Synthesis and hydrogel formation of fluorine‐containing amphiphilic ABA triblock copolymers

Matsumoto, Kozo; Nishimura, Ryuji; Mazaki, Hiroaki; Matsuoka, Hideki; Yamaoka, H.

doi:10.1002/pola.10011

Cited by 13 publications

(12 citation statements)

References 28 publications

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“…Due to the strong stabilizing effect of the oxygen atom next to the vinyl group, the activation energy associated with the addition of a vinyl ether monomer to a given carbocation is relatively low compared to that of other alkene monomers . The ability to control the reactivity of a vinyl ether cation has enabled the preparation of a wide variety of polymers with well‐defined architectures and composition, such as amphiphilic block copolymers , thermoplastic elastomers (TPE) , graft copolymers , telechelic polymers , and multi‐arm star polymers . Thus, for the polymerization of 2‐VOES, it was thought that the reactivity of the carbocationic species could be tailored such that propagation could only occur through the vinyl ether groups.…”

Section: Homopolymerization and Homopolymer Propertiesmentioning

confidence: 99%

2‐(Vinyloxy)ethyl soyate as a versatile platform chemical for coatings: An overview

Alam

Kalita

Jayasooriya

et al. 2013

Euro J Lipid Sci & Tech

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A plant oil-based polymer technology was recently developed that enables high molecular weight polyvinylether polymers to be produced using cationic polymerization. The plant oil monomer synthesis involves simple base-catalyzed transesterification of a plant oil triglyceride with a hydroxy-functional vinyl, ether such as 4-(vinyloxy)butanol or 2-(vinyloxy)ethanol, to produce a mixture of vinyl ether monomers that possess fatty acid ester groups in their structure. A key aspect of the technology involves the polymerization process that allows for high molecular weight polymers to be produced by polymerization exclusively through the vinyl ether double bonds. This feature enables polymers to be produced that possess unsaturation in the fatty acid ester pendent groups derived from the plant oil starting material. As has been done for conventional plant oil triglycerides, the double bonds can be used to produce thermoset materials either directly through an oxidative process or by derivatization to produce other functional groups, such as epoxides, acrylates, and hydroxyls that can be subsequently used to produce crosslinked networks. The polymerization process also results in a "living" polymerization that allows for control of polymer molecular weight, narrow molecular weight distributions, and the production of unique polymer architectures such as block copolymers. Another very important feature of the technology involves the ability to copolymerize the plant oil-based vinyl ether monomers with other monomers to tailor polymer properties such as glass transition temperature, mechanical properties, and solubility/compatibility with other materials. This document provides an overview of the present state of the technology using soybean oil as a representative plant oil source.

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Section: Homopolymerization and Homopolymer Propertiesmentioning

confidence: 99%

2‐(Vinyloxy)ethyl soyate as a versatile platform chemical for coatings: An overview

Alam

Kalita

Jayasooriya

et al. 2013

Euro J Lipid Sci & Tech

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“…14 The investigation of multicompartment micelles formed by linear styrene-based ABC-triblock copolymers have been also reported by Laschewsky et.al.. 15,16 The majority of fluorine-containing polymers reported in literature is based on poly(meth)acrylates. [17][18][19][20][21][22][23] The synthesis of poly-2-oxazolines with fluorophilic blocks suffers from the difficulties of synthesis and polymerization of fluorophilic monomers. The deceleration effect of the perfluoroalkyl substituent in 2-substituted-2-oxazoline was described by Saegusa and coworkers.…”

Section: Introductionmentioning

confidence: 99%

Fluorophilic–Lipophilic–Hydrophilic Poly(2-oxazoline) Block Copolymers as MRI Contrast Agents: From Synthesis to Self-Assembly

et al. 2018

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This work focused on the synthesis and self-assembly of triphilic poly(2-oxazoline) triblock copolymers with high fluorine content towards our future aim of developing poly(2-oxazoline) MRI contrast agents. A highly fluorinated 2-substituted-2-oxazoline monomer, namely 2-(1H,1H,2H,2H-perfluorooctyl)-2-oxazoline was synthesized using the Grignard reaction. The polymerization kinetics of the synthesized monomer was studied and it was used for the preparation of triblock copolymers with hydrophilic 2-methyl-2-oxazoline, hydrophobic 2octyl-2-oxazoline and fluorophilic blocks by Cationic Ring-Opening Polymerization yielding polymer with low relatively dispersity (1.2-1.4). The presence of the blocks with the different nature in one copolymer structure facilitated self-assembly of the copolymers in water and dimethylsulfoxide as observed by dynamic light scattering, cryo-transmition electron microscopy, and small-angle neutron scattering. The nanoparticle morphology is strongly influenced by the order and length of each block and the nature of solvent, leading to nanoparticles with core-shell structure as confirmed by small angle neutron scattering. The reported poly(2-oxazoline) block copolymers with high fluorine content have high potential for future development of MRI contrast agents.

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“…14-16 Telechelic polymers are important materials to form extended interpenetrating networks or act as crosslinkers for hydrogel formation. 17-19 Additionally, dimeric polymer-conjugates can be synthesized from these linear telechelic polymers. 2,3,12,20,21 Homodimeric biomolecule-conjugates promise to have higher affinity for the desired end-target as a result of multivalency.…”

Section: Introductionmentioning

confidence: 99%

Aminooxy and Pyridyl Disulfide Telechelic Poly(poly(ethylene glycol) acrylate) by RAFT Polymerization

et al. 2012

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An efficient method to synthesize telechelic, bio-reactive polymers is described. Homotelechelic polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization in one step by employing bifunctional chain transfer agents (CTAs). A bis-carboxylic acid CTA was coupled to N-BOC-aminooxy ethanol or pyridyl disulfide ethanol resulting in a bis-N-BOC-aminooxy CTA and a bis-pyridyl disulfide CTA, respectively. RAFT polymerization of polyethylene glycol (PEG) acrylate in the presence of both CTAs resulted in a series of polymers over a range of molecular weights (~8.4 kDa to 35.2 kDa; polydispersity indices, PDIs of 1.11 to 1.44) with retention of end-groups post-polymerization. The polymers were characterized by 1H NMR spectroscopy and gel permeation chromatography (GPC). Conjugations of small molecules and peptides resulted in homotelechelic polymer conjugates.

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Synthesis and hydrogel formation of fluorine‐containing amphiphilic ABA triblock copolymers

Cited by 13 publications

References 28 publications

2‐(Vinyloxy)ethyl soyate as a versatile platform chemical for coatings: An overview

2‐(Vinyloxy)ethyl soyate as a versatile platform chemical for coatings: An overview

Fluorophilic–Lipophilic–Hydrophilic Poly(2-oxazoline) Block Copolymers as MRI Contrast Agents: From Synthesis to Self-Assembly

Aminooxy and Pyridyl Disulfide Telechelic Poly(poly(ethylene glycol) acrylate) by RAFT Polymerization

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