Studies on Comb-like Polymers. 2. Poly(octadecylethylene oxide)

Andruzzi, F.; Lupinacci, Domenico; Magagnini, Pier Luigi

doi:10.1021/ma60073a003

Cited by 25 publications

(10 citation statements)

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“…Changes in the values of d B in P4VP_CnBr and P4VP‐ r ‐PI_CnBr series, for a given number of carbons on the pendant side chain, is due to the difference in the mole fractions of the pendant side‐chain monomer units in the quaternized homopolymer and random copolymer. The larger the fraction of the pendant side‐chain unit, the greater the d B . A characteristic feature of d B is its linear correlation with number of carbons as can be observed in the P4VP_CnBr series.…”

Section: Resultsmentioning

confidence: 92%

“…Upon quaternization, the VDW spacing decreased from its value in the pristine polymer. This indicates tighter packing of polymer chains . Given that a decrease in VDW spacing have not been observed in noncharged, comb‐shaped polymers, this decrease in VDW spacing from the unquaternized (P4VP) to the quaternized polymer series (P4VP_CnBr) may have resulted from the introduction of charges.…”

Section: Resultsmentioning

confidence: 98%

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Pendant side‐chain sterics against electrostatic forces: Influencing short‐range ordering in random polyelectrolytes

Nwosu

Coughlin

2019

J Polym Sci B Polym Phys

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The length of pendant side chains in charged, random, comb-shaped polymers dictates the nature of their short-range ordering. Random copolymers, and terpolymer, of 4-vinylpyridine (4VP), styrene, and isoprene were synthesized and subsequently fully quaternized with 1-alkylbromides having varying number of carbons on the alkyl group ranging from 2 to 8. Evaluation by wide angle X-ray scattering revealed that dipole-dipole attraction facilitates the formation of ionomer cluster morphology in samples with two carbons on the pendant side chain, whereas for samples with four or more carbons on the pendant side chains, side-chain sterics was dominant resulting in periodic backbone spacing.Copolymers with isoprene, having flexible backbones, favor the formation of ionomer cluster morphology while styrene copolymers having rigid backbones disfavor the formation of ionomer clusters. An "in-line" dipole model was developed to predict the separation distance at which both ionomer cluster and backbonebackbone morphologies could coexist.Another short-range ordering that can be observed in WAXS for random polyelectrolytes is the periodic spacing between adjacent polymer backbones. Polyelectrolytes with pendant side chains, for example, poly(1-n-alkyl-3-vinylimidazoliumbromide), show this kind of morphology. 18 The characteristic spacing obtained from the backbone-backbone morphology has similar dimensions to the cluster-cluster spacing present in the ionomer cluster morphology. However, this short-range order is a consequence of the separation between adjacent polymer backbones. The length of the pendant side chains dictates the spacing between adjacent backbones by sterically repelling other pendant side chains on adjacent polymer backbones. 19 The spacing between adjacent backbones, the so-called backbone-backbone spacing, increases with increasing length of the pendant side chains Additional Supporting Information may be found in the online version of this article.

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Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 98%

Pendant side‐chain sterics against electrostatic forces: Influencing short‐range ordering in random polyelectrolytes

Nwosu

Coughlin

2019

J Polym Sci B Polym Phys

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“…Between different polymerizations the individual monomers were stored under Ar atmosphere. Polymerization (Scheme ) was carried out in bulk under slight argon overpresssure with a acetylacetone/water/AlEt 3 catalyst known to be able to produce high molecular weight polymers from epoxides. − Similar catalyst systems like dmg/Ni/AlEt 3 which were used to polymerize, e.g., octadecylethylene oxide, failed with our monomers. Anionic polymerization using sodium naphtalide or potassium alcoholates produced only oligomers with a degree of polymerization between three and five.…”

Section: Methodsmentioning

confidence: 99%

New Nonionic Head Type Polysoaps: A Way to Reversed Liquid Crystalline Phases

Schwarzwälder

Meier

1997

Macromolecules

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The preparation and characterization of new oligooxyethylene alkyl ether surfactants and their corresponding polysoaps are described. The monomers are epoxy-terminated at their hydrophilic end, which allows an AcAc/H2O/AlEt3 catalyzed polymerization to high molecular weight polymers with a water-soluble backbone. The behavior of the monomers and polymers in water and organic solvents is characterized by static and dynamic light scattering. The binary phase diagrams of these surfactants with water display broad lyotropic liquid crystalline phases. The identical chemical constitution of the polymeric backbone and the hydrophilic head groups of the surfactant units enables the formation of reversed aggregates. As a consequence, for the first time, a reversed hexagonal phase in side-chain polymeric surfactants is observed.

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“…The appearance of a new reflection certainly reflected the development of new ordering in the layers. Side‐chain polymers having alkyl side chains without sulfone groups had a sharp reflection at ∼4.17 Å when the side chains were long enough to be crystallized in a hexagonal fashion 20–23. Thus, this reflection suggested that the structure with sulfone groups in the side chain was different from that having only alkyl side chains.…”

Section: Resultsmentioning

confidence: 99%

Effects of the alkyl side‐chain length on the structures of poly[oxy(N‐alkylsulfonylmethyl)ethylene]s

Park¹,

Farmer²,

Lee³

2004

J Polym Sci B Polym Phys

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The structures of poly[oxy(N‐alkylsulfonylmethyl)ethylene]s (ASE‐Ns) were examined with X‐ray, IR, DSC, and polarized optical microscopy. The structures of ASE‐Ns were strongly dependent on the alkyl side‐chain length. ASE‐2 and ASE‐3, the shortest ones, were amorphous materials. ASE‐4 and ASE‐5 showed nematic characteristics. ASE‐6–ASE‐12 had smectic A structures. ASE‐14 and ASE‐16 could be labeled as more ordered structures higher than smectic A (probably smectic B or smectic E). The d‐spacings of the first small‐angle reflections were double the most extended side‐chain length and linearly increased with a slope of 2.50 Å per methylene unit, regardless of the structural phases. The maintenance of the double‐layered structure in all ASE‐Ns may be due to the strong dipole–dipole interactions at both sides of the layers against the main chain for all amorphous, nematic, and smectic phases of ASE‐Ns. The double‐layered structure was maintained above the isotropic temperature, indicating that dipole–dipole interactions were not destroyed although the alkyl side chains melted during the isotropic transition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1868–1874, 2004

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Studies on Comb-like Polymers. 2. Poly(octadecylethylene oxide)

Cited by 25 publications

References 0 publications

Pendant side‐chain sterics against electrostatic forces: Influencing short‐range ordering in random polyelectrolytes

Pendant side‐chain sterics against electrostatic forces: Influencing short‐range ordering in random polyelectrolytes

New Nonionic Head Type Polysoaps: A Way to Reversed Liquid Crystalline Phases

Effects of the alkyl side‐chain length on the structures of poly[oxy(N‐alkylsulfonylmethyl)ethylene]s

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