Philippe Zinck

Catalyse et Chimie Moléculaire
Catalyse et synthèse éco-compatible (CASECO)


Professeur des universités

(Enseignants chercheurs)


Téléphone :03 20 43 68 70
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Adresse :Université Lille
Cité Scientifique, Bâtiment C3
59650 Villeneuve d'Ascq Cedex
France

 

RESEARCH TOPIC: CATALYSIS FOR FUNCTIONAL AND BIOBASED POLYMERS

 

Coordinative chain transfer polymerization (CCTP)

 

The principle of CCTP is to allow a growing macromolecular chain to transmetallate from a transition metal based catalyst to a main group metal based chain transfer agent. CCTP opens to way to a large array of applications useful for the synthetic chemist that includes not only molecular weight control, atom economy and polymer functionalization, but also the control and design of polymer microstructure. While exploring this fascinating area of polymerization catalysis, we discovered that CCTP affords fine control over the microstructure of polydienes, and that it can be considered as new concept for the control of the composition of statistical copolymers. The concepts were recently extended to the statistical copolymerization of conjugated dienes, to terpolymerizations and to a biobased conjugated diene, myrcene.

 

 

We also extended the chain shuttling copolymerization approach discovered by researchers of the Dow Chemical Co. to the synthesis of a new family of thermoplastic elastomers. These unique materials exhibit a fully amorphous multiblock microstructure of soft and hard segments. The composition of the blocks and the resulting glass transition temperatures can be easily tuned by changing the feed and/or the relative amount of the catalysts. We further reported a second catalytic combination for isoprene chain shuttling polymerization. The halflanthanocene / dilakylmagnesium catalytic system represented hereafter combined to neodymium trichloride / trialkylaluminum, allows the access to a (1,4-trans / 1,4-cis) stereomultiblock polyisoprene that self-assembles at room temperature.

 

 

Organocatalysis for the ring-opening polymerization of cyclic esters and their functionalization with carbohydrates and biomolecules

 

 

Biodegradable polyesters based notably on renewable resources are used in biomedical areas and for consumer goods and packaging applications. Metal mediated polymerizations can lead to the presence of residual metal traces in the material, which can be detrimental for the targeted applications. This can be circumvented by the use of organic molecules as polymerization catalysts. We reported recently in this frame the use of a binol derived phosphoric acid (binaphthyl-diyl hydrogen phosphate) as catalyst for the controlled ring-opening polymerization of lactones in mild conditions, as well as the controlled ring-opening polymerization of lactide using various bifunctional acid/base combinations. In particular, we assessed acid base equilibria involving two bases as catalytic systems, which led to increased activities, a better control of the molecular weight and prevent form undesirable transesterification reactions.

 

 

 

The functionalization of aliphatic polyesters with carbohydrates is an important strategy to tailor their properties while keeping a biocompatible character. We discovered new reactivities in this field using both well known, readily available and new, home-made organocatalysts for the ring-opening polymerization of cyclic esters. The resulting macromolecular objects have shown promising potential in materials science and pharmaceuticals.

 

 

We also reported the quantitative polymerization of -caprolactone in water using various Brönsted acids as organocatalysts. The approach was further conducted in the presence of water-soluble polysaccharides, enabling an easy, mild and one-step access to poly(-caprolactone)-graft-dextran and poly(-caprolactone)-graft-methylcellulose copolymers.

 

 

Nucleobase-functionalized polymers are widely used in the fields of supramolecular chemistry and self-assembly,and their development for biomedical applications is also an area of interest. They are usually synthesized by tedious multistep procedures. We have shown that L-Lactide can be quantitatively polymerized in the presence of adenine. Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine end-capped polylactide in a simple one-step procedure, in bulk, without additional catalyst, which is promising for biomedical applications. DFT calculations show that the polymerization occurs via hydrogen bond catalysis.

