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Synthesis of Functionalized Polyamide 6 by Anionic Ring-Opening Polymerization Deniz Tunc

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Synthesis of Functionalized Polyamide 6 by Anionic Ring-Opening Polymerization Deniz Tunc Synthesis of functionalized polyamide 6 by anionic ring-opening polymerization Deniz Tunc To cite this version: Deniz Tunc. Synthesis of functionalized polyamide 6 by anionic ring-opening polymerization. Poly- mers. Université de Bordeaux; Université de Liège, 2014. English. NNT : 2014BORD0178. tel- 01281327 HAL Id: tel-01281327 https://tel.archives-ouvertes.fr/tel-01281327 Submitted on 2 Mar 2016 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Logo Université de cotutelle THÈSE PRÉSENTÉE POUR OBTENIR LE GRADE DE DOCTEUR DE L’UNIVERSITÉ DE BORDEAUX ET DE L’UNIVERSITÉ DE LIEGE ÉCOLE DOCTORALEDE SCIENCES CHIMIQUES (Université de Bordeaux) ÉCOLE DOCTORALE DE CHIMIE (Université de Liège) SPÉCIALITÉ POLYMERES Par Deniz TUNC Synthesis of functionalized polyamide 6 by anionic ring-opening polymerization Sous la direction de Stéphane CARLOTTI et Philippe LECOMTE Soutenue le 30 octobre 2014 Membres du jury: M. PERUCH, Frédéric Directeur de recherche, Université de Bordeaux Président M. HOOGENBOOM, Richard Professeur, Ghent University Rapporteur M. MONTEIL, Vincent Chargé de recherche, Université Claude Bernard Rapporteur M. YAGCI, Yusuf Professeur, Istanbul Technical University Examinateur M. AMEDURI, Bruno Directeur de recherche, Institut Charles Gerhardt Examinateur M. SERVANT, Laurent Professeur, Université de Bordeaux Invité Preamble This PhD had been performed within the framework of the IDS FunMat joint doctoral programme. IDS-FunMat is “International Doctoral School in Functional Materials” funded by ERASMUS MUNDUS Programme of the Europen Union. IDS FunMat PhD School offers PhD project in Functional Material Science which has to be carried out in co-supervision between universities from different countries. In most projects, an industrial partner is also involved. As one of the criteria, PhD candidate must spends at least 6 months in each university and ideally 1.5 year in each of the university. In this PhD project, two partner universities were University of Bordeaux (LCPO, France) and University of Liége (CERM, Belgium), BASF (Ludwingshafen , Germany) was the industrial partner. TABLE OF CONTENTS Acknowledgment…………………......……………………………………..……..….............................i-ii List of Abbreviations………………………………………………………..……..…...........................iii-v General Introduction…………………………………………………………..……..…...........................1 Chapter I. Literature Review: Synthesis and Functionalization of Polyamides Introduction ................................................................................................................... 13 1. Synthesis of aliphatic polyamides ............................................................................ 14 1.1. Synthesis of aliphatic polyamides by polycondensation ..................................... 14 1.2. Anionic ring-opening polymerization of cyclic amides (lactams) ......................... 14 1.2.1. Mechanism of the anionic polymerization of lactams ............................ 15 1.3. Anionic (co)polymerization of ɛ-caprolactam and ω-laurolactam ........................ 24 1.3.1. Homopolymerization of ɛ-caprolactamand -laurolactam .................... 24 1.3.2. Copolymerization of ɛ-caprolactam and -laurolactam ......................... 26 1.3.3. Copolymerization of Lactams and Lactones ............................................ 26 1.3.4. Polyamide-based copolymers with non-polyamide blocks ..................... 27 1.3.5. Industrial processes using AROP of ɛ-caprolactam and -laurolactam .. 28 1.4. Anionic polymerization of other lactams ............................................................ 29 1.4.1. β-lactams ................................................................................................. 29 1.4.2. 2-pyrrolidone ........................................................................................... 30 1.4.3. 2-piperidone ............................................................................................ 31 1.4.4. Bicyclic lactams ........................................................................................ 31 2. Synthesis of aromatic polyamides ............................................................................ 32 2.1. Step-growth condensation polymerization ......................................................... 33 2.2. Chain-growth condensation polymerization ....................................................... 34 2.2.1. Mechanism of the polymerization: synthesis of aromatic polyamides .. 37 2.3. Synthesis of copolymers based on aromatic polyamide by chain-growth polycondensation .............................................................................................. 42 2.3.1. Sequential condensative chain polymerization....................................... 42 2.3.2. Block copolymers by a coupling reaction ................................................ 44 2.3.3. Macro-initiator approach ........................................................................ 47 2.4. Complex architectures of aromatic polyamides .................................................. 49 3. Crosslinking of polyamide 6 ..................................................................................... 50 3.1. Radiation crosslinking of polyamide 6 ................................................................ 50 3.2. Crosslinked polyamide 6 by chemical modification ............................................. 51 3.3. Stimuli Responsive Polymers ............................................................................. 53 3.3.1. pH and thermo responsive groups .......................................................... 53 3.3.2. Photoresponsive groups .......................................................................... 54 3.4. Photoreactions .................................................................................................. 55 3.4.1. Photoisomerization ................................................................................. 55 3.4.2. Photocleavage ......................................................................................... 57 3.4.3. Photodimerization ................................................................................... 57 4. Fluorinated aromatic and aliphatic polyamides ........................................................ 63 4.1. Multilayered film preparation ............................................................................ 64 4.2. Blending hydrophilic and hydophobic polymers ................................................. 65 4.3. Surface modification .......................................................................................... 65 4.4. Incorporation of fluoro-monomer to polyamide by copolymerization ................ 65 4.4.1. Aromatic fluorinated polyamides ............................................................ 66 4.4.2. Aliphatic fluorinated polyamides ............................................................ 67 Conclusion ...................................................................................................................... 70 References ...................................................................................................................... 71 Chapter II. Copolymerization of ԑ-caprolactam and fluorinated derivatives for increased surface hydrophobicity and thermal stability of polyamide 6 Introduction .................................................................................................................... 86 1. Synthesis of polyamide 6 with fluorinated moieties .................................................. 89 2. Rate of polymerization.............................................................................................. 94 3. Polymer characterization by NMR and ATR-IR ........................................................... 95 4. Thermal characteristics of modified polyamide 6 and investigation of degradation mechanism ............................................................................................................... 98 5. Hydrophobicity and Water Uptake Determination .................................................. 106 Conclusion ..................................................................................................................... 109 Experimental and supporting informations .................................................................... 111 Annexe: Supporting Information .................................................................................... 114 References ..................................................................................................................... 121 Chapter III. Synthesis of reversible and irreversible crosslinked polyamide 6 Introduction .................................................................................................................. 128 1. Synthesis of irreversible crosslinked polyamide 6 .................................................... 129 1.1. Synthesis of polyamide 6 ................................................................................. 130 1.2. Synthesis of
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