Highly Asymmetric Phase Diagram of a Poly(1,2‐octylene oxide)–Poly(ethylene oxide) Diblock Copolymer System Comprising a Brush‐Like Poly(1,2‐octylene oxide) Block

Hamley, Ian W.; O'Driscoll, Ben; Lötze, Gudrun; Moulton, C. M.; Allgaier, J. B.; Frielinghaus, Henrich

doi:10.1002/marc.200900474

Cited by 10 publications

(20 citation statements)

References 22 publications

(24 reference statements)

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“…Hexene oxide and higher α-olefin oxide homologues, however, are solely commercialized as fine chemicals. Therefore, poly(alkylene oxide)s beyond poly(butylene oxide) are of little industrial interest, and the majority of studies are performed in academia, mainly to explore modern polymerization strategies, while only limited attention has been devoted to the examination of their materials properties so far. − …”

Section: Poly(alkylene Oxide) Structures: Innovative Polyether Struct...mentioning

confidence: 99%

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

et al. 2015

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The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a "polyether universe" may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.

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Section: Poly(alkylene Oxide) Structures: Innovative Polyether Struct...mentioning

confidence: 99%

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

et al. 2015

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“…Theoretically, asymmetric chain conformations of the two blocks can result in asymmetry of the BCP phase diagrams and may stabilize metastable states . A highly asymmetric phase diagram was experimentally observed in poly(1,2-octylene oxide)- block -poly(ethylene oxide) (POO- b -PEO), a similar coil-brush BCP with strong conformational asymmetry . In that system, the lamellar phase was observed at f POO < 0.5, and structures with curvatures were more widely observed when POO (with eight carbon alkyl tails) was the majority block.…”

Section: Resultsmentioning

confidence: 94%

“…36 A highly asymmetric phase diagram was experimentally observed in poly(1,2-octylene oxide)-block-poly(ethylene oxide) (POO-b-PEO), a similar coil-brush BCP with strong conformational asymmetry. 29 In that system, the lamellar phase was observed at f POO < 0.5, and structures with curvatures were more widely observed when POO (with eight carbon alkyl tails) was the majority block. In the previously reported coil-comb PS-b-P4VP(PDP) supramolecular system, lamellar morphology was observed at 0.3 < f comb < 0.53, 28 and the comb block prefers to be on the convex side of a curved structure.…”

Section: ∫ ∫mentioning

confidence: 84%

“…The effect of the long alkyl tail of LA in the BCP resembles the long alkyl tail of PDP small molecules in the supramolecular system for NP assembly . The alkyl tail of LA can also extend the backbone of the RCP block to a comb conformation . A brush-like conformation may lower the polymer entanglement. , MA was added to modulate the density of the long alkyl side chain in the RCP block.…”

Section: Resultsmentioning

confidence: 99%

“…11 The alkyl tail of LA can also extend the backbone of the RCP block to a comb conformation. 29 A brush-like conformation may lower the polymer entanglement. 30,31 MA was added to modulate the density of the long alkyl side chain in the RCP block.…”

Section: ∫ ∫mentioning

confidence: 99%

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Nanocomposites Based on Coil-Comb Diblock Copolymers

et al. 2021

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Polymer chain architecture is an important factor determining the phase behavior of nanoparticle (NP) assembly in polymer matrices. Block copolymers (BCPs) containing a random copolymer (RCP) block present a convenient variation on traditional BCPs to tune the interaction parameters between the polymer blocks and the nanofillers as well as to evaluate the effect of chain architecture on the NP arrangements within BCP microdomains. Here, we synthesized BCPs with a coil polystyrene (PS) block and a comb RCP block through reversible addition-fragmentation chain transfer polymerization. The RCP block consists of methyl-and 1 lauryl acrylates, the latter which confers a long-chain alkyl moiety to favorably interact with alkyl-passivated NPs. BCPs showing lamellar, cylindrical, and mixed morphologies were obtained by varying the volume fractions of the RCP block (f RCP ). In comparison to coil-coil BCP, the coil-comb BCPs show highly asymmetric phase behavior with respect to f RCP , where lamellar morphologies were observed at f RCP from 0.31 to 0.51. NPs in the size of 4-5 nm were successfully incorporated in the RCP block of the BCPs with periodicities of 30-60 nm. An order-to-order phase transition from lamellae to PS cylinders was observed after the addition of only 1-2 vol% of 5 nm NPs into the BCP with a periodicity of 25 nm and f RCP of 0.51. Selfconsistent field theory-density functional theory simulations qualitatively described the observed morphologies and phase transitions in the nanocomposites. The current study presents a platform to fabricate nanocomposites with NP assemblies in coil-comb BCPs that contain a random copolymer block, and provides insight into how polymer chain architecture can affect the phase behavior of BCPs and nanocomposites.

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Role of the segment distribution in the microphase separation of acrylic diblock and triblock terpolymers

Bergman¹,

Cochran²,

Heinen³

2014

Polymer

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Highly Asymmetric Phase Diagram of a Poly(1,2‐octylene oxide)–Poly(ethylene oxide) Diblock Copolymer System Comprising a Brush‐Like Poly(1,2‐octylene oxide) Block

Cited by 10 publications

References 22 publications

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Nanocomposites Based on Coil-Comb Diblock Copolymers

Role of the segment distribution in the microphase separation of acrylic diblock and triblock terpolymers

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