Two-arm PCL and PLLA macrophotoinitiators with benzoin end-functional groups by combination of ROP and click chemistry and their use in the synthesis of A2B2 type miktoarm star copolymers

Uyar, Zafer; Durgun, Mustafa; Yavuz, M. Sukru; Abaci, M. Bahattin; Arslan, Ulku; Degirmenci, Mustafa

doi:10.1016/j.polymer.2017.07.019

Cited by 21 publications

(12 citation statements)

References 25 publications

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“…It is well-known that non-crystalline PCHO is a thermally stable polymer with a decomposition temperature over 400 C. It seems introducing this durable block into the structure of the polymer has enhanced its thermal stability judging from its boosted decomposition temperature in comparison with the prepolymers (24). Figure 8 shows that terminal alkyne groups also contribute to the thermal stability of the polymer positively compared to other homopolymers, (…”

Section: Synthesis Of the Star-shaped Telechelic Macrophotoinitiator (Plla-pi)4mentioning

confidence: 99%

“…Practically, macrophotoinitiators are used as photoreactive agents in photopolymerization to synthesize copolymers such as block and graft (19)(20)(21). Recently, we have successfully applied the combination of ROP and click chemistry to prepare well-defined macrophotoinitiators whose core were connected to both photoreactive group(s) such as benzoin and polymer chain(s) such as PCL or PLLA (22)(23)(24).…”

Section: Telechelicmentioning

confidence: 99%

“…Ring opening polymerization (ROP) of lactides such as L-lactide (LLA) with stannous-2ethylhexanoate, Sn(Oct)2 catalyst, and an OH functionalized initiator is a very convenient method for synthesizing polylactides with welldefined structures (24). Here, we have applied ROP to prepare a tetra-arm star-shaped poly(Llactide) with controlled molecular weight and low molecular weight distribution.…”

Section: Synthesis Of (Plla-oh)4 and (Plla-alkyne)4mentioning

confidence: 99%

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Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

Uyar

Kaya

2018

Journal of the Turkish Chemical Society Section A: Chemistry

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A multi-step reaction process was applied for the synthesis of a novel and well-defined starshaped telechelic macrophotoinitiator with four poly(L-lactide) (PLLA) arms connected to photoinitiating benzoin groups at the chain ends (PLLA-PI)4. To achieve this, 2,2-bis(hydroxymethyl)-1,3-propanediol was used as the initiator which constitutes the core of the star-shaped polymeric scaffold. Benzoin photoreactive end groups of the telechelic (PLLA-PI)4, capable of entering into further polymerization, allowed its use as a polymeric photoinitiator in photoinduced free radical promoted cationic polymerization of cyclohexene oxide (CHO) monomer at =350 nm to produce an (AB)4-type star-shaped block copolymer composed of both esteric L-lactide and etheric cyclohexene oxide chains on each arm, (PLLA-PCHO)4. Structural analysis and characterization of all intermediate and final compounds were done by a series of analytical and spectral methods. Molecular weights of the prepared polymers up to telechelic macrophotoinitiator (PLLA-PI)4 were determined based on 1 H-NMR (Mn H-NMR), GPC (Mn exp) analyses and theoretical calculations (Mn theo) and were found to be in good agreement with each other. Thermal properties and degradations of the prepared polymers were examined by thermogravimetric and differential thermal analyses (TG/DTA). The melting temperature for (PLLA-PCHO)4 was found higher compared to the other homo-type polymers in the literature. The thermogravimetric (TG) analyses showed that incorporation of the thermally stable PCHO block into the structure via photopolymerization improved its stability by increasing its decomposition temperature compared to the prepolymers.

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Section: Synthesis Of the Star-shaped Telechelic Macrophotoinitiator (Plla-pi)4mentioning

confidence: 99%

Section: Telechelicmentioning

confidence: 99%

Section: Synthesis Of (Plla-oh)4 and (Plla-alkyne)4mentioning

confidence: 99%

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Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

Uyar

Kaya

2018

Journal of the Turkish Chemical Society Section A: Chemistry

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“…Moreover, functional groups have often been added to PCL to transform it into a reactive intermediate in order to subsequently use them in coupling reactions. These reactions led to various macromolecular structures [ 26 , 30 ], macroinitiators [ 31 , 32 ], and, very importantly, well-defined macromonomers [ 33 , 34 , 35 ]. Macromonomers are, in fact, oligomer or polymer chains that are functionalized with polymerizable end-groups.…”

Section: Introductionmentioning

confidence: 99%

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2021

Polymers

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End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional “hydrophobic amphiphile”, was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a “block-molecule”. According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL’s propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl3 at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

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“…The preparation of CCS polymers can be accomplished using both synthetic methods along with various controlled radical polymerization (CRP) techniques. [35][36][37][38] Herein, we report here the synthesis of a new polymeric photoinitiator by ATRP technique which has advantage of high absorption properties due to benzoin units in multi-arm polymer structure and several additional contributions such as solubility, compatibility. 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of multiarm (Benzoin‐PS)_m‐polyDVB star polymer as a polymeric photoinitiator for polymerization of acrylates and methacrylates

Esen

Yigit

Tunca

et al. 2021

Journal of Polymer Science

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In this study, a new benzoin-based multi-arm star polymer was synthesized by using ATRP, and characterization was achieved by spectrophotometric and chromatographic methods. Obtained multiarm (Benzoin-PS) m -polyDVB star polymer was employed as a polymeric photoinitiator for polymerization of methacrylates and acrylates. Photophysical properties of this initiator were determined by fluorescence and phosphorescence measurements, the phosphorescence lifetime was calculated as 29 ms hence the lowest triplet state nature was n-π* character, and laser flash photolysis technique was additionally used to get more information about triplet state and triplet lifetime which was calculated as 1.34 ms. Photokinetics of difunctional acrylate such as HDDA was studied with a multi-arm (Benzoin-PS) m -polyDVB star polymeric initiator using Photo-DSC.

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Two-arm PCL and PLLA macrophotoinitiators with benzoin end-functional groups by combination of ROP and click chemistry and their use in the synthesis of A2B2 type miktoarm star copolymers

Cited by 21 publications

References 25 publications

Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Synthesis and characterization of multiarm (Benzoin‐PS)_m‐polyDVB star polymer as a polymeric photoinitiator for polymerization of acrylates and methacrylates

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Two-arm PCL and PLLA macrophotoinitiators with benzoin end-functional groups by combination of ROP and click chemistry and their use in the synthesis of A2B2 type miktoarm star copolymers

Cited by 21 publications

References 25 publications

Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

Synthesis of an (AB)4-type Star Block Copolymer of L-lactide and Cyclohexene Oxide from a Tetra-Arm Telechelic Macrophotoinitiator

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Synthesis and characterization of multiarm (Benzoin‐PS)m‐polyDVB star polymer as a polymeric photoinitiator for polymerization of acrylates and methacrylates

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Synthesis and characterization of multiarm (Benzoin‐PS)_m‐polyDVB star polymer as a polymeric photoinitiator for polymerization of acrylates and methacrylates