Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequential addition of monomers

Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

doi:10.1016/j.polymer.2012.12.070

Cited by 16 publications

(23 citation statements)

References 24 publications

(27 reference statements)

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“…40 In addition, a comparison of the molecular weights and its accompanying dispersities between GPC and MALLS measurements, indicates the over estimation of the GPC, as dispersities obtained via MALLS measurements all show values below 1.5, underpinning the living behavior of PPV monomers via the anionic sulfinyl route using dedicated anionic initiators. 31 Further UV-Vis and fluorescent results indicate the considerable influence of the inclusion of the CN pre-monomer, see Figure 4. Upon 10 % CN-monomer feed, a decrease in λ max from 489 nm to 472 nm is seen.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 98%

“…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%

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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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Section: Please Do Not Adjust Marginsmentioning

confidence: 98%

Section: Post Functionalization Of Copolymersmentioning

confidence: 99%

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

et al. 2016

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“…Purification of the MDMO-PPV-b-PEG block copolymer from the homopolymer leftovers is far from trivial. Residual PEG can relatively easily be removed by washing the mixture with water, residual MDMO-PPV can only be removed by preparative recycling SEC, as was done before [44]. Figure 7.…”

Section: Conjugation Of Ppv Block Copolymers Using Cuaac Conditionsmentioning

confidence: 99%

Facile Synthesis of Well-Defined MDMO-PPV Containing (Tri)Block—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

et al. 2015

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A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene) (PPV) materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA) concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ· mol −1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC). PPVs with molecular weights ranging from thousands to ten thousands g· mol −1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark-Houwink-Kuhn-Sakurada (MHKS) parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy)]-1,4-phenylenevinylene) to α = 0.809 and k = 0.00002 mL· g −1 . Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP) with acrylates and styrene. OPEN ACCESSPolymers 2015, 7 419A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP). In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC) was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(pphenylene vinylene)-block-poly(tert-butyl acrylate)-block-poly(ethylene glycol) (PPV-bPtBuA-b-PEG).

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“…There are two promising approaches to enhance the application of PPV-type polymers: (i) attachment of strongly electrophilic moieties like cyano or fluorine to the polymeric backbone, such moieties increase the stability of the double bond to photooxidation [9]; and (ii) creation of copolymers that have a donor-acceptor (D-A) structure. In this case, a proper combination of donor and acceptor units in the copolymer gives the possibility of tuning the electronic energy levels and thus to produce materials with higher efficiency [10][11][12][13][14][15][16]. In fact, cyanosubstituted PPVs initially attracted great attention because of their high electron affinities compared to PPV itself, facilitating electron injection and electronic mobility, a fact that allows the use of electrodes with lower work functions and, consequently, higher stabilities.…”

Section: Introductionmentioning

confidence: 99%

Evaluation of the photocurrent value for poly(2,5-dicyano- p -phenylene-vinylene)-co-(p-phenylene-vinylene) (DCN-PPV/PPV)

Santos

Bertuzzi

Pedroso

et al. 2016

J Solid State Electrochem

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A method to obtain poly(2,5-dicyano-p-phenylenevinylene)-co-(p-phenylene-vinylene) (DCN-PPV/PPV) block copolymer was developed. The structural characteristics of the copolymer and its capability to generate a photocurrent were evaluated. IR spectra indicate the complete conversion of precursor copolymer into DCN-PPV/PPV at 250°C under lowpressure conditions. The DCN-PPV/PPV polymer optical band gap was determined based on the observed UV-Vis spectral data by using Tauc's equation. The two linear regions in the Tauc curve (E g = 2.63 eVand 2.02) revealed the formation of a block copolymer. Thermal analysis showed that DCN-PPV/PPV has a higher stability than PPV and starts to degrade at 317°C in air. The electronic parameters of DCN-PPV/PPV (IP = 5.25 eV, EA = 3.30 eV, and E g = 1.95 eV) indicate that the cyano groups reduce the LUMO energy level without affecting the HOMO energy by much. DCN-PPV/PPV photoactivity measurements show higher photocurrent values compared to those for PPV.

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Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequential addition of monomers

Cited by 16 publications

References 24 publications

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

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

Facile Synthesis of Well-Defined MDMO-PPV Containing (Tri)Block—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

Evaluation of the photocurrent value for poly(2,5-dicyano- p -phenylene-vinylene)-co-(p-phenylene-vinylene) (DCN-PPV/PPV)

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