Thiol-ene oligomers as dental restorative materials

Carioscia, Jacquelyn A.; Lu, Hui; Stanbury, Jeffrey W.; Bowman, Christopher N.

doi:10.1016/j.dental.2005.04.002

Cited by 160 publications

(125 citation statements)

References 25 publications

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“…Although a number of strategies have been developed to avoid the use of copper for azide-alkyne click reactions, it is often argued that at least in the near future these approaches will not be able to replace the copper(I) catalyzed coupling reaction. 13 To avoid the use of a copper catalyst, a number of alternative click strategies have been recently proposed, 15 and in particular (hetero) Diels-Alder cycloaddition reactions 7,16 as well as thiol-ene reactions [17][18][19][20][21] are becoming increasingly widespread. Among these, the thiol-ene radical addition reactions are believed to have significant potential to become as popular as the Cu(I)-catalyzed azide-alkyne click cycloaddition reaction, CuAAC, since the introduction of terminal alkene and thiol groups is straightforward and the coupling procedure can be conducted even without a catalyst in the presence of UV-light.…”

Section: Introductionmentioning

confidence: 99%

Limitations of radical thiol‐ene reactions for polymer–polymer conjugation

Koo

Stamenović

Ramaswamy

et al. 2010

J. Polym. Sci. A Polym. Chem.

238

228

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In the current work, we report our findings on the use of radical thiol-ene chemistry for polymerpolymer conjugation. The manuscript combines the results from the Preparative Macromolecular Chemistry group from Karlsruhe Institute of Technology (KIT) and the Polymer Chemistry Research group from Ghent University (UGent), which allowed for an investigation over a very broad range of reaction conditions. In particular, thermal and UV initiation methods for the 2 radical thiol-ene process were compared. In the KIT group, the process was studied as a tool for the synthesis of star polymers by coupling multi-functional thiol core molecules with poly(nbutyl acrylate) macromonomers (MM), employing thermally decomposing initiators. The product purity and thus reaction efficiency was assessed via electrospray ionization mass spectrometry. Although the reactions with 10 or 5 equivalents of thiol with respect to macromonomer were successful, the coupling reaction with a one-to-one ratio of MM to thiol yielded only a fraction of the targeted product, besides a number of side products. A systematic parameter study such as a variation of the concentration and nature of the initiator and the influence of thiol to ene ratio was carried out for a one-to-one ratio of MM to thiol content.Further experiments with poly(styrene) and poly(isobornyl acrylate) containing a vinylic end group confirmed that thermal thiol-ene conjugation is far from quantitative in terms of achieving macromolecular star formation. In parallel, the UGent group has been focusing on photo-initiated thiol-ene chemistry for the synthesis of functional polymers on the one hand and block copolymers consisting of poly(styrene) (PS) and poly(vinyl acetate) (PVAc) on the other hand.Various functionalization reactions showed an overall efficient thiol-ene process for conjugation reactions of polymers with low molecular weight compounds (~90% coupling yield). However, while SEC and FT-IR analysis of the conjugated PS-PVAc products indicated qualitative evidence for a successful polymer-polymer conjugation, 1 H NMR and elemental analysis revealed a low conjugation efficiency of about 23% for a thiol-to-ene ratio equal to one. Blank reactions using typical thiol-ene conditions indicated that bimolecular termination reactions 3 occur as competitive side reactions explaining why a molecular weight increase is observed even though the thiol-ene reaction was not successful. The extensive study of both research groups indicates that radical thiol-ene chemistry should not be proposed as a straightforward conjugation tool for polymer-polymer conjugation reactions. Head-to-head coupling is a major reaction pathway, which interrupts the propagation cycle of the thiol-ene process.

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Section: Introductionmentioning

confidence: 99%

Limitations of radical thiol‐ene reactions for polymer–polymer conjugation

Koo

Stamenović

Ramaswamy

et al. 2010

J. Polym. Sci. A Polym. Chem.

238

228

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“…[8] Auch Materialien für Anwendungen in der Medizin und besonders der Zahnmedizin [9] wurden mit dieser Methode hergestellt. Allerdings wurde der Klick-Aspekt der TEC auf dem Gebiet der Polymerwissenschaften erst vor kurzem erkannt.…”

Section: Zu Beginn Dieses Jahrzehnts Stellten Sharpless Et Al Dasunclassified

Die Entwicklung der Thiol‐En‐Kupplung als Klick‐Prozess für die Materialwissenschaften und die bioorganische Chemie

Dondoni

2008

Angewandte Chemie

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“…Thiol-ene-methacrylate systems have proven to be able to reduce stress without prejudice to the elastic modulus in vitro. 82 The mechanism for stress reduction relies on the fact that thiol-ene polymerizations progress via step-growth, a process in which gelation and vitrification are not reached until much later in conversion, so any strain can be accommodated before it generates stresses at the interface. 83,84 There are some disadvantages of using thiol-enes, such as a potential for decreased modulus in methacrylate polymerizations, and malodor of small molecule thiols.…”

Section: Modifications In the Restorative Composite Formulationmentioning

confidence: 99%

Polymerization shrinkage stress of composite resins and resin cements – What do we need to know?

et al. 2017

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Polymerization shrinkage stress of resin-based materials have been related to several unwanted clinical consequences, such as enamel crack propagation, cusp deflection, marginal and internal gaps, and decreased bond strength. Despite the absence of strong evidence relating polymerization shrinkage to secondary caries or fracture of posterior teeth, shrinkage stress has been associated with postoperative sensitivity and marginal stain. The latter is often erroneously used as a criterion for replacement of composite restorations. Therefore, an indirect correlation can emerge between shrinkage stress and the longevity of composite restorations or resin-bonded ceramic restorations. The relationship between shrinkage and stress can be best studied in laboratory experiments and a combination of various methodologies. The objective of this review article is to discuss the concept and consequences of polymerization shrinkage and shrinkage stress of composite resins and resin cements. Literature relating to polymerization shrinkage and shrinkage stress generation, research methodologies, and contributing factors are selected and reviewed. Clinical techniques that could reduce shrinkage stress and new developments on low-shrink dental materials are also discussed.

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Thiol-ene oligomers as dental restorative materials

Cited by 160 publications

References 25 publications

Limitations of radical thiol‐ene reactions for polymer–polymer conjugation

Limitations of radical thiol‐ene reactions for polymer–polymer conjugation

Die Entwicklung der Thiol‐En‐Kupplung als Klick‐Prozess für die Materialwissenschaften und die bioorganische Chemie

Polymerization shrinkage stress of composite resins and resin cements – What do we need to know?

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