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Synthesis of Segmented Polymer Structures Based on Renewable Resources

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Department of Organic and Macromolecular Chemistry Polymer Chemistry Research Group Synthesis of segmented polymer structures based on renewable resources Sanne DE SMET Promotor: Prof. Dr. Filip Du Prez Ghent, 2016 Thesis submitted to obtain the degree of Doctor of Science: Chemistry Exam Commission Prof. F. Du Prez (promotor, UGent) Prof. R. Hoogenboom (UGent) Prof. S. Van Vlierberghe (UGent) Prof. S. De Wildeman (UGent and University of Maastricht) Prof. M. Meier (Karlsruhe Institute of Technology) Prof. B. Klumperman (University of Capetown) Dankwoord Een doctoraat afronden is een werk van lange adem en vraagt bloed, zweet en (in mijn geval veel) tranen. En hoewel er op de cover van deze thesis enkel plaats was voor mijn naam, besef ik maar al te goed dat ik de eindmeet nooit had gehaald zonder de inzet, steun en energie van de vele mensen rondom mij. Eén voor één verdienen ze een standbeeld, maar een oprechte dankjewel aan het begin van deze thesis leek me al een stap in de goede richting. Allereerst wil ik mijn promotor Prof. Dr. Filip Du Prez bedanken voor de opportuniteit die hij me gaf door me te laten doctoreren in zijn onderzoeksgroep. Hij gaf mij, geen hardcore scheikundige, maar een bio-ingenieur met een fascinatie voor plastiek, de kans om deze fascinatie verder uit te diepen en nog meer verwonderd te staan van de diversiteit en de mogelijkheden van de polymeerwereld. Uiteraard wil ik ook al mijn collega’s bedanken die allemaal stuk voor stuk hebben bijgedragen aan de toffe werksfeer, de hulp op wetenschappelijk gebied en de nodige afleiding op tijd en stond. Graag had ik toch een aantal mensen in het bijzonder vermeld: - Lab manager Bernhard: ik denk dat het moeilijk is om jouw rol in de PCR-groep te onderschatten. Niet alleen hield je de groep draaiende door allerlei technische problemen op te lossen, je stond ons ook bij met raad en daad in de dagelijkse werking. Maar er is nog zo veel meer: bedankt voor de mailtjes die opgevrolijkt werden met wat droge humor, voor de ‘interessante’ ganggesprekken, vooral op vrijdagmiddag. Bedankt om me niet tegen te houden als ik weer enthousiast een toestel wilde opvrolijken met een persoonlijke naam/sticker, bedankt voor alles. - Zophie, in je eerste jaar in de PCR-groep mocht ik je inleiden in de wondere wereld van de polymeren. Onze begeleider/thesisstudent strategie was meer gebaseerd op samenwerken en leren van elkaar dan het ‘ik zeg, jij doet’ principe. Het is mede door deze strategie dat we later eerst fijne collega’s werden en nu nog steeds samenkomen voor een naainamiddag. Je was altijd paraat voor een fijne babbel, een laat-je-frustratie-los gesprek of gewoon wat gelach in het labo. - Oğuz: thank you for bringing back the spark in me, your enthusiasm was contagious. Working together on the ADMET project pushed me to not give up. I still think you’re Oğuzome! - Benjamin, Kevin, Laetitia, Jonas, Steven, Wim, Frank, Bastiaan, Daniël, Stef, Hannes, Niels en iedereen die ik hier vergeet: bedankt voor de gezellige middagmalen, de koffiepauzes, de babbels in de gang, de schrale muziek, de vette schijven tijdens de cleaning days en het luisterend oor. Ik ben hierdoor nog meer van overtuigd dat een job alleen écht leuk kan zijn, met de juiste mensen in de groep. Ik ben blij dat ik in jullie team zat. Dankwoord Alle mensen van het administratief en het technisch personeel van de vakgroep Organische Chemie wens ik te bedanken voor de praktische ondersteuning en de vlotte samenwerking. Verder zou ik graag volgende mensen uit verschillende onderzoeksgroepen bedanken voor hun bijdrage aan mijn doctoraatsonderzoek: - Prof. Martins en Tim voor de NMR metingen - Prof. Hoogenboom voor het gebruik van het DLS-toestel - Prof. Sels en Dr. Dusselier voor de samenwerking rond de functionalisatie van PLA Hoewel het buiten de mensen in mijn ‘wetenschappelijke kring’ onmogelijk was geweest om deze thesis tot een goed einde te brengen, zijn er nog een heleboel anderen die zeker ook een dikke dankjewel verdienen. Ook zonder hen zou ik de eindmeet niet gehaald hebben. In de voorbije jaren werd me vaak gevraagd “Hoe gaat het met je doctoraat?”, “Waar ging je thesis weer over?” of “Heb je al iets ontdekt?” en kwamen er steunende woorden als “Nog even doorzetten, je bent er bijna”. Bedankt aan al mijn vrienden en (schoon)familie voor de interesse en de aanmoedigingen, voor de gezellige avonden uit, de uitstapjes, de babbels, de familiebijeenkomsten op zondag. Een dikke merci aan mijn ouders, zus, broer, schoonbroer en schoonzus en alle kleine pagadders die daarbij horen. Elke vrijdagavond kijk ik uit naar onze spaghetti-avond waar iedereen gewoon zichzelf kan zijn. Hoewel het vaak een drukte van jewelste is, was het voor mij tijdens mijn thesis en is het nu nog steeds een rustpunt in de week. Back to reality, terug naar de dingen die écht van belang zijn. Mama, papa, dank je om me te blijven aanmoedigen en me de kans te geven om deze weg in te slaan. Zoals ze zeggen: save the best for last. Als allerlaatste wil ik graag nog even de tijd nemen om de belangrijkste persoon in mijn leven te bedanken. Je hebt elke stap van mijn doctoraat meegemaakt en was steeds mijn rots in de branding. Je geduld werd vaak op de proef gesteld, maar steeds kon ik bij je terecht voor veel begrip, steun, een dikke knuffel. Tijdens de laatste maanden nam jij meer taakjes over zodat ik me kon concentreren op mijn thesis. Dat ik met jou een winnend lot uit de loterij heb gewonnen, daar ben ik van overtuigd. Kurt, mijn liefje, piefje, poepie, met jou aan mijn zij kan ik alles aan. Bedankt voor alles! Sanne Table of Content Table of Content List of Abbreviations ............................................................................................................................... vii Chapter 1: General Introduction, Aim and Outline ........................................................................... 