An All‐ROMP Route to Graft Copolymers

Hilf, Stefan; Kilbinger, Andreas F. M.

doi:10.1002/marc.200700083

Cited by 53 publications

(48 citation statements)

References 29 publications

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“…used this concept in the ROMP of norbornenes, synthesizing diblock copolymers whereby dioxepins were used to form the second block that was then sacrificed . This method showed high efficiency and further reaction of the alcohol with a range of functional moieties was demonstrated, indicating the versatility of this method as a single functionality insertion approach . This concept was further developed using vinyl lactones, dithiepins, and diazaphosphepins .…”

Section: Introductionmentioning

confidence: 99%

Degradable precision polynorbornenes via ring‐opening metathesis polymerization

Moatsou

Nagarkar

Kilbinger

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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ABSTRACT:In an attempt to introduce monomer sequence control in a growing polynorbornene via ring-opening metathesis polymerization, we employ dioxepins to efficiently determine the location of the monomers on the macromolecule backbone. Owing to the acid-labile acetal group, dioxepins allow scission of the polymer at the point of the dioxepin insertion and thus provide an indirect way to determine the monomer location. Additionally, dioxepins are used as spacers in the synthesis of multiblock polynorbornenes that are readily cleavable to afford the individual polynorbornene blocks.

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Section: Introductionmentioning

confidence: 99%

Degradable precision polynorbornenes via ring‐opening metathesis polymerization

Moatsou

Nagarkar

Kilbinger

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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“…ROMP was the only polymerization technique required for the synthesis of this macromolecular architecture. [17] for example size exclusion chromatograms before and after cleavage of the sacrificial block. However, it is a two-step process, requires liberation of the macroscopically protected end-functionality and is certainly not 'atom-economic'.…”

Section: General Methods Of Endfunctionalizationmentioning

confidence: 99%

Developing New Methods for the Mono-end Functionalization of Living Ring Opening Metathesis Polymers

Kilbinger¹

2012

Chimia

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In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer–protein conjugates are two examples for the former and polymer-?-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

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“…Generally, there are three methods to synthesize graft polymers: (1) the “grafting from” method, where comonomers can propagate from initiation sites that are incorporated onto the polymer backbone ( Scheme a ); (2) the “grafting onto” method, where the backbone is endowed with randomly distributed functional groups that are capable of coupling with end‐functionalized graft chains (Scheme b); (3) the “grafting through” method, where macromonomers with polymerizable terminal group are copolymerized with comonomers, and the branches are “sewn” into the main chain (Scheme c).…”

Section: Precise Synthesize Of Multigraft Copolymers By Iterative Methodsmentioning

confidence: 99%

“…Generally, there are three methods to synthesize graft polymers: [22] (1) the "grafting from" method, [23][24][25][26][27] where comonomers can propagate from initiation sites that are incorporated onto the polymer backbone (Scheme 1a); (2) the "grafting onto" method, [28][29][30] where the backbone is endowed with randomly distributed functional groups that are capable of coupling with end-functionalized graft chains (Scheme 1b); (3) the "grafting through" method, [31][32][33] where macromonomers with polymerizable terminal group are copolymerized with comonomers, and the branches are "sewn" into the main chain (Scheme 1c). Much progress have been made in synthesizing graft copolymers by living/controlled polymerization techniques, such as reversible addition-fragmentation chain transfer polymerization (RAFT), [34][35][36][37] atom transfer radical polymerization (ATRP), [27,34,38,39] ring-opening metathesis polymerization (ROMP), [33,[40][41][42] and living anionic polymerization, [43][44][45] using grafting from/onto/through methods. However, graft copolymers prepared by these methods generally have side chains randomly grafted along the backbone.…”

Section: Precise Synthesize Of Multigraft Copolymers By Iterative Methodsmentioning

confidence: 99%

Design and Synthesis of Multigraft Copolymer Thermoplastic Elastomers: Superelastomers

Wang

et al. 2017

Macro Chemistry & Physics

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worldwide elastomer market, as sealants, coatings, adhesives, sporting good components, automotive parts, footwear, and as biomedical materials. [1] Prepared by living anionic polymerization, styrenic thermoplastic elastomers (S-TPEs), including polystyrene-blockpolyisoprene-block-polystyrene (SIS) and polystyrene-block-polybutadiene-blockpolystyrene (SBS), were first developed by Holden and Millkvich in the early 1960s and have since then become widely used in our daily life. [2,3] The exceptional mechanical properties of S-TPEs are attributed to the microphase separation between the two chemically incompati ble domains where hard polystyrene (PS) domains serve as physical cross-links for the soft polybutadiene (PB) or polyisoprene (PI) matrix. Mechani cal properties, such as tensile strength, Young's modulus, and elasticity, are tunable based on volume fractions of hard and soft domains. One limitation of S-TPEs is the restricted upper service temperature (UST), which is limited by the glass transition temperature (T g ) of polystyrene (T g ≈ 100 °C). When the service temperature is approaching 100 °C, softening of PS domains disrupts the physical cross-links, leading to a sharp drop of storage modulus. Numerous studies have been carried to increase the UST of S-TPEs by either replacing polystyrene with another higher T g polymer [4][5][6][7][8] or using catalytic hydrogenation to fully saturate PS into polyvinylcyclohexane (T g ≈ 150 °C). [9] With recent advances in living/controlled polymerization, various nonlinear architectures, including star, [10][11][12][13][14] graft, and cyclic [15,16] architectures, or their combinations, [17][18][19][20] have been synthesized during the past three decades. These nonlinear macromolecular architectures deliver additional parameters for chemists to use in tuning mechanical properties, as well as incorporating additional functionality to TPEs [21] (Figure 1).In this short review, we focus on the progress in design and synthesis of well-defined multigraft copolymers and their application as thermoplastic elastomers. Progress in precise synthesis of graft copolymers and mechanical properties of multigraft copolymers is first summarized. Recent work on all-acrylic graft copolymer TPEs and a low-cost emulsion polymerization approach to prepare multigraft copolymers are introduced subsequently. Finally, we finish the review with conclusions and some future prospectives. Living Anionic PolymerizationsThermoplastic elastomers (TPEs) have been widely studied because of their recyclability, good processibility, low production cost, and unique performance. The building of graft-type architectures can greatly improve mechanical properties of TPEs. This review focuses on the advances in different approaches to synthesize multigraft copolymer TPEs. Anionic polymerization techniques allow for the synthesis of well-defined macromolecular structures and compositions, with great control over the molecular weight, polydispersity, branch spacing, number of branch points, and branch point ...

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An All‐ROMP Route to Graft Copolymers

Cited by 53 publications

References 29 publications

Degradable precision polynorbornenes via ring‐opening metathesis polymerization

Degradable precision polynorbornenes via ring‐opening metathesis polymerization

Developing New Methods for the Mono-end Functionalization of Living Ring Opening Metathesis Polymers

Design and Synthesis of Multigraft Copolymer Thermoplastic Elastomers: Superelastomers

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