Structure Formation of Metallopolymer-Grafted Block Copolymers

Rüttiger, Christian; Appold, Michael; Didzoleit, Haiko; Eils, Adjana; Dietz, Christian; Stark, Robert W.; Stühn, Bernd; Gallei, Markus

doi:10.1021/acs.macromol.6b00577

Cited by 25 publications

(37 citation statements)

References 84 publications

(110 reference statements)

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“…hint for successful ferrocene-modification, the residue as obtained after treatment at 600 °C turned out to be magnetic, which is typical for ferrocene-containing polymers after ceramization. [54,55] This finding is in good agreement with theoretical calculations for the iron content of the block copolymers. For comparison, a TGA of PFcMA ( Figure S2, Supplementary Materials) is given.…”

Section: Functionalization Of Phema-containing Block Copolymers With supporting

confidence: 88%

“…This resulted in a smaller hydrodynamic volume and therefore an apparent smaller molecular weight of the polymer itself was observed. [17,[52][53][54] Nevertheless, molar masses can easily be obtained and calculated by 1 H NMR spectroscopy and the results are additionally compiled in Table 2. It has to be mentioned, that a second less intensive distribution, which is shifted to higher molar masses, could be observed by SEC measurements.…”

Section: Functionalization Of Phema-containing Block Copolymers With mentioning

confidence: 99%

“…This is due to the fact that the ferrocene moieties induced a decreased solution capability for the block copolymers in DMF/LiCl. This resulted in a smaller hydrodynamic volume and therefore an apparent smaller molecular weight of the polymer itself was observed [17,[52][53][54]. Nevertheless, molar masses can easily be obtained and calculated by 1 H NMR spectroscopy and the results are additionally compiled in Table 2.…”

Section: Functionalization Of Phema-containing Block Copolymers With mentioning

confidence: 99%

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Ferrocene-Modified Block Copolymers for the Preparation of Smart Porous Membranes

et al. 2017

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Abstract:The design of artificially generated channels featuring distinct remote-switchable functionalities is of critical importance for separation, transport control, and water filtration applications. Here, we focus on the preparation of block copolymers (BCPs) consisting of polystyrene-block-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA) having molar masses in the range of 91 to 124 kg mol −1 with a PHEMA content of 13 to 21 mol %. The BCPs can be conveniently functionalized with redox-active ferrocene moieties by a postmodification protocol for the hydrophilic PHEMA segments. Up to 66 mol % of the hydroxyl functionalities can be efficiently modified with the reversibly redox-responsive units. For the first time, the ferrocene-containing BCPs are shown to form nanoporous integral asymmetric membranes by self-assembly and application of the non-solvent-induced phase separation (SNIPS) process. Open porous structures are evidenced by scanning electron microscopy (SEM) and water flux measurements, while efficient redox-switching capabilities are investigated after chemical oxidation of the ferrocene moieties. As a result, the porous membranes reveal a tremendously increased polarity after oxidation as reflected by contact angle measurements. Additionally, the initial water flux of the ferrocene-containing membranes decreased after oxidizing the ferrocene moieties because of oxidation-induced pore swelling of the membrane.

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Section: Functionalization Of Phema-containing Block Copolymers With supporting

confidence: 88%

Section: Functionalization Of Phema-containing Block Copolymers With mentioning

confidence: 99%

Section: Functionalization Of Phema-containing Block Copolymers With mentioning

confidence: 99%

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Ferrocene-Modified Block Copolymers for the Preparation of Smart Porous Membranes

et al. 2017

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“…Controlled and living polymerization strategies are promising routes for the preparation of functional grafted polymers . Especially anionic polymerization, which provides access to well‐defined graft and block copolymers . Zhang et al prepared cylindrical polymer brushes featuring dendritic side chains via an iterative anionic polymerization protocol for polyisoprene‐ block ‐polystyrene (PI‐ b ‐PS) .…”

