Poly(thioacrylate)s: expanding the monomer toolbox of functional polymers

Aksakal, Suzan; Becer, C. Remzi

doi:10.1039/c6py01721e

Cited by 23 publications

(21 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thioester functional polymers can mainly be obtained by employing thioester‐containing monomers (e.g., thioacrylates, thiolactone), their generation during the polymerization process (e.g., polythioesters), or by using thioester‐containing chain transfer agents/initiators depending on the employed polymerization technique . In metal‐mediated polymerizations such as atom transfer radical polymerization (ATRP) or single‐electron transfer living radical polymerization (SET‐LRP), mostly ester‐based initiators are used due to their easy synthesis, but more importantly due to their compatibility with a wide range of monomers, which is determined by efficiency of the initiator.…”

Section: Methodsmentioning

confidence: 99%

“…

process (e.g., polythioesters), or by using thioester-containing chain transfer agents/ initiators depending on the employed polymerization technique. [6][7][8][9][10] In metalmediated poly merizations such as atom transfer radical polymerization (ATRP) or single-electron transfer living radical polymerization (SET-LRP), mostly esterbased initiators are used due to their easy synthesis, but more importantly due to their compatibility with a wide range of monomers, which is determined by efficiency of the initiator.The employed initiators in the literature have three main structural features that effect the efficiency, namely i) the initiator halogen, ii) the R-groups that substitute the α-carbon, and iii) the nature of the neighboring group (Scheme 1). Two of the most widely used ester initiators bearing a bromine chain end are methyl bromoproprionate and ethyl α-bromoisobutyrate (EBiB), which are mainly used to polymerize (meth)acrylates and acrylonitrile monomers.

…”

mentioning

confidence: 99%

See 1 more Smart Citation

Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation

Aksakal

Becer

2019

Macromol. Rapid Commun.

Self Cite

View full text Add to dashboard Cite

The synthesis of a new class of Cu‐mediated polymerization initiators with thioester functionality is demonstrated and their polymerization kinetics via single‐electron transfer living radical polymerization is reported. From periodic sampling, it is found that thioester‐ or ester‐based initiators can be employed interchangeably, resulting in very similar polymerization rates. Furthermore, a multifunctional thioester initiator is employed for the preparation of a well‐defined four‐arm star‐shaped polymer. It is further shown that the full dissociation of the star polymer into linear arms via native chemical ligation can easily be followed via size exclusion chromatography, as a result of the change in hydrodynamic volume. Finally, the obtained linear polymers are characterized via matrix‐assisted laser desorption/ionization–time of flight mass spectrometry and found to be in good agreement with the expected molecular weight distribution that confirms the successful transformation.

show abstract

Section: Methodsmentioning

confidence: 99%

“…

…”

mentioning

confidence: 99%

Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation

Aksakal

Becer

2019

Macromol. Rapid Commun.

Self Cite

View full text Add to dashboard Cite

show abstract

“…It also reduces the length of the side chains, thus limiting their flexibility which could be potentially important for applications such as cell interaction. Thus, a new sequence‐defined protocol was developed in collaboration with Becer and co‐workers, which explored the incorporation of thioacrylates and their modification using primary amines …”

Section: Methodsmentioning

confidence: 99%

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

Holloway

Mertens

Prez

et al. 2018

Macromol. Rapid Commun.

View full text Add to dashboard Cite

An automated, iterative protocol for the synthesis of multifunctional, sequence‐defined oligo‐urethane‐amides using thiolactone chemistry is reported. Here, sequenced functionalization of the backbone is easily introduced using commercially available primary amines. The chemistry is carried out on solid phase using different supports for better optimization of the synthetic protocol and in order to demonstrate the versatility of the approach. This technique is very effective for iterative synthesis and solid‐phase chemistry and enables the exploration of full automation of this approach using a robotic peptide synthesizer. As a result, this automated protocol allows for the synthesis of a sequence‐defined nonamer of high purity.

show abstract

“…Another attractive topic concerning sulfur‐containing polymers is synthesis of thioacrylate monomers and their free radical polymerization. In fact, various sulfur‐containing polymers have been synthesized using thioacrylates as monomers . However, there are no reports on introducing thioester pendants into polyethylene.…”

Section: Introductionmentioning

confidence: 99%

“…In fact, various sulfur-containing polymers have been synthesized using thioacrylates as monomers. [8][9][10] However, there are no reports on introducing thioester pendants into polyethylene.…”

mentioning

confidence: 99%

Synthesis and characterization of functional polyethylene with regularly distributed thioester pendants via ring‐opening metathesis polymerization

Song

Zhang

Liu

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

Four kinds of functional polyethylene carrying thioester pendants were synthesized via ring-opening metathesis polymerization (ROMP) of alkyl cyclopent-3-enecarbothioate catalyzed by a ruthenium-based commercial catalyst and subsequent hydrogenation of the ROMP products (alkyl 5 ethyl, nbutyl, n-octyl, or n-dodecyl). In these polymers the pendant alkyl thioester groups are precisely distributed along the backbone on every five methylene carbons. Chain structure, molecular weight and molecular weight distribution of the polymers were characterized by 1 H and 13 C NMR, and GPC. The ROMP reactions all reached high monomer conversions, and hydrogenation of the ROMP products were exhaustive. Thermal transitions and side chain crystallization behaviors of the polymer were investigated and characterized by DSC and TGA. Glass transition temperature and melting temperature of these polymers were higher than the counterparts containing ester pendants. TGA analysis indicated that all the thioester-containing polymers exhibited moderate thermal stability, and the sulfurcontaining polymers show slightly lower thermal stability than their counterparts without sulfur. The new family of functionalized polyethylenes could be used as models of ethylenethioacrylate copolymers, and find applications as novel functional materials.

show abstract

Poly(thioacrylate)s: expanding the monomer toolbox of functional polymers

Abstract: A facile method for synthesizing thioacrylate monomers and their RAFT polymerization have been demonstrated for the first time.

Cited by 23 publications

References 35 publications

Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation

Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

Synthesis and characterization of functional polyethylene with regularly distributed thioester pendants via ring‐opening metathesis polymerization

Contact Info

Product

Resources

About