One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization

Öztürk, Temel; Yavuz, M. Sukru; Göktaş, Melahat; Hazer, Baki

doi:10.1007/s00289-015-1558-2

Cited by 54 publications

(33 citation statements)

References 65 publications

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“…Many difunctional ROP–RAFT inifers (I ROP –CTA RAFT ) in which one end contains an alcohol or amine (I ROP ) and the other contains a trithiocarbonate, dithiobenzoate, or xanthogenate (CTA RAFT ) have been used to make block copolymers. These inifers have been used to copolymerize a variety of vinyl monomers with many cyclic ester monomers with dispersities lower than 1.1 . These polymerizations can be done in one pot, simultaneously or sequentially, suggesting that the polymerizations are orthogonal.…”

Section: Strategies For Dual Polymerizationsmentioning

confidence: 99%

Dual Polymerizations: Untapped Potential for Biomaterials

Lee

Lamm

Prossnitz

et al. 2018

Adv Healthcare Materials

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Block copolymers with unique architectures and those that can self‐assemble into supramolecular structures are used in medicine as biomaterial scaffolds and delivery vehicles for cells, therapeutics, and imaging agents. To date, much of the work relies on controlling polymer behavior by varying the monomer side chains to add functionality and tune hydrophobicity. Although varying the side chains is an efficient strategy to control polymer behavior, changing the polymer backbone can also be a powerful approach to modulate polymer self‐assembly, rigidity, reactivity, and biodegradability for biomedical applications. There are many developments in the syntheses of polymers with segmented backbones, but these developments are not widely adopted as strategies to address the unique constraints and requirements of polymers for biomedical applications. This review highlights dual polymerization strategies for the synthesis of backbone‐segmented block copolymers to facilitate their adoption for biomedical applications.

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Section: Strategies For Dual Polymerizationsmentioning

confidence: 99%

Dual Polymerizations: Untapped Potential for Biomaterials

Lee

Lamm

Prossnitz

et al. 2018

Adv Healthcare Materials

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show abstract

“…100 MHz, 13 C NMR spectra were recorded in CDCl 3 at 25 °C on a Bruker Avance 400 pulsed spectrometer equipped with 5-mm broadband probe and applying Waltz-16 decoupling sequence. Chemical shifts were referenced to tetramethylsilane serving as an internal standard.…”

Section: Measurementsmentioning

confidence: 99%

“…Potassium alkoxides, i.e., MeOK, i-PrOK and t-BuOK, were used for initiation of ε-CL polymerization. Analysis of the polymers obtained by 13 C NMR gave information about final groups, present in the polymer chains after treating with MeI as quenching agent. Further data concerning polymer chemical structure were obtained by the use of MALDI-TOF technique.…”

Section: Polymerization Of ε-Caprolactone Initiated With Potassium Almentioning

confidence: 99%

“…Much more interesting are block copolymers that have excellent physical properties and belong to the most important materials used in technological applications. Some examples involve poly(CL-b-styrene) block copolymers [12] or poly(MMA-b-CL) triarm block copolymers synthesized by the simultaneous ATPR and ROP in one step [13]. Copolymers including PEG and PCL unit are good transporter for hydrophobic drugs delivery [14].…”

Section: Introductionmentioning

confidence: 99%

“…All processes were carried out in tetrahydrofuran solution at room temperature. MALDI-TOF and 13 C NMR techniques were used for the determination of the structure of polymers prepared. Molar masses and dispersity of polymers were obtained by SEC chromatography.…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of ε-caprolactone polymerization in the presence of alkali metal salts: investigation of initiation course and determination of polymers structure by MALDI-TOF mass spectrometry

2018

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Various alkali metal salts were applied as initiators for ε-caprolactone anionic ringopening polymerization in tetrahydrofuran at room temperature. It was observed that potassium methoxide (MeOK), potassium isopropoxide (i-PrOK) and potassium tert-butoxide (t-BuOK) nonactivated or activated by 18-crown-6 (18C6) initiated polymerization mainly by deprotonation of the monomer. In the case of potassium hydride (KH), its basicity increased with the ability of the ligand for cation complexation. For example, KH without ligand or with weak ligands for K + as 12C4 reacted exclusively by ring opening. However, in the presence of strong ligands, as 15C5, 18C6 or cryptand C222, basicity of H − increased with the ability of the ligand for cation complexation. In the last case, ~ 32% of the monomer was deprotonated. In these systems, gaseous H 2 evolved during the initiation. Deprotonation of the monomer by some initiators resulted in macromolecules with reactive aldehyde group or lactone ring as starting groups. They took part in the reaction with potassium alkoxide active centers of growing chains leading to the formation of branched poly(ε-caprolactone)s. Sodium hydride (NaH) was inactive, but in the presence of 15-crown-5 or 18-crown-6 initiated polymerization exclusively by ring opening. MALDI-TOF mass spectrometry supported with 13 C NMR and SEC was used for analysis of the polymers obtained. Mechanism of the studied processes was proposed and discussed.

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Macro peroxide initiators based on autoxidized unsaturated plant oils: Block/graft copolymer conjugates for nanotechnology and biomedical applications

Hazer

2023

J Americ Oil Chem Soc

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The autoxidation of unsaturated fatty acids and their esters is one of the most important reactions in food and biological systems. Autoxidation is a type of reaction between air oxygen and unsaturated plant oils. This reaction starts with a hydrogen abstraction on the methylene group adjacent double bond, leaving a radical onto the carbon atom. Molecular oxygen attacks this radical leading to produce peroxide and hydroperoxide derivatives of the oligomerized unsaturated plant oils. Because peroxide groups thermally cleave to produce free radicals, hydroperoxide derivatives of unsaturated plant oil oligomers can be used in the free radical polymerization of vinyl monomers leading to the related block/graft copolymers. The obtained copolymers combined with the biodegradable natural plant oil gain superior properties such as biodegradability and softness. In this review article, the in vitro autoxidation of well‐known unsaturated plant oils‐soybean oil, linseed oil, and castor oil and some related unsaturated fatty acids‐oleic acid, linoleic acid, and ricinoleic acid was carried out under atmospheric conditions with or without exposing white light. Because the autoxidized unsaturated oil/fatty acids contain peroxide/hydroperoxide groups (they are referred to as macro peroxide initiators) that they are used in the free radical polymerization of vinyl monomers to obtain block/graft copolymers. The improved polymerization conditions, characterization, and applications of the obtained products will be discussed.

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One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization

Cited by 54 publications

References 65 publications

Dual Polymerizations: Untapped Potential for Biomaterials

Dual Polymerizations: Untapped Potential for Biomaterials

Mechanism of ε-caprolactone polymerization in the presence of alkali metal salts: investigation of initiation course and determination of polymers structure by MALDI-TOF mass spectrometry

Macro peroxide initiators based on autoxidized unsaturated plant oils: Block/graft copolymer conjugates for nanotechnology and biomedical applications

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