The Silane‐ene and Silane‐Acrylate Polymerization Process: A New Promising Chemistry?

El‐Roz, Mohamad; Lalevée, Jacques; Allonas, Xavier; Fouassier, Jean‐Pierre

doi:10.1002/marc.200800052

Cited by 27 publications

(26 citation statements)

References 16 publications

(16 reference statements)

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“…Analogously to thiols, the synthesized silane MSiH should be introduced as a potential chain transfer agent for radical photopolymerization. The expected radical silane‐ene mechanism should proceed similarly to thiol‐ene chemistry (Figure b) and has previously been reported . After formation of an initiating radical (IR•), via photoexcitation of a radical type I photoinitiator (PI) in this case, the radical fragment either initiates polymerization through propagation (P) into the CC double bond of the ene derivative or abstracts a hydrogen from a monofunctional silane (chain transfer CT step).…”

Section: Resultsmentioning

confidence: 99%

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Light-Triggered Radical Silane-Ene Chemistry Using a Monosubstituted Bis(trimethylsilyl)silane

Steindl

Svirkova

Marchetti‐Deschmann

et al. 2017

Macromol. Chem. Phys.

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Chain transfer agents (e.g., thiols) enrich radical photopolymerization for use in advanced applications such as stereolithography, optical materials, and biomedicine. Resulting thiol‐ene‐based photopolymers exhibit numerous benefits such as tunable thermomechanical properties, and give access to spatially resolved functional materials. Silane‐ene chemistry could serve as alternative to this popular thiol‐ene approach. A monosubstituted bis(trimethylsilyl)silane (MSiH) is synthesized by a simple one pot procedure. Photoinitiated radical silane‐ene chemistry has been performed with multiple enes and the conversions are assessed by 1H NMR spectroscopy. Compared to the most reactive silane from literature, tris(trimethylsilyl)silane (TTMSSiH), the radical reactivity of MSiH is reduced in all tested formulations, but the possibility for further functionalization and accessibility of multifunctional MSiH‐derivatives is upheld. A silane‐acrylate formulation is found to be most promising. In comparison to a thiol‐acrylate system, a more uniform conversion of the chain transfer agent and acrylate is shown for the silane‐acrylate formulation with MSiH. The promising results for the silane‐acrylate system are confirmed by further tests (i.e., NMR spectroscopy, GPC, and MALDI MS), giving additional information on molecular weight regulation and radical mechanism. First MSiH‐based photopolymer networks have been fabricated and analyzed via DMTA, thus paving the way for future silane‐acrylate networks.

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Section: Resultsmentioning

confidence: 99%

“…Silane‐ene chemistry has been proposed as a further potential candidate by implementing silanes with abstractable hydrogens. Additionally, such silanes are also of significant interest for photografting applications on silicon surfaces and in silicon polymer science .…”

Section: Introductionmentioning

confidence: 99%

Light-Triggered Radical Silane-Ene Chemistry Using a Monosubstituted Bis(trimethylsilyl)silane

Steindl

Svirkova

Marchetti‐Deschmann

et al. 2017

Macromol. Chem. Phys.

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“…Silane is reported to be more efficient than an amine in FRP or free radical promoted cationic polymerization (FRPCP). 37–40 For the TTMSS silyl radical, a high reactivity with addition rate constant ( k add ~ 2:2×10 7 M −1 s −1 ) to methylacrylate was noted 38 . For the EDMAB generated radical, this value was 5 × 10 5 M −1 s −1 .…”

Section: Discussionmentioning

confidence: 98%

Development of methacrylate/silorane hybrid monomer system: Relationship between photopolymerization behavior and dynamic mechanical properties

Song

et al. 2015

J Biomed Mater Res

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Resin chemistries for dental composite are evolving as noted by the introduction of silorane-based composites in 2007. This shift in the landscape from methacrylate-based composites has fueled the quest for versatile methacrylate-silorane adhesives. The objective of this study was to evaluate the polymerization behavior and structure/property relationships of methacrylate-silorane hybrid systems. Amine compound ethyl-4-(dimethylamino) benzoate (EDMAB) or silane compound tris(trimethylsilyl) silane (TTMSS) was selected as coinitiators. The mechanical properties of the copolymer were improved significantly at low concentrations (15, 25, or 35 wt %) of silorane when EDMAB was used as coinitiator. The rubbery moduli of these experimental copolymers were increased by up to 260%, compared with that of the control (30.8 ± 1.9 MPa). Visible phase separation appeared in these formulations if the silorane concentrations in the formulations were 50–75 wt %. The use of TTMSS as coinitiator decreased the phase separation, but there was a concomitant decrease in mechanical properties. In the neat methacrylate formulations, the maximum rates of free-radical polymerization with EDMAB or TTMSS were 0.28 or 0.06 s−1, respectively. In the neat silorane resin, the maximum rates of cationic ring-opening polymerization with EDMAB or TTMSS were 0.056 or 0.087 s−1, respectively. The phase separation phenomenon may be attributed to differences in the rates of free-radical polymerization of methacrylates and cationic ring-opening polymerization of silorane. In the hybrid systems, free-radical polymerization initiated with EDMAB led to higher crosslink density and better mechanical properties under dry/wet conditions. These beneficial effects were, however, associated with an increase in heterogeneity in the network structure.

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“…[70][71][72] Photoinitiation with disilanes having an Si-Si bond is also possible through electron transfer and Si-Si bond dissociation. It has been found that silane compounds can be efficiently employed as co-initiator to initiate photopolymerization in the presence of photoinitiators.…”

Section: Methodsmentioning

confidence: 99%

Shining a light on an adaptable photoinitiator: advances in photopolymerizations initiated by thioxanthones

2015

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Photochemistry has been playing a central role in the synthetic polymer community. Aromatic ketones, examples of which include benzophenone, thioxanthone, camphorquinone, among others, are renowned for their excellent optical characteristics and have been extensively taken advantage of photochemically induction of polymerization processes. Of particular interest is thioxanthone due to its adaptability for bearing different functionalities and applications in various modes of photopolymerization which accomplishes photoinitiation in conjunction with other co-initiator compounds; a behavior that is referred to as bi-molecular photoinitiation. In this paper, we review the photochemistry of thioxanthonebased systems and their use in different modes of photoinitiated polymerizations. Citing examples from literature, the development of various photoinitiating systems based on thioxanthones along with an understanding of their mechanistic behavior has been elucidated in advance.Scheme 1 Typical representation of the photolysis of the radical photoinitiators based on Type I (top) and Type II (bottom) systems on the example of a benzoin derivative and thioxanthone, respectively.Scheme 3 Synthesis of thioxanthones by condensation of thiosalicylic acid and aromatic compounds in the presence of concentrated sulfuric acid.

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The Silane‐ene and Silane‐Acrylate Polymerization Process: A New Promising Chemistry?

Cited by 27 publications

References 16 publications

Light-Triggered Radical Silane-Ene Chemistry Using a Monosubstituted Bis(trimethylsilyl)silane

Light-Triggered Radical Silane-Ene Chemistry Using a Monosubstituted Bis(trimethylsilyl)silane

Development of methacrylate/silorane hybrid monomer system: Relationship between photopolymerization behavior and dynamic mechanical properties

Shining a light on an adaptable photoinitiator: advances in photopolymerizations initiated by thioxanthones

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