol-yne resin or the pure methacrylate resin. The stress relaxation benefit associated with AFCT increased with increasing allyl sulfide concentration as shown by a decrease in the relative stress from 0.98 to 0.53. The allyl sulfide-based thiol-yne-methacrylate system exhibits stress relaxation up to 55% and increased T(g) up to 40°C compared with the control, AFCT-incapable thiol-yne. This ternary system has less than 1/3 of the stress of conventional dimethacrylate monomer resins while possessing similarly outstanding mechanical behavior.

SUBMITTER: Park HY

PROVIDER: S-EPMC3498503 | biostudies-literature | 2012 Jul

REPOSITORIES: biostudies-literature

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Stress Reduction and T(g) Enhancement in Ternary Thiol-Yne-Methacrylate Systems via Addition-fragmentation Chain Transfer.

Park Hee Young HY Kloxin Christopher J CJ Fordney Mark F MF Bowman Christopher N CN

Macromolecules 20120703 14

Since polymerization-induced shrinkage stress is detrimental in many applications, addition-fragmentation chain transfer (AFCT) was employed to induce network relaxation and adaptation that mitigate the shrinkage stress. Here, to form high glass transition temperature, high modulus polymers while still minimizing stress, multifunctional methacrylate monomers were incorporated into allyl sulfide-containing thiol-yne resins to provide simultaneously high glass transition temperatures and a facile ...[more]

PMID: 23162167

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Project description:To reduce shrinkage stress which arises during the polymerization of crosslinked polymers, allyl sulfide functional groups were incorporated into methacrylate polymerizations to determine their effect on stress relaxation via addition-fragmentation chain transfer (AFCT). Additionally, stoichiometrically balanced thiol and allyl sulfide-containing norbornene monomers were incorporated into the methacrylate resin to maximize the overall functional group conversion and promote AFCT while also enhancing the polymer's mechanical properties. Shrinkage stress and reaction kinetics for each of the various functional groups were measured by tensometry and Fourier-transform infrared (FTIR) spectroscopy, respectively. The glass transition temperature (T(g)) and elastic moduli (E') were measured using dynamic mechanical analysis. When the allyl sulfide functional group was incorporated into dimethacrylates, the polymerization-induced shrinkage stress was not relieved as compared with analogous propyl sulfide-containing resins. These analogous propyl sulfide containing monomers are incapable of undergoing AFCT while having similar chemical structure and crosslink density to the allyl sulfide containing methacrylates. Here, a monomethacrylate monomer that also contains a cyclic allyl sulfide (PAS) was found to increase the crosslinking density nearly 20 times as compared to an analogous monomethacrylate in which the allyl sulfide was replaced with an ethyl sulfide. Despite the much higher crosslink density, the PAS formulation exhibited no concomitant increase in stress. Thiol-norbornene resins were copolymerized in PAS to promote AFCT as well as to synergistically combine the ring opening benefits associated with the thiol-ene reaction. AFCT resulted in a 63% reduction of polymerization stress and a 45°C enhancement of the glass transition temperature in the allyl sulfide-containing thiol-norbornene-methacrylate system compared with rubbery dimethacrylates. When compared with conventional glassy dimethacrylates, this combined system has less than 10% of the typical shrinkage stress level while having similarly excellent mechanical properties.

Project description:Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016 , 7 , 5078 - 5090 ). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization.

Dataset Information

Stress Reduction and T(g) Enhancement in Ternary Thiol-Yne-Methacrylate Systems via Addition-fragmentation Chain Transfer.

Publications

Stress Reduction and T(g) Enhancement in Ternary Thiol-Yne-Methacrylate Systems via Addition-fragmentation Chain Transfer.

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