Living Coupling Reaction in Living Cationic Polymerization. 2. Synthesis and Characterization of Amphiphilic A2B2Star−Block Copolymer:  Poly[bis(isobutylene)-star-bis(methyl vinyl ether)]

Bae, Young Cheol; Faust, Rudolf

doi:10.1021/ma971715y

Cited by 73 publications

(55 citation statements)

References 30 publications

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“…The vesicular aggregates are considered to be a metastable, not fully equilibrated species, which are, however, stable over months. This observation highlights the great impact of the metastability of self-assembled structures of block copolymers, which are very flexible (the glass transition temperature of PIB is about ±70 C) [22,23] but also very hydrophobic. Hence, special care in observing proper experimental conditions seems to be essential when dealing with ultrahydrophobic systems.…”

mentioning

confidence: 82%

“…Hydroboration of the terminal double bonds with 9-borabicyclo[3.3.1]nonane (9-BBN, 0.5 M in tetrahydrofuran (THF), Aldrich) and subsequent oxidative cleavage of the carbon±boron bonds with alkaline H 2 O 2 resulted in PIB-OH [22,23]. In order to remove cyclooctane-1,5-diol, a by-product formed during the treatment with 9-BBN, the crude product was dissolved in hexane and precipitated three times by the drop-by-drop addition of methanol under vigorous stirring.…”

Section: Methodsmentioning

confidence: 99%

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Polyisobutylene‐block‐Poly(ethylene oxide) for Robust Templating of Highly Ordered Mesoporous Materials

Groenewolt¹,

Brezesinski²,

Schlaad³

et al. 2005

Advanced Materials

111

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Nanocasting, the three-dimensional transformation of selfassembled organic nanostructures into hollow inorganic replicas while preserving fine structural details, has recently turned out to be a versatile tool for the synthesis of porous media with new pore topologies. In the classical synthesis of mesoporous inorganic structures, [1,2] a route called ªsynergistic precipitationº, the order present in the starting material is not maintained in the product. Nanocasting, or the ªtrue lyotropic liquid-crystal approachº, [3±7] as introduced by Attard and Göltner, is different. Here, the starting high-concentration template phase is solidified by chemical-gelation reactions. In early work, it was shown that this technique offers the possibility of making a 1:1 imprint, or negative copy, of organic mesophases. X-ray scattering measurements performed throughout the process showed that the solidified hybrid inherits all the structural features of the original matrix. In order to enable nanocasting, the cast structure must be compatible with both the liquid-precursor phase as well as the final solidified replica. If this is not the case, the enormous interfaces involved (up to 1000 m 2 g ±1 ) will add up to unfavorable interface energies and the replication will break down. This is why most work is performed with sol±gel silica, [8] for which the surface chemistry is easy to address. Handling surface energies via poly(ethylene oxide) (PEO) tails, first demonstrated by Pinnavaia and co-workers, [9±11] is presumably the most frequently applied tool. Here, the formation of hydrogen bridges between the silicic acid framework and the ether oxygen atoms of the PEO chains stabilize the interface. The gelation of the SiO 2 network is preferentially performed at about pH 2, close to the isoelectric point of silicic acid. More recent work on the generation of mesoporous films of other crystalline inorganic materials by evaporation-induced self-assembly (EISA) [12] indicates that a second property of the templates severely influences the quality of the formed mesoporous films. This is the ªrobustnessº of the self-assembly process against processing conditions, such as temperature, alcohol content, or moisture level in the gaseous headspace.[13±15] Ozin and co-workers were able to produce mesoporous crystalline titania films on the basis of the commonly used pluronics poly(ethylene oxide)±poly(propylene oxide) block copolymers, but they relied on the specific replacement of ethanol by the more hydrophobic butanol in their recipes. [16,17] Already, the switch from the only moderately hydrophobic poly(propylene oxide) to the more hydrophobic poly(ethylene-co-butylene) significantly improved the process and allowed the generation of more complex mesoporous materials, such as titanium oxides [18] or even perovskites, [19] under a wider range of conditions and with improved structural quality. The scope of the present work is therefore to synthesize and explore the applicability of a template with extreme hydrophobic contrast, compos...

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confidence: 82%

Section: Methodsmentioning

confidence: 99%

Polyisobutylene‐block‐Poly(ethylene oxide) for Robust Templating of Highly Ordered Mesoporous Materials

Groenewolt¹,

Brezesinski²,

Schlaad³

et al. 2005

Advanced Materials

111

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“…163 The synthetic strategy involved the reaction of 2,2-bis[4-(1-phenylethenyl)phenyl]propane and 2,2-bis[4-(1-tolylethenyl)phenyl]propane with living PIB, resulting in a di-cationic in-chain initiator. This initiator was used for the polymerization of MVE to give the (PIB) 2 (PMVE) 2 miktoarm copolymer.…”

Section: Scheme 25mentioning

confidence: 99%

Ionic Polymerization

Pitsikalis

2013

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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“…As a proof of the concept, an amphiphilic A 2 B 2 star-block copolymer (A=PIB and B=PMeVE) has been prepared by the living coupling reaction of living PIB followed by the chain-ramification polymerization of MeVE at the junction of the living coupled PIB as shown in Scheme 10 [85]. Architecture/ property studies were carried out by comparing the micellar properties of star-block copolymer ((IB 45 ) 2 -b-(MeVE 170 ) 2 ) and the corresponding linear diblock analogues with same total molecular weight and composition (IB 90 -b-MeVE 340 ) or with same segmental lengths (IB 45 -b-MeVE 170 ).…”

Section: Synthesis Of Hetero-arm Star-block Copolymers Using Bis-dpe mentioning

confidence: 99%

Synthesis of Polyisobutylene-Based Block Copolymers with Precisely Controlled Architecture by Living Cationic Polymerization

Kwon

Faust

2004

New Synthetic Methods

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During the last two decades we have witnessed the discovery and development of living cationic polymerization. As a result of persistent growth in this field, today living cationic polymerization is an equal counterpart of anionic living polymerization although the latter has a considerably longer history. Living cationic polymerization is an indispensable tool for the preparation of a wide variety of homo-, block-, graft-and functional polymers. This chapter reviews recent efforts in cationic macromolecular engineering with emphasis on fundamental concepts and advanced technologies for polyisobutylene block copolymer synthesis. For block copolymer synthesis by the simple sequential monomer addition technique rationalization is given for the selection of polymerization conditions and monomer addition order. The application of non-(homo)polymerizable monomers such as 1,1-diarylethylenes and furan analogues, coupled with changes in the synthetic approaches for various block copolymer architectures, is described in terms of three categories; capping, coupling, and living coupling reactions. These appear to be versatile synthetic tools for numerous linear di-and triblock copolymers, and block copolymers with non-linear architectures. Finally, current developments in the combination of different polymerization mechanisms are illustrated.

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Living Coupling Reaction in Living Cationic Polymerization. 2. Synthesis and Characterization of Amphiphilic A₂B₂Star−Block Copolymer: Poly[bis(isobutylene)-star-bis(methyl vinyl ether)]

Cited by 73 publications

References 30 publications

Polyisobutylene‐block‐Poly(ethylene oxide) for Robust Templating of Highly Ordered Mesoporous Materials

Polyisobutylene‐block‐Poly(ethylene oxide) for Robust Templating of Highly Ordered Mesoporous Materials

Ionic Polymerization

Synthesis of Polyisobutylene-Based Block Copolymers with Precisely Controlled Architecture by Living Cationic Polymerization

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