<p>The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to full conversion already on the timescale of mixing of the reaction components. Even at -78 degrees C almost full conversion of the monomer is observed after few seconds. BEH-PPVs are obtained in the range of 3000 to 16,000 g mol(-1), whereby dispersity decreases with decreasing molecular weight, allowing for materials with a PDI of 1.1 for the smallest PPV chain. Block copolymerizations were performed via sequential addition of monomers to make use of the living PPV chain ends. Bimodal product mixtures are obtained, consisting of block copolymer as well as PPV homopolymer. The block copolymer PPV-b-poly(tert-butyl acrylate) could nevertheless be separated by selective precipitation as well as preparative chromatography techniques. (c) 2013 Elsevier Ltd. All rights reserved.</p>

Cosemans, Inge

Junkers, Thomas

Loos, Katja

Lutsen, Laurence

Vandenbergh, Joke

Vanderzande, Dirk

Voet, Vincent S. D.

Polymer

The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to full conversion already on the timescale of mixing of the reaction components. Even at -78 degrees C almost full conversion of the monomer is observed after few seconds. BEH-PPVs are obtained in the range of 3000 to 16,000 g mol(-1), whereby dispersity decreases with decreasing molecular weight, allowing for materials with a PDI of 1.1 for the smallest PPV chain. Block copolymerizations were performed via sequential addition of monomers to make use of the living PPV chain ends. Bimodal product mixtures are obtained, consisting of block copolymer as well as PPV homopolymer. The block copolymer PPV-b-poly(tert-butyl acrylate) could nevertheless be separated by selective precipitation as well as preparative chromatography techniques. (c) 2013 Elsevier Ltd. All rights reserved.</p

Proceedings - University of Groningen

   University of GroningenAnionic PPV polymerization from the sulfinyl precursor routeCosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence;Vanderzande, Dirk; Junkers, ThomasPublished in:PolymerDOI:10.1016/j.polymer.2012.12.070IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2013Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Cosemans, I., Vandenbergh, J., Voet, V. S. D., Loos, K., Lutsen, L., Vanderzande, D., & Junkers, T. (2013).Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequentialaddition of monomers. Polymer, 54(4), 1298-1304. https://doi.org/10.1016/j.polymer.2012.12.070CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 17-07-2023SUPPORTING INFORMATION Anionic PPV Polymerization from the Sulfinyl Precursor Route: Block Copolymer Formation from Sequential addition of Monomers   Inge Cosemans,a Joke Vandenbergh,a Vincent Voet,b Katja Loos,b Laurence Lutsen,c Dirk Vanderzandea,c and Thomas Junkers*,a  Analysis UV-Vis spectra were recorded on a Varian Cary 500  UV-Vis-NIR spectrophotometer (scan rate 600 nm/min, continuous run from 200 to 800 nm). Fluorescence measurements were performed using a ‘Fluorolog® Tau-3 Lifetime System’ spectrofluorometer from Horiba Group, USA. The entire system was