Miscibility of Polyoxymethylene Blends as Revealed by High-resolution Solid-state13C-NMR Spectroscopy

Matsumoto, Akiko; Egawa, Yuichiro; Matsumoto, T.; Horii, Fumitaka

doi:10.1002/(sici)1099-1581(199704)8:4<250::aid-pat636>3.0.co;2-9

Cited by 7 publications

(8 citation statements)

References 12 publications

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“…However, the appropriate ε value to use for miscible or partially miscible blends is not obvious without some independent information on the morphology. 57 The literature on spin-diffusion studies of polymer blends reports the use of ε ) 1 [58][59][60][61][62] and ε ) 2. 63,64 For the dissolved POE, we used ε ) 1 and assumed that the important polarization gradient is 1-dimensional for a POE chain segment in intimate contact with more rigid PS chain segments.…”

Section: Poe Domain Sizes From Spin-diffusion Nmrmentioning

confidence: 99%

Miscible Blends of Cyclic Poly(oxyethylene) in Linear Polystyrene

Singla

Beckham

2008

Macromolecules

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Cyclic poly(oxyethylene) (POE) was prepared from hydroxyl-terminated linear POE with molecular weights from 400 to 1500 g/mol using a dilute-solution end-coupling route. These cyclic and linear POEs were solution-mixed with linear polystyrene (PS, 15 kg/mol) to prepare binary blends with POE concentrations from 1.5 to 40 wt %. To assess the effect of end groups, PS was also blended with methoxyl-terminated linear POE with molecular weights from 500 to 2000 g/mol. Thermal analysis was conducted using differential scanning calorimetry to measure the glass transitions (T g) in the blends. Using the Fox equation and the blend T g, we estimated the fraction of POE dissolved into the PS. Across the entire concentration and molecular weight ranges studied, cyclic POE exhibited significantly enhanced miscibility compared to the linear POEs. For the smallest POE additives at concentrations ≤10 wt %, completely miscible blends were formed with cyclic POE, partially miscible blends were formed with the methoxyl-terminated linear POE, and the hydroxyl-terminated linear POE was completely immiscible. 1H solid-state NMR spectroscopy was used to examine the POE dynamics and domain sizes in these dynamically asymmetric blends. In the completely miscible blends, the dissolved POE is characterized by typical smallest diameters of 1−1.5 nm and exhibits reduced segmental mobilities compared to pure POE. In the partially miscible blends, two dynamically distinct POE domains are detected, representing the dissolved POE and phase-separated POE. The phase-separated POE exhibits higher segmental mobilities in larger domains (>∼20 nm).

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Section: Poe Domain Sizes From Spin-diffusion Nmrmentioning

confidence: 99%

Miscible Blends of Cyclic Poly(oxyethylene) in Linear Polystyrene

Singla

Beckham

2008

Macromolecules

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“…[19][20][21][22][23] Solidstate NMR also allows to study long-range ordered structures on the 0.5-500 nm scale via 1 H spin diffusion. 19,22,24 So far, many systems have been studied by 1 H spin diffusion measurements, such as the polymer/ additive system, 25 semicrystalline polymers, 26 polymer blends, 6,15,27 block copolymers, 24 copolyureas, 28 and biopolymers. 29…”

Section: Introductionmentioning

confidence: 99%

“…This relaxation often disappears if the glass transition temperature is lowered by adding a plasticizer, the molecules of which apparently block the internal motions of the phenyl groups . Although a lot of papers concerning the structure and dynamics of single PEO ,− and PC ,− as well as those dealing with various blends containing PEO ,, and/or PC ,, have been published, no work deals with the structure of PC−PEO blends. The studied material (PC−PEO blend) is a complex system consisting of two semicrystalline components.…”

