Characterisation of Block Copolymers by On-line HPLC- 2020-07-08¢  ¢â‚¬“On-line HPLC-NMR of PS-b-PMMA

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  • Characterisation of Block Copolymers by On-line HPLC-

    NMR

    Vom Fachbereich Chemie

    der Technischen Universität Darmstadt

    zur

    Erlangung des akademischen Grades eines

    Doctor rerum naturalium

    (Dr. rer. nat.)

    genehmigte

    Dissertation

    vorgelegt von

    Pritish Sinha (M.Sc.)

    Aus Kalkutta, Indien

    Berichterstatter: Prof. Dr. H. Pasch

    Mitberichterstatter: PD. Dr. R. Meusinger

    Tag der Einreichung: 14.05.2009

    Tag der mündlichen Prüfung: 29.06.2009

    Darmstadt 2009

    D 17

  • Acknowledgement I wish to extend my deepest appreciation to my research adviser, Prof. Dr. Harald

    Pasch who believed in my abilities as a graduate student and gave me the

    opportunity to work in his research group. I am also thankful to him for providing me a

    challenging research topic and for the liberty I had for performing the research work.

    I would like to thank Dr. Wolf Hiller who introduced me to the field of nuclear

    magnetic resonance spectroscopy as well as the coupling of HPLC-NMR. His

    constant guidance and encouragement has proved invaluable in my research

    activities. I also appreciate him for his moral support, compliments and optimistic

    discussions.

    I would like to express my gratitude to all my former and present colleagues of DKI

    who morally supported me during my stay in the institute as well as for a pleasant

    working atmosphere. Moreover, I would like to appreciate all my friends who made

    my stay in Germany a pleasant one.

    Finally I thank my parents and sister for their encouragement, support and patience

    during the course of my study as well as the PhD work.

  • Diese Arbeit wurde unter der Leitung von Herrn Prof. Dr. Harald Pasch am

    Deutschen Kunststoff-Institut in der Zeit vom Februar 2006 bis zum April 2009

    durchgeführt.

  • Publications:

    1. W. Hiller, P. Sinha, H. Pasch:

    “On-line HPLC-NMR of PS-b-PMMA and Blends of PS and PMMA: LCCC-NMR at

    Critical Conditions of PS”

    Macromol. Chem. Phys., 2007, 208, 1965

    2. W. Hiller, P. Sinha, H. Pasch:

    “On-line HPLC-NMR of PS-b-PMMA and Blends of PS and PMMA: LCCC-NMR at

    Critical Conditions of PMMA”

    Macromol. Chem. Phys., 2009, 210, 605

    Oral presentation:

    1. “Characterisation of poly [(styrene)-co-(methyl methacrylate)] block copolymers by

    on-line hyphenation of liquid chromatography at critical conditions and nuclear

    magnetic resonance spectroscopy”

    3rd International Symposium on the Separation and Characterisation of Natural

    and Synthetic Macromolecules, 31.01-2.02.07, Amsterdam, Netherlands

    2. “Block copolymer analysis by coupled HPLC-NMR”

    15th DKI Colloquium, 30.03.07, Darmstadt, Germany

    3. “Analysis of block copolymers by HPLC-NMR“

    19th DKI Colloquium, 27.03.09, Darmstadt, Germany

    Posters:

    1. “Characterisation of poly (styrene-block-methyl methacrylate) copolymers with

    on-line hyphenation of HPLC-NMR”

    13th International Symposium on Separation Science, 26-29.06.07, High Tatra,

    Slovakia

    2. “Separation and characterisation of PS-b-PI copolymers by different

  • chromatographic techniques”

    21st International Symposium on Polymer Analysis and Characterisation,

    08-11.06.08, Delaware, United States of America

    3. “2D-LC Separation of fatty alcohol ethoxylates simultaneously by endgroup and

    chain length with on-line 1H-NMR”

    10th Annual UNESCO/IUPAC Conference on Macromolecules & Materials,

    08-11.09.08, Mpumalanga, South Africa

    4. “Characterisation of poly (styrene-block-isoprene) copolymers by on-line

    hyphenation of HPLC and 1H-NMR“

    International Symposium ‘Microstructural Control in Free-Radical Polymerisation’