 

TEACHING ACTIVITIES

Chemical Engineering and Biobased Polymers at the Chemistry Department of the Institute of Technology of the University of Lille

 

AFFILIATIONS

 

SFC - Société Française de Chimie (North Section Board)

GFP - Groupe Français des Polymères (North Section Board)

MCFA – Marie Curie Fellowship Association (Advisory Board)

IUPAC – International Union of Pure and Applied Chemistry

 

 SELECTED BOOK CHAPTERS

 

Y. Miao, A. Mortreux, P. Zinck

Polyesters functionalized carbohydrates via organocatalyzed ring-opening polymerization

Chapter 15 in Carbohydrates Chemistry Vol. 40, 2014, pp. 298–311, Royal Society of Chemistry

 

T. Chenal, M. Visseaux, P. Zinck

Coordinative chain transfer polymerization and copolymerization by means of rare earths organometallic catalysts for the synthesis of tailor made polymers

Chapter 27 in Advances in Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book, 1st Edition, 2014, pp. 345-358, John Wiley & Sons, Inc.

 

 

OUR GRATEFULLY ACKNOWLEDGED FUNDERS AND ONGOING PROJECTS

 

 

Project devoted to thermoplastics elastomers, with notably the development of second generation thermoplastic elastomers via chain shuttling polymerization.

 

Partners : CentexBel, Materia Nova (Mons), KU Leuven Campus Kulak (Courtrai), University of Reims Champagne-Ardenne (Reims), , IMT Lille Douai, Pôle de compétitivité PlastiWin (Liège), UP-tex (Tourcoing), Matikem (Villeneuve d'Ascq), Materiala (Charleville-Mézières).

 

More details here:

https://interreg-elastoplast.eu/fr

http://www.interreg-fwvl.eu/sites/default/files/gotos3_elasto-plast_fr_0.pdf

 

 

Development of polymeric materials based on microalgae.

 

Partners : University of Mons, University of Ghent, KU Leuven Campus Kulak (Courtrai), AgroParisTech Reims, University of Reims Champagne-Ardenne, Pôle de Compétitivité Aquimer (Boulogne-sur-Mer), GreenWin (Charleroi), IAR (Laon), PC Groenteteelt (Kruishoutem), POM West-Vlaanderen (Bruges).

 

More details here:

http://www.interreg-fwvl.eu/sites/default/files/gotos3_alpo_fr.pdf

 

Both Interreg projects belong to the Portofolio GoToS3 : www.gotos3.eu

 

            

                   

                                       

 

 

 PUBLICATIONS RÉCENTES

Publications dans la base de données : 43 (depuis 2008)
  • 2018

  • Intelligent Monte Carlo: A New Paradigm for Inverse Polymerization Engineering.
    Mohammadi Yousef, Saeb Mohammad Reza, Penlidis Alexander, Jabbari Esmaiel, Zinck Philippe, Stadler Florian J., Matyjaszewski Krzysztof.
    Macromolecular Theory and Simulations, vol. 27, pg. 1700106 (2018) DOI
     
  • Modification of starch by graft copolymerization.
    Meimoun Julie, Wiatz Vincent, Saint-Loup René, Parcq Julien, Favrelle Audrey, Bonnet Fanny, Zinck Philippe.
    Starch - Stärke, vol. 70, pg. 1-23 (2018) DOI
     
  • 2017

  • Bimetallic Catalytic Systems Based on Sb, Ge and Ti for the Synthesis of Poly(ethylene terephthalate-co-isosorbide terephthalate).
    Stanley Nicholas, Chenal Thomas, Delaunay Thierry, Saint-Loup René, Jacquel Nicolas, Zinck Philippe.
    Polymers, vol. 9, pg. 590 (2017) DOI
     
  • Silica-Grafted Lanthanum Benzyl Species: Synthesis, Characterization, and Catalytic Applications.
    Vancompernolle Tom, Valente Andreia, Chenal Thomas, Zinck Philippe, Del Rosal Iker, Maron Laurent, Taoufik Mostafa, Harder Sjoerd, Gauvin Régis M.
    Organometallics, vol. 36, pg. 3912-3920 (2017) DOI
     
