Reaction Kinetics and Volume Relaxation during Polymerizations of Multiethylene Glycol Dimethacrylates

Anseth, Kristi S.; Kline, Lauren M.; Walker, Teri A.; Anderson, Karin J.; Bowman, Christopher N.

doi:10.1021/ma00111a050

Cited by 219 publications

(246 citation statements)

References 15 publications

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“…For the polymers tested in this study, the lowest FS and E were observed for BisGMA, in spite of the very strong intermolecular interactions and the rigid backbone, due to the very low DC achieved. Among the other three monomers, the highest FS and E were presented by UDMA, in spite of the lowest conversion, probably due to a combination of stronger hydrogen bonding potential (17), shorter crosslinks (in relation to BisEMA) (21) that are expected to render less free volume (22) and less cyclization (in relation to TEGDMA) (23). Owing to these interactions and the consequences to water sorption and solubility (discussed in the following paragraphs), these dimethacrylates have been successfully combined in dental composites formulations (24).…”

Section: Discussionmentioning

confidence: 99%

Monomers used in resin composites: degree of conversion, mechanical properties and water sorption/solubility

et al. 2012

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The organic phase of resin composites is constituted by dimethacrylate resins, the most common monomers being the bisphenol A diglycidildimethacrylate (BisGMA), its ethoxylated version (BisEMA), triethylene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA). This study compared the homopolymers formed from the monomers used in restorative dental composites in terms of their degree of conversion (DC) and reaction kinetics (by near infra-red spectroscopy, n=3), mechanical properties (flexural modulus and strength in three point-bending, FM and FS, respectively, n=15), water sorption and solubility (WS and SL, respectively -ISO 4049, n=5). Materials were made photopolymerizable by the addition of camphoroquinone/dimethylamine ethyl methacrylate. TEGDMA showed the highest DC, followed by BisEMA, UDMA and BisGMA, both at 10 min and at 24h (p<0.001). UDMA showed the highest rate of polymerization, followed by TEGDMA, BisEMA and BisGMA (H 0 =13.254, p<0.001). UDMA and TEGDMA presented similar FM, significantly higher (p<0.001) than BisEMA and BisGMA, which in turn present statistically similar values (p>0.001). For FS, UDMA presented the highest value (p<0.001), followed by TEGDMA, then by BisEMA and BisGMA, which were statistically similar (p>0.001). BisGMA showed the highest WS, and TEGDMA and BisEMA the lowest. UDMA was statistically similar to all (H 0 =16.074, p<0.001). TEGDMA presented the highest SL, followed by UDMA, BisGMA and BisEMA (p<0.001). The tested homopolymers presented different behaviors in terms of polymerization kinetics, flexural properties, water sorption and solubility. Therefore, the use of copolymers is justified in order to obtain high DC and mechanical properties, as well as good resistance to water degradation.

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Section: Discussionmentioning

confidence: 99%

Monomers used in resin composites: degree of conversion, mechanical properties and water sorption/solubility

et al. 2012

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“…Indeed, different processes are known to affect the conversion-time evolution during FRP reaction, such as autoacceleration and deceleration [30][31][32] as well as termination by reaction diffusion. [30,[33][34][35][36][37][38][39][40][41][42][43][44][45] Taking into account these effects into a kinetic model requires to consider the change in the rate constants during the photopolymerization within a free radical photopolymerization model as described in the literature [46][47][48][49][50][51] and recently used to predict kinetic rate constants during dark polymerizations experiments under oxygen diffusion [52] and model layer-by-layer UVcuring. [53] Complete description of the model can be found in the Supporting Information.…”

Section: Kinetic Modeling Of Frp Initiated By a Triazine-based Type-imentioning

confidence: 99%

Triazine‐Based Type‐II Photoinitiating System for Free Radical Photopolymerization: Mechanism, Efficiency, and Modeling

