Stimuli‐Responsive Y‐Shaped Polymer Brushes Based on Junction‐Point‐Reactive Block Copolymers

Tonhauser, Christoph; Golriz, Ali A.; Moers, Christian; Klein, Rebecca; Butt, Hans‐Jürgen; Frey, Holger

doi:10.1002/adma.201202105

Cited by 43 publications

(50 citation statements)

References 51 publications

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“…We were also interested in using P2VP 68 ‐FGE‐ b ‐PEO 390 for the functionalization of AuNPs. In that way, a hetero‐brush could be generated in analogy to poly(styrene)‐ block ‐poly(ethylene oxide) (PS‐ b ‐PEO) brushes on planar surfaces . Therefore, a maleimide‐functionalized tri‐thioacetate was synthesized (Figure S1, Supporting Information) and used for the synthesis of maleimide‐functionalized AuNPs .…”

Section: Resultsmentioning

confidence: 99%

Poly(2‐vinyl pyridine)‐block‐Poly(ethylene oxide) Featuring a Furan Group at the Block Junction—Synthesis and Functionalization

Rudolph

Barthel

Kretschmer

et al. 2014

Macromol. Rapid Commun.

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Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross-linkable nanostructured materials via Diels-Alder reactions. Here, the use of FGE for the mid-chain functionalization of a P2VP-b-PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68 -FGE-b-PEO390 , which can be subsequently addressed in Diels-Alder reactions using maleimide-functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero-grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68 -FGE-b-PEO390 , a powerful tool for selective functionalization reactions, including the modification of surfaces.

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Section: Resultsmentioning

confidence: 99%

Poly(2‐vinyl pyridine)‐block‐Poly(ethylene oxide) Featuring a Furan Group at the Block Junction—Synthesis and Functionalization

Rudolph

Barthel

Kretschmer

et al. 2014

Macromol. Rapid Commun.

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“…8−10 Even more, targeting the junction between the individual blocks of block copolymers allows for an exact positioning of specific functional groups and with such systems can, for instance, subsequently be used to attach the block copolymers to planar or nanoparticle surfaces as "Ybrushes". 11,12 If a desired functional group cannot be directly introduced during polymerization, subsequent postpolymerization modification can present an alternative. 13−15 Whereas postfunctionalization in general has been used since the early days of macromolecular chemistry, today's flexibility and functional group tolerance in polymer synthesis open up entirely new avenues for exploiting highly efficient and orthogonal chemistries with and along polymer chains.…”

Section: ■ State-of-the-art: Selected Examplesmentioning

confidence: 99%

Polymer Interfaces: Synthetic Strategies Enabling Functionality, Adaptivity, and Spatial Control

2016

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Polymer interfaces are ubiquitous in Nature and technology. Equipping artificial polymer-based interfaces with highly defined functions requires advanced macromolecular chemistry and powerful chemical tools. In this Perspective, we explore the nature of anisotropici.e., spatially resolved polymer interfaces prepared via top-down and bottom-up approaches with selected examples from the recent literature. These range from self-assembly driven systems based on single polymer chains and block copolymers to lithographic encoding able to span wide spatial dimensions of patterning. Based thereon, we formulate the in our opinion required advances in polymer chemistry that will contribute significantly to preparing the next generation of structured interfaces. Among others, this includes the to-date limited orthogonality of parallelly executed ligation reactions as well as limits in λ-orthogonally addressable pericyclic ligation chemistry. Finally, we propose some long-term visions for not yet existinghowever currently soughttechnology that could drive interactive and adaptive polymer interface construction to new levels. These include the spatially resolved encoding of interfaces with molecular precision and the introduction of programmable properties to interfaces of varying shape and chemical complexity.

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“…The termination by glycidyl ethers with protected hydroxyl groups was used by Hillmyer et al and Wang and Huang in the synthesis of miktoarm star polymers. Tonhauser et al intensively studied the termination reaction using a broad range of different glycidyl ethers with versatile functionalities, as also summarized in a review . This strategy enables synthesis of block and miktoarm copolymers using ethylene oxide and other monomers …”

Section: Introductionmentioning

confidence: 99%

“…Alkoxysilanes, acyl clorides, but also catechols may be suitable functionalities depending on the chosen surface. The attachment of surface reactive silyl groups can be achieved by hydrosilylation reactions of double bonds with the appropriate silanes . Theoretical and quantitative descriptions of tethered polymer chains were published by de Gennes .…”

Section: Introductionmentioning

confidence: 99%

Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

Leibig

Messerle

Johann

et al. 2019

Journal of Polymer Science

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Well‐defined polystyrene homopolymers with surface‐adhesive triethoxysilyl end group were synthesized via living carbanionic polymerization, epoxide end‐functionalization and subsequent hydrosilylation with triethoxysilane. Grafting‐to performance of polymers with various molecular weight (Mn = 3000–14,000 g mol−1) to a silicon surface was examined in dependence of reaction time, polymer concentration, solvent and number of alkoxysilyl end groups. Crosslinkable polymers for surface modification were synthesized by statistical carbanionic copolymerization of 4‐vinylbenzocyclobutene (4‐VBCB) and styrene, followed by epoxide end‐functionalization and triethoxysilane modification (Mn = 4000–14,000 g mol−1). The copolymers were characterized by 1H‐NMR, THF‐SEC, and matrix‐assisted laser desorption and ionization time‐of‐flight mass spectrometry. In situ 1H‐NMR kinetic studies in cyclohexane‐d12 provided information regarding the monomer gradient in the polymer chains, with styrene being the more reactive monomer (rs = 2.75, r4‐VBCB = 0.23). Thin polymer films on silicon wafers were prepared by grafting‐to surface modification under conditions derived for the polystyrene homopolymer. The traceless, thermally induced crosslinking reaction of the benzocyclobutene units was studied by DSC in bulk as well as in 3–6 nm thick polymer films. Crosslinked films were analyzed by atomic force microscopy, ellipsometry, and nanoindentation, showing smooth polymer films with an increased modulus. © 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 181–192

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Stimuli‐Responsive Y‐Shaped Polymer Brushes Based on Junction‐Point‐Reactive Block Copolymers

Cited by 43 publications

References 51 publications

Poly(2‐vinyl pyridine)‐block‐Poly(ethylene oxide) Featuring a Furan Group at the Block Junction—Synthesis and Functionalization

Poly(2‐vinyl pyridine)‐block‐Poly(ethylene oxide) Featuring a Furan Group at the Block Junction—Synthesis and Functionalization

Polymer Interfaces: Synthetic Strategies Enabling Functionality, Adaptivity, and Spatial Control

Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

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