Use of carbon–carbon nuclear spin diffusion for the study of the miscibility of polymer blends

Linder, Max; Henrichs, P. M.; Hewitt, J. Michael; Massa, Dennis J.

doi:10.1063/1.448434

Cited by 91 publications

(41 citation statements)

References 51 publications

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“…Proton spin diffusion measurements can yield information about domain sizes as well as the thickness of the interphase between the domains. [7] Domain sizes from a few nm and up to 100-200 nm can be determined, depending on the spin-lattice relaxation time T 1 and the spin diffusion constant D. [27][28][29][30][31] From 1 H spin diffusion measurements, the domain sizes of microphase separated structures can be determined, using the initial rate approximation. [3,31] For systems with a relatively small interphase, i.e.…”

Section: Resultsmentioning

confidence: 99%

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using ¹H Spin Diffusion

Werkhoven¹,

Mulder²,

Zune³

et al. 2003

Macro Chemistry & Physics

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The microphase structure of polyisoprene‐block‐poly(methyl methacrylate) diblock copolymers was studied using solid‐state NMR techniques. Wideline separation spectroscopy reveals a narrow interphase between the two polymers. The domain sizes of a lamellar sample and a sample with hexagonally ordered cylinders were determined using 1H spin diffusion. The lamellar sample shows a domain size of 16 ± 2 nm for the minor polyisoprene phase and a long period of 33 ± 4 nm. The cylindrical structure has a long period of 38 ± 7 nm, the diameter of the PMMA cylinders is 21 ± 4 nm. These results are about 20% below the estimates obtained from theoretical calculations according to Helfand and Wasserman. Morphologies of an a) lamellar, and b) hexagonally ordered cylindrical sample (schematic). The triangle in (b) indicates the symmetry that can be used to calculate the dL.magnified imageMorphologies of an a) lamellar, and b) hexagonally ordered cylindrical sample (schematic). The triangle in (b) indicates the symmetry that can be used to calculate the dL.

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Section: Resultsmentioning

confidence: 99%

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using ¹H Spin Diffusion

Werkhoven¹,

Mulder²,

Zune³

et al. 2003

Macro Chemistry & Physics

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“…When several inequivalent groups of nuclei are present, each ssb manifold acquires a different phase factor of iso a T R /2 (see Eq. [5]), which cannot be cancelled simultaneously for all manifolds. Figure 3d shows a spectrum of the tropolone sample recorded by this sequence.…”

Section: Figmentioning

confidence: 96%

“…[5]) in two respects. First, for exchange involving only congruent nuclei within the same symmetry type, there is no phase twist.…”

Section: Figmentioning

confidence: 98%

Initial Conditions for Carbon-13 MAS NMR 1D Exchange Involving Chemically Equivalent and Inequivalent Nuclei

Tékély

Reichert

Zimmermann

et al. 2000

Journal of Magnetic Resonance

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“…The 13 C spin diffusion cannot be detected over the distance of 1.0 nm because of the lower gyromagnetic ratio and the less natural abundant by comparison with those of 1 H nucleus. 2 In this study, I show that the natural abundant two-dimensional (2D) exchange 13 C NMR experiment is one of useful tools to prove the existence of such an intermolecular specific interaction in the polymer materials. …”

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confidence: 99%

“…The doubly CH 2 13 C-enriched poly(ethylene terephthalate) (PET) has been examined and the k value of 19.0 s À1 is reported for the 13 C-13 C distance of 0.235 nm at room temperature. 2 Since the value of T g for PET is approximately 355 K, the molecular motion is also negligible. Consequently, we estimate the intermolecular distance between PMAA and PVAc at the 3:2 = [MAA]: [VAc] interacted portion by comparing the k values between PET and the current polymer blends.…”

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Hydrogen-Bond Interaction of PMAA/PVAc Blends: A Natural Abundant Two-Dimensional Exchange 13C NMR Investigation

