University of Groningen Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones Araya Hermosilla, Esteban Alejand

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University of Groningen

Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones

Araya Hermosilla, Esteban Alejand

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Publication date: 2019

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Araya Hermosilla, E. A. (2019). Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones. University of Groningen.

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Polymeric surfactants based on the

chemical modification of

alternating aliphatic polyketones

PhD thesis

to obtain the degree of PhD at the University of Groningen

on the authority of the Rector Magnificus prof. E. Sterken

and in accordance with the decision by the College of Deans. This thesis will be defended in public on

Monday 6 May 2019 at 11.00 hours

by

Esteban Alejandro Araya Hermosilla

born on 10 February 1984 in Providencia, Chili

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Supervisor Prof. F. Picchioni Assessment Committee Prof. M. Kobrak Prof. G.J.W. Euverink Prof. R. Rossi

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Polymeric Surfactants Based on the

Chemical Modification of Alternating

Aliphatic Polyketones

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List of Figures

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1.1 Schematic representation of the components of an organic dye molecule,

4-Hydroxyazobenzene. . . 5

1.2 Scheme of aliphatic polyketone. . . 9

1.3 Schematic representation of polyketones chemical modification via the Paal-Knorr reaction. . . 11

1.4 Schematic representation of the Paal-Knorr reaction . . . 11

2.1 Schematic representation of the chemical modification of polyke-tones (PK50) via Paal-Knorr reaction with histamine. . . 15

2.2 Structure of oxolinic acid and flumequine. . . 16

2.3 OA precipitation pH at 1 ⋅ 10−3_{M and 2 ⋅ 10}−4_{M. . . .} ₁₉

2.4 FLU precipitation pH at 1 ⋅ 10−3_{M and 2 ⋅ 10}−4_{M. . . .} ₁₉

2.5 Correlograms obtained by DLS of PK-Im at concentration of 1 ⋅ 10−3_, 1 ⋅ 10−4, and 1 ⋅ 10−5M at different values of pH. . . 21

2.6 Size and zeta potential of particles composed of OA, PK-Im, and FLU and PK-Im as a function of their relative concentration. . . 22

2.7 Size and zeta potential of OA/PK-Im nanoparticles as a function of time for OA/PK-Im at different molar ratios. . . 22

2.8 Size and zeta potential of FLU/PK-Im nanoparticles as a function of time for FLU/PK-Im a different molar ratios. . . 23

3.1 Acid and basic forms of TPPS. . . 29

3.2 Schematic representation of the chemical modification of polyketone 50 via Paal-Knorr reaction with N-(2-hydroxyethyl)ethylenediamine (HEDA). . . 30

3.3 1_{H-NMR spectra of pyrrole-HEDA model compound. . . .} ₃₃

3.4 1H-NMR spectra of PK50 modified with HEDA at different x. . . . 34

3.5 FT-IR spectra of PK50 modified with HEDA at different x. . . 35

3.6 Surface tension graph of PK50-HEDA80 as a functions of pH and concentration. . . 36

3.7 Transition pH of TPPS at a concentration of 1 ⋅ 10−6_{M. . . .} ₃₇

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viii LIST OF FIGURES 3.8 Normalized UV-vis spectra of 1 ⋅ 10−6M TTPS at different pHs. . . 37 3.9 Schematic structure of J-aggregates and H-aggregates formed by TPPS. 38 3.10 Normalized UV-vis spectra of 1 ⋅ 10−6 _{M TTPS in the presence of}

PK50-HEDA80 1 ⋅ 10−4_{M at di}_{fferent pHs. . . .} ₃₉

3.11 Fluorescence spectra of 1 ⋅ 10−6 TTPS in the presence of PK50-HEDA80 1 ⋅ 10−4at different pHs. . . 40 3.12 Transition pH shift of TPPS at 1 ⋅ 10−6in presence of the polymer at

1 ⋅ 10−4_{: PK50-HEDA80, PK50-HEDA60, and PK50-HEDA40. . .} ₄₁

3.13 Normalized visible spectra of 1 ⋅ 10−6_{M TTPS in presence of}

PK50-HEDA60 and PK50-HEDA40 at different pHs. . . 42 3.14 Fluorescence spectra of 1⋅10−6_{M TTPS in presence of PK50-HEDA60. 43}

3.15 Fluorescence spectra of 1⋅10−6M TPPS in presence of PK50-HEDA40. 44 4.1 Acid and base form of TPPS. . . 47 4.2 Schematic structure of J-aggregates and H-aggregates formed by TPPS. 47 4.3 Schematic representation of Paal-Knorr reaction on polyketones with

the amines used in this study. . . 48 4.4 1H-NMR spectra of pyrrole-IM, pyrrole-PI, and pyrrole-HEDA model

compounds. . . 52 4.5 1_{H-NMR and FT-IR spectra of polyketones before and after}

modifi-cation. . . 54 4.6 Surface tension of PK50-IM, PK50-PI and PK50-HEDA as a

func-tion of the concentrafunc-tion at various pH values. . . 56 4.7 Correlograms, size and zeta potential of the polymer solutions at a

concentration of 1 ⋅ 10−4M of functional groups and at different val-ues of pH. . . 58 4.8 Size and zeta potential of PK50-IM interacting with TPPS at di

ffer-ent concffer-entrations. . . 60 4.9 Size and zeta potential PK50PI interacting with TPPS at different

concentrations. . . 60 4.10 Size and zeta potential PK50-HEDA interacting with TPPS at di

ffer-ent concffer-entrations. . . 61 4.11 Normalized UV-vis spectra of TTPS at different concentrations in

the presence of PK50- IM80 1 ⋅ 10−4_{M at di}_{fferent pH. . . .} ₆₃

4.12 Normalized UV-vis spectra of TPPS at a different concentrations in the presence of PK50-PI 1 ⋅ 10−4_{M at di}_{fferent pH. . . .} ₆₄

