Diene Rubber Modification Using Thiol-Type Derivatives

Ceauşescu, Elena; Bittman, Silvia; Fieroiu, V.; Badea, Elena Gabriela; Gruber, E.; Ciupitoiu, A.; Apostol, Victor Daniel

doi:10.1080/00222338508056621

Cited by 14 publications

(6 citation statements)

References 13 publications

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“…The radical mechanism of thiol addition to olefins has been known since the 1930s, and the ensuing decades saw extensive development of this reaction as a powerful tool for small molecule and polymer synthesis . Initial applications of thiol–ene chemistry were largely focused on the modification of residual olefins in natural rubbers , and polybutadiene (PB). , Justynska and Schlaad provided an estimable demonstration of this chemistry in 2004, functionalizing the pendent double bonds of poly(butadiene)- b -poly(ethylene oxide) that was prepared by living anionic polymerization with amine-, ester-, and carboxylic acid-containing mercaptans via a radical-mediated addition reaction . Like Ferruti ( vide supra ) and many others before them, they highlighted the potential of postpolymerization modification for the synthesis of polymers with mutually incompatible functionality and polymerization chemistry (i.e., polymers derived from anionic polymerization that bear protic functional groups).…”

Section: Current Status: Selected Examplesmentioning

confidence: 99%

“…The radical mechanism of thiol addition to olefins has been known since the 1930s, 54 and the ensuing decades saw extensive development of this reaction as a powerful tool for small molecule and polymer synthesis. 55 Initial applications of thiol−ene chemistry were largely focused on the modification of residual olefins in natural rubbers 56,57 and polybutadiene (PB). 58,59 Justynska and Schlaad provided an estimable demonstration of this chemistry in 2004, functionalizing the pendent double bonds of poly(butadiene)-b-poly(ethylene oxide) that was prepared by living anionic polymerization with amine-, ester-, and carboxylic acid-containing mercaptans via a radical-mediated addition reaction.…”

Section: Current Status: Selected Examplesmentioning

confidence: 99%

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50th Anniversary Perspective: Polymer Functionalization

et al. 2017

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The translation of small molecule chemistries into efficient methodologies for polymer functionalization spans several decades, enabling critical advances in soft matter materials synthesis with tailored and adaptive property profiles. The present Perspective exploresbased on selected examples50 years of innovation in polymer functionalization chemistries. These span a diverse set of chemistries based on activated esters, thiol–ene/yne processes, nucleophilic systems based on isocyanates, reactions driven by the formation of imines and oximes, ring-opening processes, cycloadditions, andin a recent renaissancemulticomponent reactions. In addition, a wide variety of chain types and architectures have been modified based on the above chemistries, often with exquisite chemical control, highlighted by key examples. We conclude our journey through polymer functionalization with thein our viewmost critically required advances that have the potential to move from “science fiction” to “science fact”.

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Section: Current Status: Selected Examplesmentioning

confidence: 99%

Section: Current Status: Selected Examplesmentioning

confidence: 99%

50th Anniversary Perspective: Polymer Functionalization

et al. 2017

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“…The introduced functional groups include hydroxy, amine, carboxylic acid, alkoxy silane, and perfluoroalkane. [52][53][54][55][56] Moreover, biological structures like cysteine, sugars, or dipeptides can be covalently linked to PB, creating so-called hybrid materials. [57][58][59][60][61] Random copolymers of EO and AGE can provide an outstanding platform for the modular synthesis of various PEG derivatives.…”

Section: ' Introductionmentioning

confidence: 99%

Poly(ethylene glycol-co-allyl glycidyl ether)s: A PEG-Based Modular Synthetic Platform for Multiple Bioconjugation