controlled by DataMax software. The excitation wavelength was kept at 466 and 495 nm and the emission was scanned between respectively 490 or 520 and 800 nm. The sample was placed at an angle of 22.5°, resulting in the highest fluorescence signal with a minimum of scattering and reflection coming from the glass. The slits of both monochromators were adjusted to 5 nm. Analysis of the MWD of the polymer with UV detection at 466nm was performed using a Spectra Series P100 (Spectra Physics) pump equipped with two mixed-B columns (10 µm, 2 cm x 30 cm, Polymer Laboratories) and a Agilent 1100 DAD UV detector at 60°C. Chlorobenzene (CB) was used as the eluent at a flow rate of 1.0 mL/min. Molecular weights were determined relative to polystyrene standards. Differential scanning calorimetry (DSC) measurements were performed on a TA instruments Q200 DSC, purged with nitrogen. About 5 mg samples were sealed in aluminum crucibles (Tzero, 40 µL). The scan rate was 20 °C·min-1 for temperatures ranging from -90 °C – 120 °C. Three heating-cooling cycles were run to check the reproducibility. Thermo gravimetric analysis (TGA) was performed on a TA instruments HiRes TGA 2950 Thermo gravimetric analyzer with a heating rate of 10 °C·min-1.  Characterization for BEH-PPV-b-P(t-BuA) P2  Figure S1: 1H NMR spectrum of block copolymer P2 in CD2Cl2 In the UV-Vis spectrum (Figure S2), a blue-shift in λmax is observed if the blockcopolymer P2 (466nm) is compared to the pure PPV P1 (495nm). So, by introducing the tert-butyl block, the average conjugation length becomes shorter than for the pure PPV, meaning that the acrylate is slightly disrupting the optimal conjugation of the PPV block. The same result is found in the fluorescence spectrum, where also a blue-shifted maximal wavelength is found for the blockcopolymer compared to the pure BEH-PPV.  Figure S2: UV-Vis and fluorescence spectra measured in CHCl3 solution for BEH-PPV P1 and BEH-PPV-b-P(t-BuA) P2  To confirm the presence of a block copolymer also a GPC trace was measured with UV detection at 466 nm (CB as eluent), the maximum absorption wavelength for P2 (see Figure S2). From these data (see also Table S1), it can clearly be concluded that the acrylate block is connected to the PPV block.   Figure S3: GPC profile of P2 for UV detection at 466nm  Table S1: Molecular weight and PDI for P2 (UV detection at 466nm)  Conjugated polymer Mnapp (g·mol-1) PDI After purification, high MW fraction  43900 2.1 In the DSC profile (Figure S4), a glass transition (Tg) is visible at 34.7 °C. This glass transition can be addressed to the acrylate block. For the PPV block, no Tg could be observed in this measurement.  Figure S4: DSC profile for PPV-b-P(t-BuA) P2 To study the thermal stability of the polymers, the weight loss is recorded as a function of temperature in thermo gravimetric analysis. From the TGA profile (Figure S5), it can be observed that vaporization starts around 210 °C. The second major weight loss with a maximum around 432 °C accounts for the degradation of the conjugated system.  Figure S5: TGA profile for PPV-b-P(t-BuA) P2  

