Continuous Synthesis and Thermal Elimination of Sulfinyl-Route Poly(p-Phenylene Vinylene) in Consecutive Flow Reactions

Continuous synthesis of multistep polymerizations at microscale is made available by coupling two microstructured chip reactors in a single reactor setup. Conjugated [2-methoxy-5-(3′,7′-dimethyloctyloxy)]-1,4-phenylenevinylene (MDMO-PPV) is synthesized via the radical sulfinyl precursor route. Reactions are carried out in separate reactors and optimization of the elimination of polymer can be effectively performed in a defined temperature range, allowing for full polymer conversion within minutes and formation of conjugated materials. The combination of both processes in a single coupled reactor setup permits total monomer-to-conjugated-MDMO-PPV conversions while retaining its pristine optical properties. Polymer characteristics are comparatively good and the reduction in yield due to the lower initial monomer concentrations is compensated by the much shorter reaction times required in the flow process.

[1]  J. Vandenbergh,et al.  Polymer end group modifications and polymer conjugations via “click” chemistry employing microreactor technology , 2014 .

[2]  Erjun Zhou,et al.  Synthesis and properties of D–A copolymers based on dithienopyrrole and benzothiadiazole with various numbers of thienyl units as spacers , 2014 .

[3]  Dirk Vanderzande,et al.  A New Synthetic Route to a Soluble High Molecular Weight Precursor for Poly(p-phenylenevinylene) derivatives , 1995 .

[4]  Khai Leok Chan,et al.  Synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. , 2009, Chemical reviews.

[5]  W. R. Salaneck,et al.  Electroluminescence in conjugated polymers , 1999, Nature.

[6]  Peter H Seeberger,et al.  Microreactors as tools for synthetic chemists-the chemists' round-bottomed flask of the 21st century? , 2006, Chemistry.

[7]  Andreas Kirschning,et al.  Continuous flow techniques in organic synthesis. , 2003, Chemistry.

[8]  Paul Watts,et al.  Continuous Flow Reactors, a Tool for the Modern Synthetic Chemist , 2008 .

[9]  Holger Frey,et al.  Microstructured Reactors for Polymer Synthesis: A Renaissance of Continuous Flow Processes for Tailor‐Made Macromolecules? , 2008 .

[10]  Volker Hessel,et al.  Micro process engineering : a comprehensive handbook , 2009 .

[11]  S. Karpagam,et al.  Applications of wittig reactions in dibenzo 18‐crown‐6‐ether substituted phenylenevinylene oligomer—synthesis, photo luminescent, and dielectric properties , 2011 .

[12]  F. Krebs,et al.  Synthesis and photovoltaic properties from inverted geometry cells and roll-to-roll coated large area cells from dithienopyrrole-based donor–acceptor polymers , 2013 .

[13]  F. E. Karasz,et al.  Para‐Xylylenes and analogues by base‐induced elimination from 1,4‐bis‐(dialkylsulfoniomethyl)arene salts in poly(1,4‐arylene vinylene) synthesis by the wessling soluble precursor method , 1992 .

[14]  D. Vanderzande,et al.  Synthesis of poly(p-phenylene vinylene) and derivatives via a new precursor route, the dithiocarbamate route , 2006 .

[15]  P. Adriaensens,et al.  Polymerization Mechanism of 1-[(Butylsulfi(o)nyl)methyl]-4-(halomethyl)benzene: The Effect of Polarizer and Leaving Group , 1998 .

[16]  H. G. Gilch,et al.  Polymerization of α‐halogenated p‐xylenes with base , 1966 .

[17]  Paul Watts,et al.  Micro reactors: principles and applications in organic synthesis , 2002 .

[18]  D. Vanderzande,et al.  Verification of Radical and Anionic Polymerization Mechanisms in the Sulfinyl and the Gilch Route , 2003 .

[19]  Nam-Trung Nguyen,et al.  Micromixers?a review , 2005 .

[20]  H. Löwe,et al.  Chemistry in microstructured reactors. , 2004, Angewandte Chemie.

[21]  P. Adriaensens,et al.  Synthesis of poly(p-phenylene vinylene) materials via the precursor routes , 2012 .

[22]  Gilles Horowitz,et al.  Organic Field‐Effect Transistors , 1998 .

[23]  A. Heeger,et al.  Visible light emission from semiconducting polymer diodes , 1991 .

[24]  N. S. Sariciftci,et al.  Conjugated polymer-based organic solar cells. , 2007, Chemical reviews.

[25]  Norbert Kockmann,et al.  Micro Process Engineering , 2006 .

[26]  Wallace W. H. Wong,et al.  Continuous flow synthesis of conjugated polymers. , 2012, Chemical communications.

[27]  P. Adriaensens,et al.  The thermal conversion reaction of sulphonyl substituted poly(para-xylylene): evidence for the formation of PPV structures , 2002 .

[28]  J. Gelan,et al.  Polymerization of a p-quinodimethane derivative to a precursor of poly(p-phenylene vinylene)—indications for a free radical mechanism , 1997 .

[29]  Laurence Lutsen,et al.  The Gilch polymerisation towards OC1C10-PPV: indications for a radical mechanism , 2001 .

[30]  R. Carleer,et al.  Study of the Thermal Elimination and Degradation Processes ofn-Alkylsulfinyl-PPV and -OC1C10-PPV Precursor Polymers with in Situ Spectroscopic Techniques , 2005 .

[31]  Abhishek P. Kulkarni,et al.  Electron Transport Materials for Organic Light-Emitting Diodes , 2004 .

[32]  P. Adriaensens,et al.  Optimization of the polymerization process of sulfinyl precursor polymers toward poly(p-phenylenevinylene) , 1999 .

[33]  A. J. Lovinger,et al.  Luminescence Enhancement by the Introduction of Disorder into Poly(p-phenylene vinylene) , 1995, Science.

[34]  M. Rehahn,et al.  [2.2]Paracyclophanes with defined substitution pattern-key compounds for the mechanistic understanding of the Gilch reaction to poly(p-phenylene vinylene)s. , 2003, Angewandte Chemie.

[35]  J. Vandenbergh,et al.  Precision synthesis of acrylate multiblock copolymers from consecutive microreactor RAFT polymerizations , 2013 .

[36]  F. Motmans,et al.  Polymerization Behavior of Xanthate-Containing Monomers toward PPV Precursor Polymers: Study of the Elimination Behavior of Precursor Polymers and Oligomers with in-Situ FT-IR and UV−Vis Analytical Techniques , 2002 .