Morphology and crystallization in mixtures of poly(methyl methacrylate)-poly(pentafluorostyrene)-poly(methyl methacrylate) triblock copolymer and poly(vinylidene fluoride)

Kim, Geon Seok; Kang, Min Sung; Choi, Mi Ju; Kwon, Yong Ku; Lee, Kwang Hee

doi:10.1007/bf03218611

Cited by 7 publications

(5 citation statements)

References 34 publications

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“…The ATRP of styrene was conducted with CuBr/PMDETA as catalyst/ligand at 100 °C in toluene. 29,30 After 18 hours, the polymer was precipitated in methanol and dried under vacuum. HT-GPC results of the PM-b-PS diblock copolymer (run 3, Table 1) showed narrow polydispersity indexes (Ɖ= 1.15−1.3) and the Mn of the constituent blocks ranged from 15000 to 19000 g/mol (Figure 1c and Figure S1, SI).…”

Section: Resultsmentioning

confidence: 99%

“…We took advantage of the efficient transformation reaction from hydroxyl (PM-OH) to a-haloester (PM-Br) not only for the subsequent halogen exchange (Br → I) but also to use PM-Br as a macroinitiator for ATRP of styrene to incorporate the amorphous PS between the two crystalline (PM and PVDF) blocks. The ATRP of styrene was conducted with CuBr/PMDETA as catalyst/ligand at 100 °C in toluene. , After 18 h, the polymer was precipitated in methanol and dried under vacuum. HT-GPC results of the PM- b -PS diblock copolymer (run 3, Table ) showed narrow polydispersity indexes ( Đ = 1.15–1.3), and the M n of the constituent blocks ranged from 15000 to 19000 g/mol (Figure c and Figure S1).…”

Section: Resultsmentioning

confidence: 99%

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Poly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers

et al. 2019

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Dual crystalline diblock copolymers consisting of polymethylene (PM) and poly(vinylidene fluoride) (PVDF) blocks as well as triblock terpolymers with polystyrene (PS) as middle block were synthesized. For the synthesis, two/three different polymerization methods such as polyhomologation, atom transfer radical polymerization (ATRP) and iodine transfer polymerization (ITP) along with chain-end post-polymerization reactions were employed. Solid-state NMR spectroscopy revealed the characteristic peaks of all constituent blocks while gel permeation chromatography (GPC) results demonstrated the controlling/living nature of all implemented polymerization methods. The analysis of crystallization behavior based on differential scanning calorimetry (DSC) indicates the presence of different PVDF crystalline phases (α, β, and γ) upon the incorporation of PM and PS blocks. Further analysis with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopies revealed the co-existence of α-and β-phases in diblock and βand γ-phases in triblock terpolymer. An initial study on self-assembly in DMF, a selective solvent for PVDF and PS, was performed by dynamic light scattering (DLS) and atomic force microscopy (AFM). electroactive β-phase but also non electroactive α-phase for the diblock copolymer while β-and γphase for triblock terpolymers. Furthermore, according to DSC, XRD and IR results, the presence of a PS intermediate block between PM and PVDF led to the formation of mainly γ-phase. Efforts to extend the synthesis of a variety of semi-fluorinated polymers, as well as to gain additional insights into their morphology, self-assembly, and dispersive properties are currently underway in our laboratory. These type of PVDF-based copolymer could be potentially used as polymer binders for lithium-ion batteries optimizing properties like adhesion strength and flexibility. Finally, this study opens new horizons towards the synthesis of PM-b-PVDF-based complex macromolecular architectures.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Poly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers

et al. 2019

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“…It is well reported that a variety of morphologies, such as lamellae, cylinders, spheres and double gyroids, have been identified for diblock copolymers on the nanoscale, as a result of the microphase separation of the different blocks . There are a few studies of blending PVDF with block copolymers such as polystyrene (PS)–poly(methyl methacrylate) (PMMA) diblock copolymer, PMMA–poly(pentafluorostyrene)–PMMA triblock copolymer and poly[(butyl acrylate)‐ co ‐(hydroxyethyl methacrylate)]–PMMA diblock copolymer . Choi and Jo have reported a poly(styrene‐ co ‐(styrenesulfonic acid)]‐ b ‐PMMA/PVDF blend system as proton exchange membrane.…”

