Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy

Cosemans, Inge; Vandenbergh, Joke; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

doi:10.1039/c3py00303e

Cited by 17 publications

(24 citation statements)

References 19 publications

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“…Of the known routes to prepare PPVs,17 only anionic polymerization18 and ROMP of cyclophane‐based systems19 are able to consistently afford polymers with narrow dispersities. Other routes, such as step‐growth Wittig polymerizations, Heck couplings, and iterative syntheses, have proven useful to attain PPVs with ease, yet suffer from high dispersity, scarce functionalization strategies, or are limited to forming soluble oligomers 17.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of Supramolecular Semiconductor Block Copolymers by Ring‐Opening Metathesis Polymerization

Elacqua

Weck

2015

Chemistry A European J

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ω-Telechelic poly(p-phenylene vinylene) species (PPVs) are prepared by living ring-opening metathesis polymerization of a [2.2]paracyclophane-1,9-diene in the presence of Hoveyda-Grubbs 2nd generation initiator, with terminating agents based on N(1) ,N(3) -bis(6-butyramidopyridin-2-yl)-5-hydroxyisophthalamide (Hamilton wedge), cyanuric acid, Pd(II) -SCS-pincer, or pyridine moieties installing the supramolecular motifs. The resultant telechelic polymers are self-assembled into supramolecular block copolymers (BCPs) via metal coordination or hydrogen bonding and analyzed by (1) H NMR spectroscopy. The optical properties are examined, whereby individual PPVs exhibit similar properties regardless of the nature of the end group. Upon self-assembly, different behaviors emerge: the hydrogen-bonding BCP behaves similarly to the parent PPVs whereas the metallosupramolecular BCP demonstrates a hypsochromic shift and a more intense emission owing to the suppression of aggregation. These results demonstrate that directional self-assembly can be a facile method to construct BCPs with semiconducting networks, while combating solubility and aggregation.

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Section: Introductionmentioning

confidence: 99%

Fabrication of Supramolecular Semiconductor Block Copolymers by Ring‐Opening Metathesis Polymerization

Elacqua

Weck

2015

Chemistry A European J

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“…This approach yields polymers that are in principle available for further chain extension in SET-LRP reactions, as we had demonstrated before. [31][32][33] The CPM-monomer feed ratios were carefully chosen, to result in the 5 [MDMO] : [CPM] copolymer composition ratios as given in Table 3. Without any further change of the copolymers, all materials obtained were hydrophobic and only soluble in unipolar media.…”

Section: Post Functionalization Of Copolymersmentioning

confidence: 99%

Modifiable poly(p-phenylene vinylene) copolymers towards functional conjugated materials

et al. 2016

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The copolymerization behavior of poly[2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylene vinylene] (MDMO-PPV) with poly[2-methoxy-5-(carboxypentyloxy)-p-phenylene vinylene] (CPM-PPV) and poly[2,5-dicyano-p-phenylene vinylene] (CN-PPV) in the anionic sulfinyl precursor route is studied and copolymerization parameters are determined. (MDMO/CPM)-PPV shows similar reactivity ratios for both monomers -r1 = 0.74 ± 0.09 and r2 = 0.90 ± 0.10 -when reactions were performed to almost full conversion (> 90 %). Kinetics of (MDMO/CN)-PPV on the other hand clearly indicate the preference to fully enrich the copolymer with MDMO as r1 = 0.65 ± 0.16 and r2 = 0.015 ± 0.02. Although deviations from the ideal behavior are observed for (MDMO/CN)-PPV, already a small amount of CN leads to significant difference in absorption and emission of the material, allowing to tune the color of the material. Further, post polymerization modification via transesterification of the CPM groups with poly(ethylene glycol) (PEG) or propargyl alcohol via the DCC/DMAP procedure leads to a versatile way of synthesizing a variety of (water soluble) PPV copolymers, without affecting the optical properties of the PPV materials. All reactions are carried out on the anionic polymerization pathway of the sulfinyl route, hence allowing to incorporate these polarity and wavelength tunable PPVs into more complex structures.Scheme 3: General reaction scheme for the post-polymerization reactions of (MDMO/CPM)-PPV via the DCC/DMAP procedure, leading to an alkyne 16 or polyethylene glycol (PEG) 17 functionality in the side chain.

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“…As mentioned above, the “site transformation” strategy is the feasible approach to construct block copolymers of allene derivatives and vinyl monomers, in which end‐functionalized polyallene can be employed as macromolecular initiator or mediation agent to initiate or mediate the polymerization of the second monomer with diverse polymerization techniques, including ATRP, SET‐LRP, and reversible addition‐fragmentation chain transfer (RAFT) polymerization, which have been used for preparing diverse block copolymers. ATRP appears to be the most popular process among different reversible‐deactivation radical polymerization (RDRP) techniques because of its mild reactions conditions, tolerance of monomer functionalities, and variety of monomers, and it has been extensively used to prepare copolymers with different architectures.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of PS-b-PPOA-b-PS triblock copolymer via sequential free radical polymerization and ATRP

Ding

Guo

et al. 2017

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

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A novel ABA triblock copolymer comprising double‐bond‐containing poly(phenoxyallene) (PPOA) and polystyrene (PS) segments was synthesized by sequential conventional free radical polymerization and atom transfer radical polymerization (ATRP) via the site transformation strategy. A new bifunctional initiator containing azo and Br‐containing ATRP initiating groups was prepared using 2‐bromopropionyl chloride, hydroquinone, and 4,4′‐azobis(4‐cyanopentanoic acid) as starting materials. Conventional free radical homopolymerization of phenoxyallene with cumulated double bond was performed in toluene to provide a polyallene‐based macroinitiator bearing ATRP initiating groups at both ends, which is stable under UV irradiation and free radical circumstances. PS‐b‐PPOA‐b‐PS triblock copolymer was then obtained by bulk ATRP of styrene initiated by PPOA‐based macroinitiator. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1366–1372

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Synthesis of well-defined PPV containing block polymers with precise endgroup control by a dual-initiator strategy

Abstract: The initiator efficiency in PPV polymerization was tested and PPV-b-(P-tBuA) block copolymers were synthesized. Via hydrolysis amphiphilic materials undergoing micelle formation were obtained.

Cited by 17 publications

References 19 publications

Fabrication of Supramolecular Semiconductor Block Copolymers by Ring‐Opening Metathesis Polymerization

Fabrication of Supramolecular Semiconductor Block Copolymers by Ring‐Opening Metathesis Polymerization

Modifiable poly(p-phenylene vinylene) copolymers towards functional conjugated materials

Synthesis of PS-b-PPOA-b-PS triblock copolymer via sequential free radical polymerization and ATRP

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