2011

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A series of random copolymers comprising ethylene oxide (EO) and 0-100% allyl glycidyl ether (AGE) has been prepared by anionic ring-opening polymerization with molecular weights between 5000 and 13,600 g/mol and polydispersity indices in the range of 1.04-1.19. As key for the homogeneity of the PEG conjugates, real-time ¹H NMR polymerization kinetics, ¹³C NMR analysis of triad sequence distribution, and analysis of the thermal behavior by differential scanning calorimetry (DSC) revealed a distinctive random copolymer structure. Via thiol-ene coupling (TEC), showing mainly "click" characteristics and nearly quantitative yields, PEG derivatives with multiple amino, carboxy, or hydroxy functionalities have been prepared, providing suitable reactivities for further attachment. Without further modification, P(EO-co-AGE)s were conjugated with cysteine or the tripeptide glutathione (GSH) via TEC, resulting in well-defined hybrid materials with multiple peptide units conjugated to the PEG backbone. The results demonstrate superior loading capacity of the copolymers in comparison to the PEG homopolymer.

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“…84 Thus antioxidants, like 4-(mercaptoacetamido)-diphenylamine, add -SH groups to the double bonds of cis-polyisoprene and polybutadiene in the presence of free-radical initiators. 84 Thiol compounds also add photochemically to polymers containing double bonds. For instance, unsaturation can be introduced into polyepichlorohydrin by a partial elimination reaction.…”

Section: Diels-alder Condensationsmentioning

confidence: 99%

Reactions of Polymers

Ravve¹

1995

Principles of Polymer Chemistry

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In consideration of various chemical reactions of macromolecules, the reactivity of their functional groups must be compared to those of small molecules. The comparisons have stimulated many investigations and led to conclusions that functional groups exhibit equal reactivity in both large and small molecules, if the conditions are identical. These conclusions are supported by theoretical evidence. i ,2 Specifically, they apply to the following situations i :1. Reactions that take place in homogeneous fluid media with all reactants, intermediates, and end products fully soluble. These conditions exits from the start to the end of the reactions. 2. All elementary steps involve only individual functional groups. The other reacting species are small and mobile. 3. The steric factors in the low molecular weight compounds selected for comparison must be similar to those of the large molecules.The above can be illustrated by a few examples. For instance, the rates of photochemical cis-trans isomerization of azobenzene residues on the backbones of flexible polymeric chains are analogous to those of small molecules? Another example is the activation energy for cis-trans isomerization of azoaromatic polyuria. It is the same for low molecular weight analogs. 4 A third example is an experiment in comparing conformational transitions of some eximers in large and small molecules. A sandwich complex forms between an excited aromatic chromophore, Ar, and a similar chromophore in the ground state when irradiated with light of an appropriate wavelength. The conformation required by such an excimer can correspond to a prohibitive energy requirement for the unexcited molecule. All conformational transitions must take place during the lifetime of the excited state of the chromophore that is of the types:The ratio of the fluorescence intensity of an excimer and a normal molecule is a measure of the probability that the conformational transition takes place during the excited lifetime. A polyamide with only a small proportion of the following units was used for comparison: 403A. Ravve, Principles of Polymer Chemistry © Springer Science+Business Media New York 1995 Diffusion-Controlled ReactionsReactions that are bimolecular can be affected by the viscosity of the medium. 9 The translational motions of flexible polymeric chains are accompanied by concomitant segmental rearrangements. Whether this applies to a particular reaction, however, is hard to tell. For instance, two dynamic processes affect reactions, like termination rates, in chain-growth polymerizations. !fthe termination processes are controlled by translational motion, the rates of the reactions might be expected to vary with the translational diffusion coefficients of the polymers. Termination reactions, however, are not controlled by diffusions of entire molecules, but only by segmental diffusions within the coiled chains. IO The reactive ends assume positions where they are exposed to mutual interaction and not affected by the viscosity of the medium. Paired Group and Ne...

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Diene Rubber Modification Using Thiol-Type Derivatives

Cited by 14 publications

References 13 publications

50th Anniversary Perspective: Polymer Functionalization

50th Anniversary Perspective: Polymer Functionalization

Poly(ethylene glycol-co-allyl glycidyl ether)s: A PEG-Based Modular Synthetic Platform for Multiple Bioconjugation

Reactions of Polymers

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