Section: Introductionmentioning

confidence: 99%

“…Also, in blends with PVDF‐rich composition, the morphology varies from the PMMA‐cylindrical to the lamellar and the PS‐cylindrical structure . Kim et al have investigated PVDF/PMMA–PPFS–PMMA triblock copolymer. It was found that the PVDF phase is entirely localized within the PMMA microdomains without the occurrence of phase separation .…”

Section: Introductionmentioning

confidence: 99%

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Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene blends

Seraji

Guo

2019

Polymer International

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An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane-block-poly(methyl methacrylate)-block-polystyrene (PDMS-b-PMMA-b-PS) triblock copolymer was synthesized by the atom-transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS-b-PMMA-b-PS blends were studied within the whole range of concentration. In this A-b-B-b-C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self-assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 ∘ C reveals that both and crystalline phases of PVDF are present in PVDF/PDMS-b-PMMA-b-PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of to phase of semicrystalline PVDF. Introduction of PDMS-b-PMMA-b-PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small-angle X-ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. RESULTS AND DISCUSSION Characterization of PDMS-b-PMMA-b-PS triblock copolymerThe final copolymer, PDMS-b-PMMA-b-PS, was characterized using 1 H NMR. The -SiCH 3 group of PDMS block, the -OCH 3 group of PMMA block and the -C 6 H 5 of PS gave three characteristic peaks, as shown in Fig. 2, centred at 0 .0, 3.63 and 6.5-7.16 ppm, respectively. 32 According to the above results, the molecular weights (M n ) of PMMA and PS are 10 300 and 6300 g mol −1 , respectively. The total M n of the PDMS-b-PMMA-b-PS triblock copolymer is 21 300 g mol −1 . Figure S1 presents the FTIR spectrum of the PDMS-b-PMMA-b-PS triblock copolymer. The presence of the characteristic bands of each block of the synthesised triblock copolymer analysed and the details are presented in Table S1.

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Polymorphism and crystallization in poly(vinylidene fluoride)/ poly(ϵ‐caprolactone)–block–poly(dimethylsiloxane)–block–poly(ϵ‐caprolactone) blends

Seraji

Guo

2019

Polymer International

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The miscibility, crystallization kinetics and crystalline morphology of a new system of poly(vinylidene fluoride)/poly(ϵ‐caprolactone)‐block‐poly(dimethylsiloxane)‐block‐poly(ϵ‐caprolactone) (PVDF/PCL‐b‐PDMS‐b‐PCL) triblock copolymer were investigated by a variety of techniques. The miscibility and phase behaviour of PVDF/PCL‐b‐PDMS‐b‐PCL were studied by determination of the melting point temperature, crystallization kinetics and Fourier transform infrared (FTIR) mapping. Chemical imaging was used as a new technique to characterize the interaction of polymer blends in crystalline morphology. The results demonstrate the existence of characteristic peaks of both PVDF and PCL in the chosen crystalline area. The crystalline structures of PVDF were affected by the PCL‐b‐PDMS‐b‐PCL triblock copolymer and facilitate the formation of the β polymorph which was illustrated by FTIR analysis. The β crystal phase fraction increases significantly on increasing the composition of the PCL‐b‐PDMS‐b‐PCL triblock copolymer. In addition, confined crystallization of PCL within PVDF inter‐lamellar and/or inter‐fibrillar regions was confirmed through polarizing optical microscopy, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering analysis. © 2019 Society of Chemical Industry

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Morphology and crystallization in mixtures of poly(methyl methacrylate)-poly(pentafluorostyrene)-poly(methyl methacrylate) triblock copolymer and poly(vinylidene fluoride)

Cited by 7 publications

References 34 publications

Poly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers

Poly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers

Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene blends

Polymorphism and crystallization in poly(vinylidene fluoride)/ poly(ϵ‐caprolactone)–block–poly(dimethylsiloxane)–block–poly(ϵ‐caprolactone) blends

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