Crystallization and Cocrystallization in Supramolecular Comb Copolymer-like Systems:  Blends of Poly(4-vinylpyridine) and Pentadecylphenol

Luyten, M.C.; Ekenstein, G.O.R. Alberda van; Brinke, G. ten; Ruokolainen, Janne; Ikkala, Olli; Torkkeli, Mika; Serimaa, Ritva

doi:10.1021/ma9900481

Cited by 73 publications

(115 citation statements)

References 42 publications

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“…Furthermore, at room temperature, which is well above the T g of the complex, side chain crystallization of the PDP takes place. 32 Note that FTIR measurements show that most of the hydrogen bonds are still present at temperatures near the T ODT , and therefore the ODT is not related to broken hydrogen bonds. 26 Before the shearing started, a SAXS measurement was performed, demonstrating that the sample has a macroscopically isotropic microphase-separated mor- phology (Figure 4a,b).…”

Section: Resultsmentioning

confidence: 99%

Orientation of Supramolecular Self-Organized Polymeric Nanostructures by Oscillatory Shear Flow

Mäkinen¹,

Ruokolainen²,

Ikkala³

et al. 2000

Macromolecules

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IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2000Link to publication in University of Groningen/UMCG research database Citation for published version (APA): M"kinen, R., Ruokolainen, J., Ikkala, O., de Moel, K., ten Brinke, G., De Odorico, W., ... Makinen, R. (2000). Orientation of supramolecular self-organized polymeric nanostructures by oscillatory shear flow. Macromolecules, 33(9), 3441 -3446. DOI: 10.1021/ma991127f Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. M. StammInstitut fü r Polymerforschung, D-01069 Dresden, Germany Received July 13, 1999; Revised Manuscript Received February 14, 2000 ABSTRACT: Macroscopic orientation of self-organized supramolecular polymeric materials has been demonstrated by oscillatory shear flow using in-situ small-angle X-ray scattering (SAXS). In the case when a homopolymer poly(4-vinylpyridine) and pentadecylphenol molecules are stoichiometrically complexed to form comb copolymer-like supermolecules, the self-organized lamellar local structures align parallel when sheared below the order-disorder transition temperature at 56°C using 0.5 Hz frequency and 100% strain amplitude. Therefore, the hydrogen bonds between the phenolic and pyridine groups are strong enough to withstand the applied flow. In the case of a diblock copolymer of polystyrene and poly(4-vinylpyridine) stoichiometrically complexed with pentadecylphenol molecules to form the supermolecules, the self-organization yields lamellar-within-lamellar local structure near room temperature. The larger lamellar diblock copolymer structure showed a parallel orientation relative to the shearing plates upon shearing at 125°C (i.e., above the order-disorder transition of the short length scale comb copolymer-like structure) with initially 0.5 Hz and finally 1 Hz, both at 50% strain amplitude. On cooling, the short length scale lamellar structure, consisting of poly(4-vinylpyridine) block and pentadecylphenol, is formed inside the layers of the comb copolymer-like material in perpendicular orientation. IntroductionSelf-organization has received much attention recently as a means to achieve nanoscale structures in bulk materials and on surfaces. 1 In particular, block copolymers are able to form lamellar, cylindrical, spherical, and ...

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Section: Resultsmentioning

confidence: 99%

Orientation of Supramolecular Self-Organized Polymeric Nanostructures by Oscillatory Shear Flow

Mäkinen¹,

Ruokolainen²,

Ikkala³

et al. 2000

Macromolecules

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“…The crystal structure of alkyl chains in PEI(OA) x is different from that of complexes of linear poly(4-vinylpyridine) and pentadecylphenol reported by G. ten Brinke group. [1] Hexagonal and orthorhombic and triclinic packing of alkyl chains may occur in PEI(OA) x with 0.32 f x f 4.16 and the hexagonal packing still occurs at high content of OA. The ordered packing of alkyl chains is determined by the binding mode of OA in PEI(OA) x as well as the specimen-preparing process.…”