English

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

University of Groningen

Dissertations of the University of Groningen

   University of GroningenAnionic PPV polymerization from the sulfinyl precursor routeCosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence;Vanderzande, Dirk; Junkers, ThomasPublished in:PolymerDOI:10.1016/j.polymer.2012.12.070IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2013Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Cosemans, I., Vandenbergh, J., Voet, V. S. D., Loos, K., Lutsen, L., Vanderzande, D., & Junkers, T. (2013).Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequentialaddition of monomers. Polymer, 54(4), 1298-1304. https://doi.org/10.1016/j.polymer.2012.12.070CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 11-10-2022SUPPORTING INFORMATION Anionic PPV Polymerization from the Sulfinyl Precursor Route: Block Copolymer Formation from Sequential addition of Monomers   Inge Cosemans,a Joke Vandenbergh,a Vincent Voet,b Katja Loos,b Laurence Lutsen,c Dirk Vanderzandea,c and Thomas Junkers*,a  Analysis UV-Vis spectra were recorded on a Varian Cary 500  UV-Vis-NIR spectrophotometer (scan rate 600 nm/min, continuous run from 200 to 800 nm). Fluorescence measurements were performed using a ‘Fluorolog® Tau-3 Lifetime System’ spectrofluorometer from Horiba Group, USA. The entire system was controlled by DataMax software. The excitation wavelength was kept at 466 and 495 nm and the emission was scanned between respectively 490 or 520 and 800 nm. The sample was placed at an angle of 22.5°, resulting in the highest fluorescence signal with a minimum of scattering and reflection coming from the glass. The slits of both monochromators were adjusted to 5 nm. Analysis of the MWD of the polymer with UV detection at 466nm was performed using a Spectra Series P100 (Spectra Physics) pump equipped with two mixed-B columns (10 µm, 2 cm x 30 cm, Polymer Laboratories) and a Agilent 1100 DAD UV detector at 60°C. Chlorobenzene (CB) was used as the eluent at a flow rate of 1.0 mL/min. Molecular weights were determined relative to polystyrene standards. Differential scanning calorimetry (DSC) measurements were performed on a TA instruments Q200 DSC, purged with nitrogen. About 5 mg samples were sealed in aluminum crucibles (Tzero, 40 µL). The scan rate was 20 °C·min-1 for temperatures ranging from -90 °C – 120 °C. Three heating-cooling cycles were run to check the reproducibility. Thermo gravimetric analysis (TGA) was performed on a TA instruments HiRes TGA 2950 Thermo gravimetric analyzer with a heating rate of 10 °C·min-1.  Characterization for BEH-PPV-b-P(t-BuA) P2  Figure S1: 1H NMR spectrum of block copolymer P2 in CD2Cl2 In the UV-Vis spectrum (Figure S2), a blue-shift in λmax is observed if the blockcopolymer P2 (466nm) is compared to the pure PPV P1 (495nm). So, by introducing the tert-butyl block, the average conjugation length becomes shorter than for the pure PPV, meaning that the acrylate is slightly disrupting the optimal conjugation of the PPV block. The same result is found in the fluorescence spectrum, where also a blue-shifted maximal wavelength is found for the blockcopolymer compared to the pure BEH-PPV.  Figure S2: UV-Vis and fluorescence spectra measured in CHCl3 solution for BEH-PPV P1 and BEH-PPV-b-P(t-BuA) P2  To confirm the presence of a block copolymer also a GPC trace was measured with UV detection at 466 nm (CB as eluent), the maximum absorption wavelength for P2 (see Figure S2). From these data (see also Table S1), it can clearly be concluded that the acrylate block is connected to the PPV block.   Figure S3: GPC profile of P2 for UV detection at 466nm  Table S1: Molecular weight and PDI for P2 (UV detection at 466nm)  Conjugated polymer Mnapp (g·mol-1) PDI After purification, high MW fraction  43900 2.1 In the DSC profile (Figure S4), a glass transition (Tg) is visible at 34.7 °C. This glass transition can be addressed to the acrylate block. For the PPV block, no Tg could be observed in this measurement.  Figure S4: DSC profile for PPV-b-P(t-BuA) P2 To study the thermal stability of the polymers, the weight loss is recorded as a function of temperature in thermo gravimetric analysis. From the TGA profile (Figure S5), it can be observed that vaporization starts around 210 °C. The second major weight loss with a maximum around 432 °C accounts for the degradation of the conjugated system.  Figure S5: TGA profile for PPV-b-P(t-BuA) P2  