    05-08.10.08, Clausthal, Germany

    5. “Characterisation of blends of PS and PI by HPLC-NMR"

    4th International Symposium on the Separation and Characterisation of Natural

    and Synthetic Macromolecules, 28-30.01.07, Amsterdam, Netherlands

  • CONTENT 1. Summary in German………………………………………………………………...8

    2. Introduction and Motivation………………………………………………………..10

    3. Basic Theoretical Principles……………………………………………………….13

    3.1 High Performance Liquid Chromatography (HPLC)……………………………13

    3.2 Size Exclusion Chromatography (SEC)………………………………………….14

    3.3 Liquid Adsorption Chromatography (LAC)………………………………………15

    3.4 Liquid Chromatography at Critical Conditions (LC-CC)………………………..16

    3.4.1 Analysis of block copolymers by LC-CC…………………………………………18

    3.5 Basic Principles of NMR and direct coupling of HPLC and NMR……………..20

    3.5.1 Basic Principles of NMR…………………………………………………………...20

    3.5.2 1H-NMR experiment………………………………………………………………..23

    3.5.3 13C-NMR experiment………………………………………………………………24

    3.5.4 NMR spectroscopy in a flowing liquid……………………………………………26

    3.5.5 Design of continuous NMR flow probes………………………………………….27

    3.5.6 Solvent suppression………………………………………………………………..29

    3.5.7 Different working modes in HPLC-NMR…………………………………………32

    3.5.8 Purity of HPLC grade solvents…………………………………………………....34

    4. Results and Discussion……………………………………………………………36

    4.1 Analysis of PS-b-PMMA copolymers and blends of PS and PMMA………….36

    4.1.1 Method development for establishing the critical conditions of PMMA………36

    4.1.2 LC-CC-1H-NMR of PS-b-PMMA copolymers at critical conditions of PMMA..38

    4.1.3 Method development for establishing the critical conditions of PS…………...49

    4.1.4 LC-CC-1H-NMR of PS-b-PMMA copolymers at critical conditions of PS…….50

    5. Analysis of 1,4-polyisoprene and 3,4-polyisoprene by using chromatography

    at critical conditions………………………………………………………………..64

    5.1 Development of critical conditions for 1,4-polyisoprene by using solvent

    mixtures…………………………………………………………………………….64

    5.2 On-line coupling of LC-CC-NMR for the analysis of blends of 1,4-PI and

    3,4-PI by operating at the critical conditions of 1,4-PI…………………………65

    6. Analysis of PS-b-PI copolymers………………………………………………….76

    6.1 Method development for establishing the critical conditions of PS by using

    solvent mixtures……………………………………………………………………76

    6.2 LC-CC-1H-NMR of PS-b-PI copolymers at critical conditions of PS………….77

  • 6.3 Comparison of sequential living anionic polymerisation and coupling of living

    precursor blocks for the analysis of PS-b-PI copolymers by on-line HPLC-

    NMR………………………………………………………………………………….79

    6.4 Method development for establishing the critical conditions of 1,4-PI by using

    solvent mixtures…………………………………………………………………….93

    6.5 LC-CC-1H-NMR of PS-b-PI copolymers at critical conditions of 1,4-PI………94

    6.6 Comparison of on-flow HPLC-NMR of PS-b-PI copolymers synthesised by

    sequential living anionic polymerisation and coupling of living precursor blocks

    at critical conditions of 1,4-PI……………………………………………………...95

    7. Analysis of PI-b-PMMA copolymers…………………………………………….107

    7.1 Method development for critical conditions of PI using a single solvent as

    mobile phase………………………………………………………………………107

    7.2 LC-CC-1H-NMR of PI-b-PMMA copolymers at critical conditions of PI……..108

    7.3 Method development for critical conditions of PMMA using a single solvent as

    mobile phase………………………………………………………………………121

    7.4 LC-CC-1H-NMR of PI-b-PMMA copolymers at critical conditions of PMMA. 122

    8. Experimental Part…………………………………………………………………132

    8.1 Chemicals……