Section: Materials and Sample Preparationmentioning

confidence: 99%

“…[2,5] Recently G. ten Brinke group reported the crystallization and co-crystallization in the complexes of linear poly-(4-vinylpyridine) and pentadecylphenol (P4VP(PDP) x ). [1] They found that the crystal structure of alkyl chains in P4VP(PDP) x is essentially similar to that of comb-like copolymers. Little attention has been paid to the branched polymer-amphiphile complexes.…”

Section: Introductionmentioning

confidence: 98%

Crystalline Polymorphism of Alkyl Chains in Supramolecular Complexes of Polyethyleneimine with Octadecanoic Acid

Cai

Wang

et al. 2001

Macromol. Chem. Phys.

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The supramolecular complexes of branched polyethyleneimine and octadecanoic acid (PEI(OA)x) were prepared via interfacial reaction and homogeneous solution complexation. The binding mode and the crystalline polymorphism of alkyl chains in PEI(OA)x were investigated by FTIR spectroscopy and WAXS. There are three kinds of OA exist in the complexes, the first one is bound by primary amines through proton transferring, the second one associated with PEI through hydrogen‐bonding, and the third one free OA. The crystal structure of alkyl chains in PEI(OA)x is different from that of complexes of linear poly(4‐vinylpyridine) and pentadecylphenol reported by G. ten Brinke group.[1] Hexagonal and orthorhombic and triclinic packing of alkyl chains may occur in PEI(OA)x with 0.32 ⪇ x ⪇ 4.16 and the hexagonal packing still occurs at high content of OA. The ordered packing of alkyl chains is determined by the binding mode of OA in PEI(OA)x as well as the specimen‐preparing process.

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“…23 If P4VP(PDP) is a block of a diblock copolymer-based supramolecule such as PS-b-P4VP(PDP), where PS is polystyrene, the above-mentioned additional ordering principle is introduced. This results in characteristic two length scale hierarchically ordered structures such as lamellar-within-lamellar or, when the P4VP(PDP) blocks form the minority phase, lamellar-within-cylinders and lamellar-within-spheres.…”

Section: Introductionmentioning

confidence: 99%

Shear Alignment at Two Length Scales: Comb-Shaped Supramolecules Self-Organized as Cylinders-within-Lamellar Hierarchy

et al. 2003

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Large-amplitude oscillatory shear alignment of a hierarchically ordered system of combshaped supramolecules and the preparation of core-corona nanorods thereof are reported. The supramolecules consist of nearly symmetric polystyrene-b-poly(4-vinylpyridine) diblock copolymers with pentadecylphenol side chains hydrogen bonded to the poly(4-vinylpyridine) blocks. The polystyrene blocks, accounting for approximately 20% (w/w) of the supramolecules, are segregated in hexagonally ordered cylinders inside a matrix formed by the comb-shaped poly(4-vinylpyridine)-based blocks. The matrix further self-organizes in a layered structure below the order-disorder transition temperature of 70 °C. Thus, a cylinder-within-lamellar morphology is formed. Imposing shear leads to considerable alignment of both structures. The cylinders align along the shear flow with the (10) plane parallel with respect to the shear plane. The matrix layers align perpendicular to the cylinders, transverse to the flow. After elimination of pentadecylphenol by dialysis, crew-cut rods of 20-25 nm in diameter and 5-10 µm in length are obtained.

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Crystallization and Cocrystallization in Supramolecular Comb Copolymer-like Systems: Blends of Poly(4-vinylpyridine) and Pentadecylphenol

Cited by 73 publications

References 42 publications

Orientation of Supramolecular Self-Organized Polymeric Nanostructures by Oscillatory Shear Flow

Orientation of Supramolecular Self-Organized Polymeric Nanostructures by Oscillatory Shear Flow

Crystalline Polymorphism of Alkyl Chains in Supramolecular Complexes of Polyethyleneimine with Octadecanoic Acid

Shear Alignment at Two Length Scales: Comb-Shaped Supramolecules Self-Organized as Cylinders-within-Lamellar Hierarchy

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