ARTS repository - University of Groningen

   University of GroningenAnionic PPV polymerization from the sulfinyl precursor routeCosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence;Vanderzande, Dirk; Junkers, ThomasPublished in:PolymerDOI:10.1016/j.polymer.2012.12.070IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2013Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Cosemans, I., Vandenbergh, J., Voet, V. S. D., Loos, K., Lutsen, L., Vanderzande, D., & Junkers, T. (2013).Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequentialaddition of monomers. Polymer, 54(4), 1298-1304. https://doi.org/10.1016/j.polymer.2012.12.070CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 07-06-2022SUPPORTING INFORMATION Anionic PPV Polymerization from the Sulfinyl Precursor Route: Block Copolymer Formation from Sequential addition of Monomers   Inge Cosemans,a Joke Vandenbergh,a Vincent Voet,b Katja Loos,b Laurence Lutsen,c Dirk Vanderzandea,c and Thomas Junkers*,a  Analysis UV-Vis spectra were recorded on a Varian Cary 500  UV-Vis-NIR spectrophotometer (scan rate 600 nm/min, continuous run from 200 to 800 nm). Fluorescence measurements were performed using a ‘Fluorolog® Tau-3 Lifetime System’ spectrofluorometer from Horiba Group, USA. The entire system was controlled by DataMax software. The excitation wavelength was kept at 466 and 495 nm and the emission was scanned between respectively 490 or 520 and 800 nm. The sample was placed at an angle of 22.5°, resulting in the highest fluorescence signal with a minimum of scattering and reflection coming from the glass. The slits of both monochromators were adjusted to 5 nm. Analysis of the MWD of the polymer with UV detection at 466nm was performed using a Spectra Series P100 (Spectra Physics) pump equipped with two mixed-B columns (10 µm, 2 cm x 30 cm, Polymer Laboratories) and a Agilent 1100 DAD UV detector at 60°C. Chlorobenzene (CB) was used as the eluent at a flow rate of 1.0 mL/min. Molecular weights were determined relative to polystyrene standards. Differential scanning calorimetry (DSC) measurements were performed on a TA instruments Q200 DSC, purged with nitrogen. About 5 mg samples were sealed in aluminum crucibles (Tzero, 40 µL). The scan rate was 20 °C·min-1 for temperatures ranging from -90 °C – 120 °C. Three heating-cooling cycles were run to check the reproducibility. Thermo gravimetric analysis (TGA) was performed on a TA instruments HiRes TGA 2950 Thermo gravimetric analyzer with a heating rate of 10 °C·min-1.  Characterization for BEH-PPV-b-P(t-BuA) P2  Figure S1: 1H NMR spectrum of block copolymer P2 in CD2Cl2 In the UV-Vis spectrum (Figure S2), a blue-shift in λmax is observed if the blockcopolymer P2 (466nm) is compared to the pure PPV P1 (495nm). So, by introducing the tert-butyl block, the average conjugation length becomes shorter than for the pure PPV, meaning that the acrylate is slightly disrupting the optimal conjugation of the PPV block. The same result is found in the fluorescence spectrum, where also a blue-shifted maximal wavelength is found for the blockcopolymer compared to the pure BEH-PPV.  Figure S2: UV-Vis and fluorescence spectra measured in CHCl3 solution for BEH-PPV P1 and BEH-PPV-b-P(t-BuA) P2  To confirm the presence of a block copolymer also a GPC trace was measured with UV detection at 466 nm (CB as eluent), the maximum absorption wavelength for P2 (see Figure S2). From these data (see also Table S1), it can clearly be concluded that the acrylate block is connected to the PPV block.   Figure S3: GPC profile of P2 for UV detection at 466nm  Table S1: Molecular weight and PDI for P2 (UV detection at 466nm)  Conjugated polymer Mnapp (g·mol-1) PDI After purification, high MW fraction  43900 2.1 In the DSC profile (Figure S4), a glass transition (Tg) is visible at 34.7 °C. This glass transition can be addressed to the acrylate block. For the PPV block, no Tg could be observed in this measurement.  Figure S4: DSC profile for PPV-b-P(t-BuA) P2 To study the thermal stability of the polymers, the weight loss is recorded as a function of temperature in thermo gravimetric analysis. From the TGA profile (Figure S5), it can be observed that vaporization starts around 210 °C. The second major weight loss with a maximum around 432 °C accounts for the degradation of the conjugated system.  Figure S5: TGA profile for PPV-b-P(t-BuA) P2  

Inge Cosemans

Joke Vandenbergh

Vincent S.D. Voet

Katja Loos

Laurence Lutsen

Dirk Vanderzande

Thomas Junkers

Crossref

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

The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to full conversion already on the timescale of mixing of the reaction components. Even at -78 degrees C almost full conversion of the monomer is observed after few seconds. BEH-PPVs are obtained in the range of 3000 to 16,000 g mol(-1), whereby dispersity decreases with decreasing molecular weight, allowing for materials with a PDI of 1.1 for the smallest PPV chain. Block copolymerizations were performed via sequential addition of monomers to make use of the living PPV chain ends. Bimodal product mixtures are obtained, consisting of block copolymer as well as PPV homopolymer. The block copolymer PPV-b-poly(tert-butyl acrylate) could nevertheless be separated by selective precipitation as well as preparative chromatography techniques. (c) 2013 Elsevier Ltd. All rights reserved