Asano

2004

Polym J

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ABSTRACT:The natural abundant two-dimensional exchange 13 C NMR revealed the very close proximity between the carboxyl carbon of PMAA and carbonyl carbon of PVAc in the miscible PMAA/PVAc = 3/1 blend. The estimated distance between the CO carbons is approximately 0.37 nm. This close distance is induced by a strong hydrogen bond between the hydrogen of carboxyl group for PMAA and the oxygen of carbonyl group for PVAc. The molecular mechanics (MM) calculation reveals that the distance of the hydrogen bond between the hydrogen of the carboxyl group and the oxygen of the carbonyl group is approximately 0.2 nm by fixing the intermolecular (inter-polymer) C-C distance between the CO carbons to be 0.37 nm. This value is reasonable for the very strong hydrogen bonding interaction. This interaction makes the 13 C chemical shift value of PVAc carbonyl carbon peak toward lower field by 4 ppm and that of PMAA carboxyl carbon peak to change toward upper field by 4 ppm. The MM calculation also showed that the distance between the backbone carbons of PMAA and PVAc is less than 1 nm. This very cross proximity for the interacted region is important to create the homogenous PMAA/PVAc blends on a scale of 2-5 nm.KEY WORDS Hydrogen Bond / Polymer Blends / CPMAS 13 C NMR / Two-Dimensional Exchange 13 C NMR / Poly(methacrylic acid) / Poly(vinyl acetate) /In the previous study, 1 I showed that the excellent miscibility on a scale of 2-5 nm of the poly(metha-blends is achieved by the specific intermolecular hydrogen bonding interaction at the unit molar ratio of 3:2 = [MAA]: [VAc] between the PMAA and PVAc: here, the word of ''intermolecular'' refers to ''interpolymer'' between PMAA and PVAc, while ''intramolecular'' means the inside of PMAA or PVAc, respectively. It has been also found that the amount of the intermolecular 3:2 = [MAA]: [VAc] interaction is needed over 30 % to be a miscible blend on a scale of 2-5 nm. The PMAA-rich/PVAc blends have the interacted portion over 30 %, resulting that it shows the excellent miscibility on the 2-5 nm scale. On the other hand, the miscibility of the PMAA/PVAc-rich blends is not established on the 2-5 nm scale because the blends have the portion less than 25 % only. 1The intermolecular hydrogen bonding is strong as the chemical shift of PVAc-CO carbon move toward the lower field by 4 ppm: the bulk PVAc-CO carbon resonate at 171 ppm and the interacted CO carbon at 175 ppm. Furthermore, the interacted PMAA-COOH carbon is appeared at the upper field by 4 ppm (179 ppm) relative to the chemical shift value of the bulk PMAA-COOH carbon at 183 ppm; because the strength of intermolecular hydrogen bonding interaction is weaker than that of intramolecular PMAA, the peak of the intermolecular interacted PMAA-COOH carbon shifts toward the upper field not but the lower field: the similar chemical shift change is observed in a PMAA/PEO complex 3 and explained by the difference of the strength between the intermolecular and intramolecular hydrogen bonding. These shifts of the individual peaks produce the c...

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Use of carbon–carbon nuclear spin diffusion for the study of the miscibility of polymer blends

Cited by 91 publications

References 51 publications

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using ¹H Spin Diffusion

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using ¹H Spin Diffusion

Initial Conditions for Carbon-13 MAS NMR 1D Exchange Involving Chemically Equivalent and Inequivalent Nuclei

Hydrogen-Bond Interaction of PMAA/PVAc Blends: A Natural Abundant Two-Dimensional Exchange 13C NMR Investigation

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Use of carbon–carbon nuclear spin diffusion for the study of the miscibility of polymer blends

Cited by 91 publications

References 51 publications

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using 1H Spin Diffusion

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using 1H Spin Diffusion

Initial Conditions for Carbon-13 MAS NMR 1D Exchange Involving Chemically Equivalent and Inequivalent Nuclei

Hydrogen-Bond Interaction of PMAA/PVAc Blends: A Natural Abundant Two-Dimensional Exchange 13C NMR Investigation

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Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using ¹H Spin Diffusion

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using ¹H Spin Diffusion