  • Unspoken aspects of chain shuttling reactions: Patterning the molecular landscape of olefin multi-block copolymers.
    Saeb Mohammad Reza, Mohammadi Yousef, Kermaniyan Tayebeh Sadat, Zinck Philippe, Stadler Florian J.
    Polymer, vol. 116, pg. 55-75 (2017) DOI
     
  • Isoprene chain shuttling polymerisation between cis and trans regulating catalysts: straightforward access to a new material.
    Phuphuak Y., Bonnet F., Stoclet G., Bria M., Zinck P.
    Chemical Communications, vol. 53, pg. 5330-5333 (2017) DOI
     
  • 2016

  • Adenine as an organocatalyst for the ring-opening polymerization of lactide: scope, mechanism and access to adenine-functionalized polylactide.
    Nogueira Guilherme, Favrelle Audrey, Bria Marc, Prates Ramalho João P., Mendes Paulo J., Valente Andreia, Zinck Philippe.
    React. Chem. Eng., (2016) DOI
     
  • Isoprene polymerization mediated by vanadium-[ONNO] complexes.
    Phuphuak Yupin, Bonnet Fanny, Vendier Laure, Lorber Christian, Zinck Philippe.
    Dalton Trans., vol. 45, pg. 12069-12077 (2016) DOI
     
  • Unexpected reactivities in chain shuttling copolymerizations.
    Zinck Philippe.
    Polymer International, vol. 65, pg. 11-15 (2016) DOI
     
  • β-Diketiminate-supported magnesium alkyl: synthesis, structure and application as co-catalyst for polymerizations mediated by a lanthanum half-sandwich complex.
    Georges Sébastien, Bonnet Fanny, Roussel Pascal, Visseaux Marc, Zinck Philippe.
    Applied Organometallic Chemistry, vol. 30, pg. 26-31 (2016) DOI
     
  • 2015

  • Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations.
    Bonnet Fanny, Dyer Hellen E., El Kinani Yassine, Dietz Carin, Roussel Pascal, Bria Marc, Visseaux Marc, Zinck Philippe, Mountford Philip.
    Dalton Trans., vol. 44, pg. 12312-12325 (2015) DOI
     
  • New acid/base salts as co-catalysts for the organocatalyzed ring opening polymerization of lactide.
    Miao Yong, Stanley Nicholas, Favrelle Audrey, Bousquet Till, Bria Marc, Mortreux André, Zinck Philippe.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 53, pg. 659-664 (2015) DOI
     
  • 2014

  • Isoprene-Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half-Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers.
    Valente Andreia, Stoclet Gregory, Bonnet Fanny, Mortreux André, Visseaux Marc, Zinck Philippe.
    Angewandte Chemie International Edition, vol. 53, pg. 1-5 (2014) DOI
     
  • Brønsted acid-catalyzed polymerization of ε-caprolactone in water: A mild and straightforward route to poly(ε-caprolactone)-graft-water-soluble polysaccharides.
    Stanley Nicholas, Bucataru Georgiana, Miao Yong, Favrelle Audrey, Bria Marc, Stoffelbach Francois, Woisel Patrice, Zinck Philippe.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 52, pg. 2139-2145 (2014) DOI
     
  • Coordinative Chain Transfer Copolymerization and Terpolymerization of Conjugated Dienes.
    Georges Sébastien, Touré Ahmed Osmane, Visseaux Marc, Zinck Philippe.
    Macromolecules, vol. 47, pg. 4538-4547 (2014) DOI
     
  • Polymyrcene microstructure revisited from precise high-field nuclear magnetic resonance analysis.
    Georges Sébastien, Bria Marc, Zinck Philippe, Visseaux Marc.
    Polymer, vol. 55, pg. 3869-3878 (2014) DOI
     