4.13 Normalized UV-vis spectra of TTPS at different concentrations in the presence of PK50-HEDA 1 ⋅ 10−4M at different pH. . . 65 4.14 Fluorescence spectra of TTPS at 1 ⋅ 10−6_{M in presence of PK50-IM}

at 1 ⋅ 10−4_{M at di}_{fferent pHs. . . .} ₆₇

4.15 Fluorescence spectra of TTPS at 5 ⋅ 10−6_{M in presence of PK50-IM}

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LIST OF FIGURES ix 4.16 Fluorescence spectra of TTPS at 1 ⋅ 10−5M in presence of PK50-IM

at 1 ⋅ 10−4M at different pHs. . . 69 4.17 Fluorescence spectra of TTPS at 1 ⋅ 10−6M in presence of PK50-PI

at 1 ⋅ 10−4M at different pHs. . . 72 4.20 Fluorescence spectra of TTPS at 1 ⋅ 10−6 M in presence of

PK50-HEDA at 1 ⋅ 10−4M at different pHs. . . 73 4.21 Fluorescence spectra of TTPS at 5⋅10−6M in presence of PK50HEDA80

at 1 ⋅ 10−4M at different pHs. . . 74 4.22 Fluorescence spectra of TTPS at 1⋅10−5M in presence of PK50HEDA80

at 1 ⋅ 10−4M at different pHs. . . 75 5.1 Functionalization of aliphatic polyketones with ABA via the

Paal-Knorr reaction. . . 79 5.2 1_{H-NMR and ATR FT-IR spectra of PK50ABAx at di}_{fferent values}

of x. . . 83 5.3 Optical images of 10−3_{M of PK50ABAx at basic and acid pH, and}

correlograms obtained upon titration of the corresponding basic so-lutions with HCl, for different values of x. . . 83 5.4 1_{H-NMR spectra in D}

2O of TTC 10−3M, PK50ABAx 10−2M, and

their corresponding mixtures at different x values . . . 85 5.5 600 MHz NOESY spectra in D2O of 10−3M of TTC in the presence

PK50ABA37, PK50ABA53, and PK50ABA69. . . 86 5.6 Optical images of samples containing 10−2_{M of PK50ABA37,}

PK50-ABA53, and PK50ABA69. . . 87 5.7 Apparent size (left) and zeta potential (right) of TF nanoparticle

sam-ples containing PK50ABA37, PK50ABA53, and PK50ABA69 after reduction of variable amounts of TTC with ASC. . . 88 5.8 Optical images after reduction of 5 ⋅ 10−4_{M of TTC with ASC in the}

presence of PK50ABA37, PK50ABA53, and PK50ABA69 at acid and basic pH. . . 89 6.1 Polyketones modified with HEDA and ABA. . . 94 6.2 Surface tension graph of PK50-HEDA and of PK50-ABA as a

func-tions of pH and concentration. . . 96 6.3 Emulsion stability in a function of the concentration of PK50-HEDA

and pH. . . 97 6.4 Stability of the emulsions produced with PK50ABA at a

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x LIST OF FIGURES 6.5 Phase inversion point of emulsions assisted by PK50HEDA at di

ffer-ent concffer-entrations. . . 98 6.6 Possible products of the reaction CO2with epoxides. . . 100

6.7 Scheme of a catalytic cycle via the cooperative activation of epoxide with a Lewis acid (Mg) and a nucleophile (Br−_{ion). . . 101}

6.8 Schematic representation of a polyketones about to undergo a Paal-Knorr reaction with IM and the alkylation of imidazole group. . . . 102 6.9 Schematic representation of a polyketones about to undergo a

Paal-Knorr reaction with IM, FU and the alkylation of imidazole group. . 103 6.10 1_{H-NMR spectrum of pyrrole-imidazole model compound and after}

the alkylation of the imidazole group. . . 107 6.11 1H-NMR spectrum of PK50, PK30 modified with IM and PK50

modified with IM and FU. . . 109 6.12 Mechanism proposed for synthesis of cyclic carbonates through the

cyclic intermediate using inonic liquids immobilized onto polyketones.110 6.13 1H-NMR spectrum of a reaction aliquot from the reaction of CO2

with styrene oxide, CO2with 1,2-epoxyhexane. . . 113

6.14 FT-IR spectrum of a reaction aliquot from the reaction of CO2with

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List of Tables

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2.1 Size, PDI values, and zeta potential of PK-Im aggregates at different

pHs at a PK-Im concentration of 1 ⋅ 10−3_{M. . . .} ₂₅

2.2 Size, PDI values, and zeta potential of PK-Im aggregates at different pHs at a PK-Im concentration of 1 ⋅ 10−4M. . . 25

2.3 Size, PDI values, and zeta potential of PK-Im aggregates at different pHs at a PK-Im concentration of 1 ⋅ 10−5M. . . 26

2.4 Final pH and component concentration of the formulation containing OA and PK-Im. . . 26

2.5 Final pH and component concentration of the formulation containing OA and PK-Im. . . 26

3.1 Amounts in the feed and carbonyl conversion (x) in the Paal-Knorr reaction between PK50 and HEDA. . . 32

4.1 Functionalization of PK50 with HEDA, IM, and PI . . . 50

5.1 PK50 and ABA feed ratios and the corresponding x. . . 81

6.1 Functionalization of PK50 and PK30 with IM. . . 105

6.2 Alkylation of PK50IM and PK30IM. . . 105

6.3 Cyclic carbonates conversion by PK50IM and PK30IM. . . 111

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University of Groningen Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones Araya Hermosilla, Esteban Alejand