NARCIS 

   University of GroningenAnionic PPV polymerization from the sulfinyl precursor routeCosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence;Vanderzande, Dirk; Junkers, ThomasPublished in:PolymerDOI:10.1016/j.polymer.2012.12.070IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:2013Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Cosemans, I., Vandenbergh, J., Voet, V. S. D., Loos, K., Lutsen, L., Vanderzande, D., & Junkers, T. (2013).Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequentialaddition of monomers. Polymer, 54(4), 1298-1304. https://doi.org/10.1016/j.polymer.2012.12.070CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 09-09-2023SUPPORTING INFORMATION Anionic PPV Polymerization from the Sulfinyl Precursor Route: Block Copolymer Formation from Sequential addition of Monomers   Inge Cosemans,a Joke Vandenbergh,a Vincent Voet,b Katja Loos,b Laurence Lutsen,c Dirk Vanderzandea,c and Thomas Junkers*,a  Analysis UV-Vis spectra were recorded on a Varian Cary 500  UV-Vis-NIR spectrophotometer (scan rate 600 nm/min, continuous run from 200 to 800 nm). Fluorescence measurements were performed using a ‘Fluorolog® Tau-3 Lifetime System’ spectrofluorometer from Horiba Group, USA. The entire system was controlled by DataMax software. The excitation wavelength was kept at 466 and 495 nm and the emission was scanned between respectively 490 or 520 and 800 nm. The sample was placed at an angle of 22.5°, resulting in the highest fluorescence signal with a minimum of scattering and reflection coming from the glass. The slits of both monochromators were adjusted to 5 nm. Analysis of the MWD of the polymer with UV detection at 466nm was performed using a Spectra Series P100 (Spectra Physics) pump equipped with two mixed-B columns (10 µm, 2 cm x 30 cm, Polymer Laboratories) and a Agilent 1100 DAD UV detector at 60°C. Chlorobenzene (CB) was used as the eluent at a flow rate of 1.0 mL/min. Molecular weights were determined relative to polystyrene standards. Differential scanning calorimetry (DSC) measurements were performed on a TA instruments Q200 DSC, purged with nitrogen. About 5 mg samples were sealed in aluminum crucibles (Tzero, 40 µL). The scan rate was 20 °C·min-1 for temperatures ranging from -90 °C – 120 °C. Three heating-cooling cycles were run to check the reproducibility. Thermo gravimetric analysis (TGA) was performed on a TA instruments HiRes TGA 2950 Thermo gravimetric analyzer with a heating rate of 10 °C·min-1.  Characterization for BEH-PPV-b-P(t-BuA) P2  Figure S1: 1H NMR spectrum of block copolymer P2 in CD2Cl2 In the UV-Vis spectrum (Figure S2), a blue-shift in λmax is observed if the blockcopolymer P2 (466nm) is compared to the pure PPV P1 (495nm). So, by introducing the tert-butyl block, the average conjugation length becomes shorter than for the pure PPV, meaning that the acrylate is slightly disrupting the optimal conjugation of the PPV block. The same result is found in the fluorescence spectrum, where also a blue-shifted maximal wavelength is found for the blockcopolymer compared to the pure BEH-PPV.  Figure S2: UV-Vis and fluorescence spectra measured in CHCl3 solution for BEH-PPV P1 and BEH-PPV-b-P(t-BuA) P2  To confirm the presence of a block copolymer also a GPC trace was measured with UV detection at 466 nm (CB as eluent), the maximum absorption wavelength for P2 (see Figure S2). From these data (see also Table S1), it can clearly be concluded that the acrylate block is connected to the PPV block.   Figure S3: GPC profile of P2 for UV detection at 466nm  Table S1: Molecular weight and PDI for P2 (UV detection at 466nm)  Conjugated polymer Mnapp (g·mol-1) PDI After purification, high MW fraction  43900 2.1 In the DSC profile (Figure S4), a glass transition (Tg) is visible at 34.7 °C. This glass transition can be addressed to the acrylate block. For the PPV block, no Tg could be observed in this measurement.  Figure S4: DSC profile for PPV-b-P(t-BuA) P2 To study the thermal stability of the polymers, the weight loss is recorded as a function of temperature in thermo gravimetric analysis. From the TGA profile (Figure S5), it can be observed that vaporization starts around 210 °C. The second major weight loss with a maximum around 432 °C accounts for the degradation of the conjugated system.  Figure S5: TGA profile for PPV-b-P(t-BuA) P2  

University of Groningen Research Database

  
 University of Groningen
Anionic PPV polymerization from the sulfinyl precursor route
Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent; Loos, Katja; Lutsen, Laurence;
Vanderzande, Dirk; Junkers, Thomas
Published in:
Polymer
DOI:
10.1016/j.polymer.2012.12.070
IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from
it. Please check the document version below.
Document Version
Publisher's PDF, also known as Version of record
Publication date:
2013
Link to publication in University of Groningen/UMCG research database
Citation for published version (APA):
Cosemans, I., Vandenbergh, J., Voet, V. S. D., Loos, K., Lutsen, L., Vanderzande, D., & Junkers, T. (2013).
Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequential
addition of monomers. Polymer, 54(4), 1298-1304. DOI: 10.1016/j.polymer.2012.12.070
Copyright
Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the
author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).
Take-down policy
If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately
and investigate your claim.
Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the
number of authors shown on this cover page is limited to 10 maximum.
Download date: 11-02-2018
SUPPORTING INFORMATION 
Anionic PPV Polymerization from the Sulfinyl Precursor 
Route: Block Copolymer Formation from Sequential addition 
of Monomers  
 