  • 2013

  • First polymer “ruthenium-cyclopentadienyl” complex as potential anticancer agent.
    Valente Andreia, Garcia Maria Helena, Marques Fernanda, Miao Yong, Rousseau Cyril, Zinck Philippe.
    Journal of Inorganic Biochemistry, vol. 127, pg. 79-81 (2013) DOI
     
  • Coordinative Chain Transfer Polymerization.
    Valente Andreia, Mortreux André, Visseaux Marc, Zinck Philippe.
    Chemical Reviews, vol. 113 (5), pg. 130207123620002 (2013) DOI
     
  • Ring-opening polymerization of lactones using binaphthyl-diyl hydrogen phosphate as organocatalyst and resulting monosaccharide functionalization of polylactones.
    Miao Yong, Phuphuak Yupin, Rousseau Cyril, Bousquet Till, Mortreux André, Chirachanchai Suwabun, Zinck Philippe.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 51, pg. 2279-2287 (2013) DOI
     
  • Balancing crystalline and amorphous domains in PLA through star-structured polylactides with dual plasticizer/nucleating agent functionality.
    Phuphuak Yupin, Miao Yong, Zinck Philippe, Chirachanchai Suwabun.
    Polymer, vol. 54, pg. 7058-7070 (2013) DOI
     
  • Trans-stereospecific polymerization of butadiene and random copolymerization with styrene using borohydrido neodymium/magnesium dialkyl catalysts.
    Ventura A., Chenal T., Bria M., Bonnet F., Zinck P., Ngono-Ravache Y., Balanzat E., Visseaux M.
    European Polymer Journal, vol. 49, pg. 4130-4140 (2013) DOI
     
  • 2012

  • Ring-opening polymerization of cyclic esters initiated by cyclodextrins.
    Miao Yong, Zinck Philippe.
    Polymer Chemistry, vol. 3, pg. 1119 (2012) DOI
     
  • Tuning polyolefins and polydienes microstructure and architecture via coordinative chain transfer polymerization.
    Zinck Philippe.
    Polymer International, vol. 61, pg. 2-5 (2012) DOI
     
  • Highly stereoselective coordination polymerization of β-myrcene from a lanthanide-based catalyst: Access to bio-sourced elastomers.
    Loughmari Saliha, Hafid Abderrafia, Bouazza Aicha, El Bouadili Abdelaziz, Zinck Philippe, Visseaux Marc.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 50, pg. 2898-2905 (2012) DOI
     
  • Precipitation polymerization of ε-caprolactone in water using metal triflates as catalysts.
    Scullion Rachel, Zinck Philippe.
    Polymer Bulletin, vol. 69, pg. 757-763 (2012) DOI
     
  • Isoprene polymerization using a neodymium phenolate pre-catalyst combined to aluminum based co-catalysts.
    Vitorino M.J., Zinck P., Visseaux M.
    European Polymer Journal, vol. 48, pg. 1289-1294 (2012) DOI
     
  • 2011

  • Borohydrido rare earth based coordinative chain transfer copolymerization: A convenient tool for tuning the microstructure of isoprene/styrene copolymers.
    Valente Andreia, Zinck Philippe, Mortreux André, Visseaux Marc.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 49, pg. 1615-1620 (2011) DOI
     
  • Half-lanthanocene/dialkylmagnesium-mediated coordinative chain transfer copolymerization of styrene and hexene.
    Valente Andreia, Zinck Philippe, Mortreux Andre , Bria Marc, Visseaux Marc.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 49, pg. 3778-3782 (2011) DOI
     
  • Polymerization of ɛ-caprolactone using ruthenium(II) mixed metallocene catalysts and isopropyl alcohol: Living character and mechanistic study.
    Valente Andreia, Zinck Philippe, Mortreux André, Visseaux Marc, Mendes Paulo J.G., Silva Tiago J.L., Garcia M. Helena.
    Journal of Molecular Catalysis A: Chemical, vol. 346, pg. 102-110 (2011) DOI
     
