Synthesis of well‐defined aromatic polyamide‐<i>graft</i>‐poly(tetrahydrofuran) by chain‐growth condensation polymerization of macromonomer

Sugi, Ryuji; Tate, D. P.; Yokozawa, Tsutomu

doi:10.1002/pola.26671

Cited by 14 publications

(12 citation statements)

References 42 publications

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“…The polytetrahydrofuran (PTHF) is widely used in thermoplastic elastomers polyurethanes, novel copolymers, and composite materials, and is produced through a polymerization reaction of tetrahydrofuran (THF), which is one of the most common cationic ring‐opening polymerizations (CROP) . It has been demonstrated earlier that CROP of THF proceeds as a process with fast initiation, rapid propagation, uncontrollable chain transfer, and non‐termination, which is closely connected to the yield and molecular weight of PTHF product.…”

Section: Introductionmentioning

confidence: 99%

Real‐time monitoring of ring‐opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy

Hang-jun

Shen

et al. 2014

J of Applied Polymer Sci

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The polymerization of tetrahydrofuran (THF) was carried out in CH2Cl2 by using phosphotungstic heteropolyacid as initiator and epichlorohydrin as promoter. This cationic ring‐opening polymerization process was monitored by in situ mid‐infrared spectroscopy system (ReactIR) to further study the thermodynamics and kinetics of THF polymerization. It was observed that the sharp infrared peak of COC stretching vibrations will shift from about 1068 to 1109 cm−1 in THF ring‐opening step. The changes in absorbance intensity of the two characteristic peaks were used for determining instantaneous concentration of linear polymer and ring monomer. The experimental results demonstrated that the kinetics of THF polymerization proved to be typically first‐order. Thermodynamic parameters were determined from the temperature dependence of the monomer equilibrium concentration [M]e over the range from −5 to 25°C. The values of kapp were obtained via the plots of ln{([M]0−[M]e)/([M]t−[M]e)} vs reaction time, for polymerization under specific conditions. The apparent activation energy (Ea) and frequency (A) were determined from the Arrhenius plot of kapp vs. T−1. Besides, the in situ kinetic investigation revealed that more chain‐transfer occurred at higher temperatures, leading to a reduction in propagation species concentration and a deviation from first‐order propagation at the later stage of polymerization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40503.

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Section: Introductionmentioning

confidence: 99%

Real‐time monitoring of ring‐opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy

Hang-jun

Shen

et al. 2014

J of Applied Polymer Sci

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“…The third “grafting through” approach, which carried out by the polymerization of MM, has been proved to be the most efficient method to synthesis of graft copolymers with 100% grafting density (every repeating unit containing one side chain). This method is convenient since it affords the most precise and easiest control of side chain length and main chain length . Ring‐opening metathesis polymerization (ROMP) of MM using transition metals, such as molybdenum and ruthenium, has been demonstrated to be efficient in synthesis of brush polymers with low polydispersity index (PDI) and high molecular weight .…”

Section: Introductionmentioning

confidence: 99%

“…This method is convenient since it affords the most precise and easiest control of side chain length and main chain length. [ 23 ] Ring-opening metathesis polymerization (ROMP) of MM using transition metals, such as molybdenum and ruthenium, has been demonstrated to be effi cient in synthesis of brush polymers with low polydispersity index (PDI) and high molecular weight. [ 24,25 ] However, the use of costly rare metals and the limited functional group tolerance and air and moisture sensitivity of the catalysts great restrain their applications.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of High‐Molecular‐Weight Brush Polymers via RAFT Polymerization within the Micellar Nanoreactor of a PEG‐Based Macromonomer

Liu

et al. 2014

Macro Chemistry & Physics

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The RAFT polymerization of an amphipathic PEG‐based macromonomer (mPEG‐g‐S) in water is performed. It is found that the polymerization proceeds via a micellar polymerization process. The polymerization kinetics, polymer chain extension, and polymer particle evolution of RAFT micellar polymerization are evaluated. It is demonstrated that the polymerization possesses a fast rate and high monomer conversion due to locally concentrating and orienting the hydrophobic polymerizing groups within the micellar nanoreactor. Moreover, the RAFT micellar polymerization is under good control since the polydispersity index (PDI) value of the synthesized brush copolymer is below 1.3 in most cases, even under polymerization conditions with the ratio of RAFT agent to macromonomer at 1:400. Polymerization leads to the formation of a completely grafted brush copolymer, and the as‐synthesized brush copolymer will self‐assemble into spherical particles during the polymerization process. This strategy is anticipated to be an efficient way for the controlled synthesis of completely grafted brush polymers with high molecular weights and their corresponding self‐assembled particles.

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“…The synthetic route started with the polymerization of 3 from a monofunctional initiator, followed with the introduction of a fluorobenzophenone unit at the polymer terminal, and finished with the polymerization of the polyether monomer. Regarding graft copolymers, Sugi et al described a well-defined aramid grafted with poly(tetrahydrofuran) by chain growth polymerization of 4-aminobenzoic acid ester having a poly(tetrahydrofuran) residue 5a on the amino group [22]. The polymerization of monomer 5a at −10 °C was accompanied with self-polycondensation.…”

Section: Introductionmentioning

confidence: 99%

Functional Aromatic Polyamides

et al. 2017

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Abstract:We describe herein the state of the art following the last 8 years of research into aromatic polyamides, wholly aromatic polyamides or aramids. These polymers belong to the family of high performance materials because of their exceptional thermal and mechanical behavior. Commercially, they have been transformed into fibers mainly for production of advanced composites, paper, and cut and fire protective garments. Huge research efforts have been carried out to take advantage of the mentioned characteristics in advanced fields related to transport applications, optically active materials, electroactive materials, smart materials, or materials with even better mechanical and thermal behavior.

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Synthesis of well‐defined aromatic polyamide‐graft‐poly(tetrahydrofuran) by chain‐growth condensation polymerization of macromonomer

Cited by 14 publications

References 42 publications

Real‐time monitoring of ring‐opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy

Real‐time monitoring of ring‐opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy

Synthesis of High‐Molecular‐Weight Brush Polymers via RAFT Polymerization within the Micellar Nanoreactor of a PEG‐Based Macromonomer

Functional Aromatic Polyamides

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