1 1.1 General Introduction and aim ..................................................................................................... 1 1.2 Outline ......................................................................................................................................... 2 References ............................................................................................................................................... 3 Chapter 2: Theoretical Description ................................................................................................... 7 2.1 Biosourced polymers ................................................................................................................... 7 2.1.1 Introduction and definition ................................................................................................ 7 2.1.2 Renewable resources as raw materials for polymers ......................................................... 9 2.1.2.1 Natural polymers and derivatives ................................................................................... 9 2.1.2.2 Polyhydroxyalkanoates.................................................................................................. 10 2.1.2.3 Polymers produced using monomer from fermentation processes ............................. 10 2.1.3 Conclusion ......................................................................................................................... 15 2.2 Segmented polymer structures and their functions ................................................................. 15 2.2.1 AB block copolymers ......................................................................................................... 16 2.2.2 ABA block copolymers ....................................................................................................... 17 2.2.3 Graft copolymers ............................................................................................................... 18 2.2.4 Other segmented polymer structures ............................................................................... 19 2.3 Synthesis of segmented polymer structures ............................................................................. 19 2.3.1 Introduction ....................................................................................................................... 19 2.3.2 Controlled Radical Polymerization .................................................................................... 20 2.3.2.1 Introduction ................................................................................................................... 20 2.3.2.2 RAFT Polymerization...................................................................................................... 21 2.3.3 Polyesters: different synthetic pathways .......................................................................... 25 i Table of Content 2.3.4 Acyclic Diene Metathesis polymerization ......................................................................... 27 2.3.5 Click reactions .................................................................................................................... 31 2.3.6 Synthetic pathway to obtain segmented polymer structures ........................................... 36 2.4 Segmented structures from renewable resources .................................................................... 40 2.4.1 AB block copolymers ......................................................................................................... 40 2.4.2 ABA triblock copolymers ..................................................................................................
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    (19) TZZ __T (11) EP 2 676 971 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08C 19/02 (2006.01) C08F 36/04 (2006.01) 08.04.2015 Bulletin 2015/15 C08F 236/12 (2006.01) C08F 8/04 (2006.01) (21) Application number: 12173165.7 (22) Date of filing: 22.06.2012 (54) Hydrogenation of a diene-based polymer latex Hydrierung eines dien-basierten Polymer-Latex Hydrogénation d’un latex polymère à base de diène (84) Designated Contracting States: (56) References cited: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB EP-A1- 2 289 621 US-A1- 2006 211 827 GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR • DATABASE COMPENDEX [Online] ENGINEERING INFORMATION, INC., NEW YORK, (43) Date of publication of application: NY, US; 3 October 2011 (2011-10-03), 25.12.2013 Bulletin 2013/52 KONGPARAKUL S ET AL: "Metathesis hydrogenation of natural rubber latex", (73) Proprietor: UNIVERSITY OF WATERLOO XP002689385, Database accession no. Waterloo, Ontario N2L 3G1 (CA) E20113714322330 -& KONGPARAKUL S ET AL: "Metathesis hydrogenation of natural rubber (72) Inventors: latex", APPLIED CATALYSIS A: GENERAL, vol. • REMPEL, Garry L. 405, no. 1-2, 3 October 2011 (2011-10-03), pages Waterloo, Ontario N2T 2H4 (CA) 129-136, XP002690182, ELSEVIER NLD DOI: • PAN, Qinmin 10.1016/J.APCATA.2011.07.039 Waterloo, Ontario N2T 2W9 (CA) • DATABASE COMPENDEX [Online] • Wu, Jialong ENGINEERING INFORMATION, INC., NEW YORK, Waterloo, Ontario N2L 4N2 (CA) NY, US; 15 April 2008 (2008-04-15), MINGOTAUD •LIU,Yin A-F ET AL: "Characterization of the micellar ring Mississauga, Ontario L5B 0E8 (CA) opening metathesis polymerization in water of a norbornene derivative initiated by Hoveyda- (74) Representative: Hollah, Dorothee Grubbs’ catalyst", XP002689386, Database Isenbruck Bösl Hörschler LLP accession no.