Inge Cosemans,a Joke Vandenbergh,a Vincent Voet,b Katja Loos,b Laurence Lutsen,c Dirk 
Vanderzandea,c and Thomas Junkers*,a 
 
Analysis 
UV-Vis spectra were recorded on a Varian Cary 500  UV-Vis-NIR spectrophotometer (scan 
rate 600 nm/min, continuous run from 200 to 800 nm). Fluorescence measurements were 
performed using a ‘Fluorolog® Tau-3 Lifetime System’ spectrofluorometer from Horiba 
Group, USA. The entire system was controlled by DataMax software. The excitation 
wavelength was kept at 466 and 495 nm and the emission was scanned between respectively 
490 or 520 and 800 nm. The sample was placed at an angle of 22.5°, resulting in the highest 
fluorescence signal with a minimum of scattering and reflection coming from the glass. The 
slits of both monochromators were adjusted to 5 nm. Analysis of the MWD of the polymer 
with UV detection at 466nm was performed using a Spectra Series P100 (Spectra Physics) 
pump equipped with two mixed-B columns (10 µm, 2 cm x 30 cm, Polymer Laboratories) and 
a Agilent 1100 DAD UV detector at 60°C. Chlorobenzene (CB) was used as the eluent at a 
flow rate of 1.0 mL/min. Molecular weights were determined relative to polystyrene 
standards. Differential scanning calorimetry (DSC) measurements were performed on a TA 
instruments Q200 DSC, purged with nitrogen. About 5 mg samples were sealed in aluminum 
crucibles (Tzero, 40 µL). The scan rate was 20 °C·min-1 for temperatures ranging from -90 °C 
– 120 °C. Three heating-cooling cycles were run to check the reproducibility. Thermo 
gravimetric analysis (TGA) was performed on a TA instruments HiRes TGA 2950 Thermo 
gravimetric analyzer with a heating rate of 10 °C·min-1. 
 
Characterization for BEH-PPV-b-P(t-BuA) P2 
 
Figure S1: 1H NMR spectrum of block copolymer P2 in CD2Cl2 
In the UV-Vis spectrum (Figure S2), a blue-shift in λmax is observed if the blockcopolymer P2 
(466nm) is compared to the pure PPV P1 (495nm). So, by introducing the tert-butyl block, 
the average conjugation length becomes shorter than for the pure PPV, meaning that the 
acrylate is slightly disrupting the optimal conjugation of the PPV block. The same result is 
found in the fluorescence spectrum, where also a blue-shifted maximal wavelength is found 
for the blockcopolymer compared to the pure BEH-PPV. 
 
Figure S2: UV-Vis and fluorescence spectra measured in CHCl3 solution for BEH-PPV P1 
and BEH-PPV-b-P(t-BuA) P2  
To confirm the presence of a block copolymer also a GPC trace was measured with UV 
detection at 466 nm (CB as eluent), the maximum absorption wavelength for P2 (see Figure 
S2). From these data (see also Table S1), it can clearly be concluded that the acrylate block is 
connected to the PPV block.  
 
Figure S3: GPC profile of P2 for UV detection at 466nm 
 
Table S1: Molecular weight and PDI for P2 (UV detection at 466nm) 
 Conjugated polymer 
Mnapp (g·mol-1) PDI 
After purification, 
high MW fraction  43900 2.1 
In the DSC profile (Figure S4), a glass transition (Tg) is visible at 34.7 °C. This glass 
transition can be addressed to the acrylate block. For the PPV block, no Tg could be observed 
in this measurement. 
 
Figure S4: DSC profile for PPV-b-P(t-BuA) P2 
To study the thermal stability of the polymers, the weight loss is recorded as a function of 
temperature in thermo gravimetric analysis. From the TGA profile (Figure S5), it can be 
observed that vaporization starts around 210 °C. The second major weight loss with a 
maximum around 432 °C accounts for the degradation of the conjugated system. 
 
Figure S5: TGA profile for PPV-b-P(t-BuA) P2 
 


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

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