Has <i>Click Chemistry</i> Lead to a Paradigm Shift in Polymer Material Design?

Barner‐Kowollik, Christopher; Inglis, Andrew J.

doi:10.1002/macp.200900139

Cited by 132 publications

(95 citation statements)

References 27 publications

(30 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…T-3 was prepared from 3 in a similar manner to T-2 using 2-chloroethanol (4.10 mL, 61.0 mmol 4 Cl aq (30 mL) and water (30 mL). The organic phase was poured into hexane (220 mL), and the precipitate was collected and dried in vacuo to give the polymer (257 mg, 99.8%).…”

Section: Synthesis Of 2-chloroethyl α-(Chloromethyl)acrylate (T-3)mentioning

confidence: 99%

“…Although a variety of functional azides and thiols are reported to be applicable, [3][4][5]15,35 benzyl azide and 2-mercaptoethanol were selected for the current model reactions in order to facilitate 1 H NMR observation of the proceeding of each reaction without any signal overlaps of the original and resulting polymers. Figure 2 shows the 1 H NMR spectra of the polymers in each step.…”

Section: Double Click Reaction Of Propargyl-terminated Pmmasmentioning

confidence: 99%

“…[3][4][5] From the viewpoint of polymer synthesis, to say nothing of the polyaddition via click chemistry, [6][7][8][9][10][11] polymers possessing clickable pendant groups 12,13 and/or end-functionalities [14][15][16] have attracted researchers' attention, as such polymers can be used as 'building blocks' for syntheses of highly functionalized polymers, 17,18 construction of sophisticated topology, 19,20 and surface modification 21,22 .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

2015

View full text Add to dashboard Cite

Isotactic and syndiotactic poly(methyl methacrylate)s with orthogonally double-clickable terminal ends, that is, α,β-unsaturated ester for Michael addition-type thiol-ene reaction and azide or alkynyl groups for azide-alkyne click reaction, were prepared via terminating reaction of stereospecific anionic polymerization with propargyl and 2-chloroethyl α-(chloromethyl)acrylates. The subsequent polymer modification via double click reaction proceeded quantitatively in one -pot system under ambient conditions. The facile and almost quantitative double-end-functionalization would open a new material design based on stereoregular PMMAs with controlled molecular weights.

show abstract

Section: Synthesis Of 2-chloroethyl α-(Chloromethyl)acrylate (T-3)mentioning

confidence: 99%

Section: Double Click Reaction Of Propargyl-terminated Pmmasmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

2015

View full text Add to dashboard Cite

show abstract

“…Without such reactions, modular approaches for the synthesis of complex macromolecules could not be taken. 41 In consequence, even though equimolar amounts of reactants are not strictly required from the original definition of click type reactions, it is the 'equimolarity feature' of efficient click reactions that causes their high value in polymer chemistry. Regardless, the click definition dictates that, if one reaction partner is used in excess, or if significant side products are formed during the reaction, that these components must be easily removable by non-chromatographic methods, that is recrystallization or distillation.…”

Section: Implications Of the Click Concept For Polymer Conjugation Rementioning

confidence: 99%

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

Koo

Stamenović

Ramaswamy

et al. 2010

J. Polym. Sci. A Polym. Chem.

Self Cite

238

228

View full text Add to dashboard Cite

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.

show abstract

“…The concept of 'click' 22 chemistry 1-8 induced a transition towards 'on-demand' preparation of tailored polymeric 2 systems. 9 The toolbox of research labs is currently loaded with a variety of established 'click' 24 reactions, offering ample possibilities for macromolecular design and synthesis. Moreover, the 25 development and valorization of novel polymer materials with a broad range of applications 26 (medicines, [10][11][12][13] electronics, [14][15][16] bioconjugation, 17-21 labeling, [22][23][24][25][26] etc.)…”

mentioning

confidence: 99%