Christmann

Allonas

Ley

et al. 2017

Macro Chemistry & Physics

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Isopropylthioxanthone, a versatile photoinitiator (PI) for free radical photopolymerization (FRP), is combined with a triazine derivative (Tz) in a Type-II photoinitiating system (PIS). Initiation ability of this system for acrylate photopolymerization is assessed using a diacrylate monomer. Involvement of a photoinduced electron transfer mechanism is demonstrated by time-resolved spectro scopic measurements. Further insights in this mechanism are obtained through the use of a photopolymerization kinetic model taking into account the main reaction steps from the absorption of photons to the formation of the polymer. Prediction ability of the model is also tested with different initial concentrations of PI and co-initiator, as well as a different Tz. This last experiment reveals the noticeable role of back electron transfer in the FRP mechanism of Type-II PIS. by the use of a photoinitiating system (PIS). It converts photons into chemical energy through the production of radicals capable of reacting with acrylic monomers to initiate macromolecular chains. Three main families of PIS have been developed, each with their own advantages and limitations. [2,[4][5][6][7][8][9] Type-I PIS rely on the photoinduced dissociation of the initiator to produce primary radicals. Despite a high quantum yield of radical production, typical bond dissociation energies require the use of UV lamps that are known to be harmful and to release ozone in the atmosphere. Therefore, Type-II PIS have been developed, which combine a photoinitiator (PI) able to absorb light and a co-initiator capable of reacting with the excited PI through hydrogen abstraction or electron transfer. Nevertheless, radical production is limited by the diffusion of the species into the viscous monomer medium and competition of the bimolecular reaction with PI deactivation pathways. In the case of hydrogen abstraction, hydrogenated PI radicals (PIH • , such as ketyl radicals) could also act as terminating agents and reduce final conversion. [10,11] Photocyclic initiating systems (PCIS) have then been developed in order to combine advantages of previous PIS, i.e.,

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“…Cross-linked PMMA is used in a variety of commercial materials such as membranes [27], dental fillings [28], dentures, latex coatings [29], computer-to-sensor data transmission links [30], composites [31], optically clear sheeting, limb prostheses, bathtubs, bathroom sinks and shower surrounds where cross-linking plays a vital role in both processing and ultimate properties. Latex properties of poly(urethane acrylate) (Pu-A) and MMA co-polymer have been studied by Zhang et al [32] They found that the cast film was significantly influenced by the amount of 2-hydoxypropyl acrylate (HPA), dimethyolpropionic acid (DMPA) and MMA.…”

Section: Methyl Methacrylate (Mma)mentioning

confidence: 99%

Co-polymerization of Acrylates

Srivastava

2009

Designed Monomers and Polymers

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Co-polymers of methyl methacrylates (MMAs) are widely used in coatings because of their film-forming capacity, which is due to better bond-forming tendency with various substrates. The adhesion of coating with various substrates such as wood, metal or plastics is an important property for protective, as well as decorative coatings. Co-polymers of MMA with different monomers such as butyl acrylate (BuA), 2-ethyl hexyl acrylate (2-EHA) and hydroxyl ethyl methacrylate (HEMA) are extensively used for coatings on different substrates to improve the roughness, acid scratch and solvent resistances. Co-polymerization of diacrylates/dimethacrylates of glycols with various alkyl esters have been investigated by several scientists. In the synthesis of these materials an understanding of polymerization mechanism and kinetics is important for better control of gel structure. The rate constant depends largely on the physical properties of the system, which in turn, are strong functions of monomer conversion. Cross-link density is one of them, and T g also depends on it, increasing with increasing cross-link density.

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Reaction Kinetics and Volume Relaxation during Polymerizations of Multiethylene Glycol Dimethacrylates

Cited by 219 publications

References 15 publications

Monomers used in resin composites: degree of conversion, mechanical properties and water sorption/solubility

Monomers used in resin composites: degree of conversion, mechanical properties and water sorption/solubility

Triazine‐Based Type‐II Photoinitiating System for Free Radical Photopolymerization: Mechanism, Efficiency, and Modeling

Co-polymerization of Acrylates

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