  • Access to new carbohydrate-functionalized polylactides via organocatalyzed ring-opening polymerization.
    Miao Yong, Rousseau Cyril, Mortreux André, Martin Patrick, Zinck Philippe.
    Polymer, vol. 52(22), pg. 5018-5026 (2011) DOI
     
  • Sample size dependence of flaw distributions for the prediction of brittle solids strength using additive Weibull bimodal distributions.
    Zinck P.
    Engineering Fracture Mechanics, vol. 78, pg. 1323-1327 (2011) DOI
     
  • 2010

  • Rare earths/main group metal alkyls catalytic systems for the 1,4-trans stereoselective coordinative chain transfer polymerization of isoprene.
    Valente Andreia, Zinck Philippe, Vitorino Marta J., Mortreux A., Visseaux M.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 48, pg. 4640-4647 (2010) DOI
     
  • Reversible coordinative chain transfer polymerization of styrene by rare earth borohydrides, chlorides/dialkylmagnesium systems.
    Zinck Philippe, Valente Andreia, Bonnet Fanny, Violante Ana, Mortreux André, Visseaux Marc, Ilinca Simona, Duchateau Rob, Roussel Pascal.
    Journal of Polymer Science Part A: Polymer Chemistry, vol. 48, pg. 802-814 (2010) DOI
     
  • Organometallic catalysis: From concepts to selected applications.
    Sauthier Mathieu, Zinck Philippe, Mortreux André.
    Comptes Rendus Chimie, vol. 13, pg. 304-314 (2010) DOI
     
  • 2009

  • Catalytic Chain Transfer (co-)Polymerization: Unprecedented Polyisoprene CCG and a New Concept to Tune the Composition of a Statistical Copolymer.
    Valente Andreia, Zinck Philippe, Mortreux André, Visseaux Marc.
    Macromolecular Rapid Communications, vol. 30, pg. 528-531 (2009) DOI
     
  • On the number-average molecular weight of poly(1,4-trans isoprene) determined by conventional GPC.
    Zinck Philippe, Terrier Michaël, Mortreux André, Visseaux Marc.
    Polymer Testing, vol. 28, pg. 106-108 (2009) DOI
     
  • One-step synthesis of polyesters specialties for biomedical applications.
    Zinck Philippe.
    Reviews in Environmental Science and Bio/Technology, vol. 8, pg. 231-234 (2009) DOI
     
  • Functionalization of syndiotactic polystyrene.
    Zinck Philippe, Bonnet Fanny, Mortreux André, Visseaux Marc.
    Progress in Polymer Science, vol. 34, pg. 369-392 (2009) DOI
     
  • 2008

  • Half-lanthanidocenes catalysts via the “borohydride/alkyl” route: A simple approach of ligand screening for the controlled polymerization of styrene.
    Zinck Philippe, Valente Andreia, Terrier Michaël, Mortreux André, Visseaux Marc.
    Comptes Rendus Chimie, vol. 11, pg. 595-602 (2008) DOI
     
  • Thermo-hydrolytic resistance of polyepoxyde - glass fibres interfaces by the microbond test.
    Zinck P, Gérard J F.
    Composites Science < Technology, vol. 68, pg. 2028-2033 (2008)
     
  • Polyepoxyde–water interactions: Influence of the chemical structure of the network.
    Zinck P, Gérard J F.
    Polymer Degradation < Stability, vol. 93, pg. 1231-1238 (2008)
     
  • Dynamics of amorphous and semi-crystalline 1,4-trans-poly(isoprene) by dielectric spectroscopy.
    Cerveny S, Zinck P, Terrier M, Arrese I S, Alegria A, Colmenero J.
    Macromolecules, vol. 41, pg. 8669-8676 (2008)
     
  • New ionic half-metallocenes of early lanthanides.
    Visseaux M., Zinck P., Terrier M., Mortreux A., Roussel P.
    Journal of Alloys and Compounds, vol. 451, pg. 352-357 (2008) DOI