Section: Introductionmentioning

confidence: 99%

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Appold

Rüttiger

Kuttich

et al. 2017

Macro Chemistry & Physics

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Common stimuli include temperature, pH, light, redox reagents, and electrical fields. [16][17][18][19][20][21][22][23] Block copolymers featuring polyvinylpyridine (PVP) segments have attracted enormous attention due to their ability to undergo microphase separation, metal ion complexation, nanoparticle complexation, as well as participate in hydrogen bonding. [24] Stamm and co-workers have reported extensively on poly(styrene-block-(4-vinylpyridine)) (PS-b-P4VP) as a system. For example, they have reported on the influence of hydrogen bonding for poly(styrene-block-(4-vinylpyridine)) (PS-b-P4VP) for microphase separation, [25] the use of sacrificial PS-b-P4VP networks as carbon precursors, [26] the use of PS-b-P4VP as polymer templates for the preparation of highly ordered arrays of metallic nanodots, [27] and the preparation of P4VP-based block copolymers for helically arranged nanoparticle complexation in cylindrical domains. [28] Besides their structure formation capabilities, PVPs have been used as pH-responsive homopolymers, or as reversibly addressable segments in smart block copolymer architectures featuring protonated pyridinium moieties. [16] For example, Li et al. reported on the pH responsiveness of Au@PVP particles, and their application as pHresponsive bimetallic catalysts. [29] Furthermore, responsive P4VP-based cross-linked films have been used as pH sensors and as surfaces with controllable surface wettability. [30] The group of Eisenberg has also reported on the morphological changes in PS-b-P4VP micelles as a function of pH range. [31] Additionally, multi-stimuli-responsive block copolymers featuring a poly(2-vinylpyridine) (P2VP)-containing block segment were investigated in thin films, [32] as micelles in water, [33,34] and as smart nanocapsules. The latter have been advantageously used for the triggered release of different payloads from the capsules' interior. [21,35] As another impressive example, PSb-P4VP was the first polymer under investigation for creating integral asymmetric membranes with highly uniform pore sizes. [36] The complexation of the P4VP block segments with copper(II) ions was utilized for a stabilization of the PS-b-P4VP micelles in solution and hence a high reproducibility of uniform pore structures was achieved. [37,38] Besides copper(II) salts, other transition metals like nickel(II), cobalt(II), and iron(II) are also capable of influencing the self-organization of Anionic PolymerizationsFunctional block copolymers are a highly relevant material platform for many potential applications in fields of nanolithography, drug delivery, and separation technologies. Here, poly(2-vinylpyridine) (P2VP)-grafted diblock copolymers consisting of polystyrene-block-polyisoprene (PS-b-PI) backbone are synthesized via an iterative anionic grafting-to polymerization strategy. P2VP macro anions having molar masses of 1.1, 3.6, and 9.9 kDa are grafted to PS-b-PI block copolymers featuring 37 mol% 1,2-polyisoprene moieties. Prior to the grafting-to strategy, the PS-b-PI is subjected to pl...

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“…demonstrated the hydrosilylation of PS‐ b ‐PI with hydrido‐heptacyclopentyl substituted silsesquioxane (POSS) for the preparation of hierarchically ordered hybrid structures . Additionally, poly(2‐vinylpyridine) (P2VP), polyvinylferrocene (PVFc), and polyferrocenyldimethylsilane (PFS) were successfully grafted to PS‐ b ‐PI by an iterative all‐anionic polymerization strategy . Very recently, the Hirao group reported on the preparation and analysis of precisely grafted PS‐ b ‐PI by taking advantage of diphenylethylene (DPE) functional groups .…”

Section: Introductionmentioning

confidence: 99%

Anionic Grafting to Strategies for Functional Polymethacrylates: Convenient Preparation of Stimuli‐Responsive Block Copolymer Architectures

Appold

Bareuther

Gallei

2019

Macro Chemistry & Physics

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Functional block copolymers (BCP) are promising candidates for many important applications in fields of separations technologies, drug delivery, or (nano)lithography. Here, a universal strategy is described for the preparation of functional poly(methacrylate)s grafted (PMA) to polystyrene‐block‐polyisoprene (PS‐b‐PI) BCPs via a convenient postmodification strategy. PS‐b‐PIs are functionalized by means of hydrosilylation protocols for the introduction of chlorosilane moieties. Subsequent anionic grafting‐to polymerization of different functional PMA macro anions leads to grafted BCP. Various functional and non‐functional homopolymers, that is, poly(di(ethylene glycol) methyl ether methacrylate), poly(methacrylic acid), and poly(3‐methacryloxypropyl)heptaisobutyl‐T8‐silsesquioxane as well as poly(methyl methacrylate), poly(n‐butyl methacrylate), poly(iso‐propyl methacrylate), poly(tert‐butyl methacrylate), and poly(2‐hydroxy ethyl methacrylate) are block‐selectively incorporated into the PI segment. Applied grafting strategies for the non‐functional PMA derivatives, which feature different sizes of the alkyl substituent, reveal a strong influence on the grafting‐to efficiency. The grafted BCP architectures are capable of undergoing microphase separation in the bulk state, while the resulting morphology is significantly influenced by the introduction of PMA segments as shown by transmission electron microscopy measurements. Additionally, the structure formation and pH‐switching capability of the poly(methacrylic acid)‐grafted BCP is studied by dynamic light scattering, proving the feasibility for the herein investigated synthesis strategy.

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Structure Formation of Metallopolymer-Grafted Block Copolymers

Cited by 25 publications

References 84 publications

Ferrocene-Modified Block Copolymers for the Preparation of Smart Porous Membranes

Ferrocene-Modified Block Copolymers for the Preparation of Smart Porous Membranes

Polyvinylpyridine‐Grafted Block Copolymers by an Iterative All‐Anionic Polymerization Strategy

Anionic Grafting to Strategies for Functional Polymethacrylates: Convenient Preparation of Stimuli‐Responsive Block Copolymer Architectures

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