Section: Introductionmentioning

confidence: 99%

“…Of particular interest is the interaction between different components, especially in the interfacial region. A stronger interaction can result in greater modification of NMR spectrum relative to that of neat components (e.g., intermolecular hydrogen-bonding interaction can cause significant “downfield” shift) . These strong hydrogen-bonding interactions support mixing of systems such as poly(oxymethylene)−TPh (terphenphenol polymer composed of terpene and phenolic moieties) 6 or blends of PEO and poly(methyl methacrylate). , For a detailed understanding of mechanical properties, it is also essential to obtain information about the distribution of mobility in the material.…”

Section: Introductionmentioning

confidence: 99%

“…There are various methods for qualitative characterization of molecular mobility, and among others, 1 H wide-line spectroscopy (WISE), where effective strength of dipolar couplings and thus molecular mobility are reflected, is well-known . The desired information about the local dynamics for dynamically heterogeneous systems is provided by heteronuclear 2D WISE experiment. − Solid-state NMR also allows to study long-range ordered structures on the 0.5−500 nm scale via 1 H spin diffusion. ,, So far, many systems have been studied by 1 H spin diffusion measurements, such as the polymer/additive system, semicrystalline polymers, polymer blends, ,, block copolymers, copolyureas, and biopolymers…”

Section: Introductionmentioning

confidence: 99%

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Order and Mobility in Polycarbonate−Poly(ethylene oxide) Blends Studied by Solid-State NMR and Other Techniques

et al. 2000

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Solid-state 1D and 2D 13 C CP/MAS NMR and 1 H CRAMPS (combined rotation and multipulse spectroscopy) and Raman spectroscopy, X-ray scattering, and DSC were used to investigate the structure, morphology, and dynamic behavior of blends of two semicrystalline polymers, polycarbonate (PC) and poly(ethylene oxide) (PEO). The splitting of aromatic carbon signals in the 13 C CP/MAS NMR spectra and the absence of spinning sidebands in the 1 H dipolar spectra (2D WISE) indicate restricted mobility and hindered cooperative motions of PC chains resulting from blending of PC with PEO and from fixed ordering due to partial crystallinity of PC itself. The observed multiple splittings of the signals of aromatic and carbonate carbons indicate comparable amounts of trans-trans and cis-trans conformational structures of the carbonate group. 2D WISE spectra prove large differences in molecular mobility of amorphous PEO and PC. High mobility of amorphous PEO is not imparted significantly to less mobile PC, despite intimate mixing in the amorphous phase of PC-PEO blends suggested by 13 C CP/MAS NMR spectra and CRAMPS 1 H-1 H homonuclear dipolar dephasing and proved by 2D CRAMPS and WISE spin diffusion measurements. The morphology and domain sizes at the nanometer scale were determined from analysis of spin diffusion processes.

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Effect of Highly Crosslinked Domains on the Dimensions of Network Polymers

Tobita

2024

Macro Theory & Simulations

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The effect of spatial inhomogeneity on the dimensions of network polymers is investigated by using model networks containing highly crosslinked domains. It is found that the dimensions of network architecture consisting of densely crosslinked domains connected by long chains are larger than those of loosely crosslinked domains connected by short chains, given the cycle rank is the same. The cases with the domains connected by the domains are also investigated. In all cases, the dimensions are larger than the corresponding randomly crosslinked homogeneous networks. This is because the loosely crosslinked regions dominate the dimensions of network polymers. The master curve relationship found for the statistical networks is applicable also for the present types of spatial inhomogeneous network polymers when the cycle rank is increased to make the network well‐developed in a homologous series of networks.This article is protected by copyright. All rights reserved

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Miscibility of Polyoxymethylene Blends as Revealed by High-resolution Solid-state13C-NMR Spectroscopy

Cited by 7 publications

References 12 publications

Miscible Blends of Cyclic Poly(oxyethylene) in Linear Polystyrene

Miscible Blends of Cyclic Poly(oxyethylene) in Linear Polystyrene

Order and Mobility in Polycarbonate−Poly(ethylene oxide) Blends Studied by Solid-State NMR and Other Techniques

Effect of Highly Crosslinked Domains on the Dimensions of Network Polymers

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