definitieve opzet Book of abstracts SPOC 02062020

Book of abstracts
Specialization Polymer
and Organic Chemistry
2019-2020
Academie voor de Technologie van
Gezondheid en Milieu
ATGM
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2

Preface
“Everything is uncertain” was what the students
within the Polymer and Organic Chemistry
specialization at ATGM had to deal with. This is the
book of abstracts of the specialization Polymer
and Organic Chemistry 2019-2020 of Avans
University of Applied Sciences. This year, the
Specialization Polymer and Organic Chemistry
went differently than expected. But that doesn’t
make the book of abstracts less fun. In this book of
abstract we present the research projects we had
prepared before the Corona crisis started. After
13 th of March our plans to do experiments in the
labs changed drastically as school and the
laboratory shut down. As book of abstracts
commission we still wanted to make this book so
that we and our students' colleagues could have a
souvenir of these crazy times during our
specialization projects. These studies come from
various research collaborations from Avans
University of Applied Sciences with external
research institutions and companies. This book of
abstracts is divided into six project groups where
each student had his/her own project. We hope
you enjoy this book of abstracts and we would like
to welcome you at the online poster session that
will be celebrated at the end of SPOC 2019-2020.
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4

Index
Preface 3
32SPOC01 – Begeleider Kees Kruithof
Derivatization of the phenol groups of curcumin
Curcumin the dye of tomorrow?
Synthesising curcumin ester derivates via a ‘green’ Steglich esterification as a
new yellow biobased colorant
32SPOC02 – Begeleider Betty Oostenbrink
The influence of chain length on the viscosity of polyvinyl acetate
The Effects of Molecular Weight on Polymer Properties
The influence of chain length on the Weissenberg effect of poly methyl
methacrylate
Ring-opening polymerisation of ε-Caprolactone
The effect of the chain length of polymers and their properties
7
9
10
11
12
14
15
16
17
18
32SPOC03 – Paula Contreras Carballada
[NiFe]-hydrogenase ligand synthesis
Development of a [NiFe]-hydrogenase analog for the catalysed production of
hydrogen
A sustainable synthesis of FK866
Three-step synthesis of β-lactame used in antibiotics
A sustainable synthesis of FK866
Synthesis of FK866 for cancer treatment as a NAMPT inhibitor
32SPOC04 – Sonny van Seeters
A study of RAFT agents
Polymerization and epoxidation of cardanol
Macro-RAFT emulsion polymerization of styrene
Design and Synthesis of RAFT Agents used for the Polymerisation of
Styrene Analogues
32SPOC05 – Nishant Sewgobind
Perkin synthesis of butylidene phthalide under reduced pressure
A Natural Medicine
Synthesis of different N-carboxyanhydrides (NCAs) for the polymerization to a
polypeptide block copolymer
Synthesis of L-lysine into a gelifyer
A Gelifyer For Cosmetic Purpose
32SPOC06 – Jack van Schijndel
Photo-catalyzed polymerization of isobutyl vinylether in batch & flow
Synthesis Of Curcumin
Synthesis Of Bisdemethoxycurcumin and alkylation of the central carbon atom
A synthesis of curcumin and related compounds
Photo-Catalyzed Flow and Batch Polymerization of Ethyl Vinyl Ether
19
21
22
23
24
25
26
27
29
30
31
32
33
35
36
37
38
39
40
42
43
44
45
46
Epilogue
Authors Book of Abstract SPOC 2019-2020
47
48
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6

32SPOC01
Kees Kruithof
Foto
docent
“Als we precies wisten wat we in
het lab aan het doen waren
noemden we het toch geen
onderzoek doen?”
~Kees Kruithof
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8

32SPOC01
Kees Kruithof
Derivatization of the phenol
groups of curcumin
Mick Hamers
Curcumin the dye of tomorrow?
Mike van der Kleij
Synthesising curcumin ester
derivates via a ‘green’ Steglich
esterification as a new yellow
biobased colorant
Aukje Laurijssen
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10

Derivatization of the phenol groups of curcumin
Mick Hamers
Keywords: Curcumin, acetylation, silylation
Abstract
Curcumin is a natural colorant that can be found in the
turmeric plant. Curcumin also has anti-tumor and antiinflammatory
properties. This makes curcumin a very
popular substance to study. The possibilities of curcumin as
colorant have not been studied as much. This is probably
due to curcumin degrading very fast under the influence of
UV-light. In order to prevent this the phenol groups in the
structure of curcumin could be derivatized. In the figure
below a few examples of these reactions are shown.
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Expected Results
Literature
Mohammad M. (2013)Efficient and Rapid Solvent-Free Acetylation of Alcohols,
Phenols, and Thiols Using Catalytic Amounts of Sodium Acetate Trihydrate.
JournalofChemistry .
11

Curcumin the dye of tomorrow?
Mike van der Kleij
Keywords: Curcumin, Rosocyanin, coloring agent, stability, colorant
Abstract
Curcumin is a natural dye with a yellow color. The research
group wants to use curcumin as a coloring agent, but
curcumin quickly degrades because of light through
autoxidation. This process is due to keto – enol
tautomerism, one of the forms ensures that the autoxidation
takes place, therefore this center will be protected with a
boron complex, this will be made with boric acid. The name
of this substance is rosocyanin and it is much more stable
than curcumin. The substance is weak against basic
medium. Therefore, an acetylation will be performed on the
rosocyanin to investigate whether this has an effect on the
half-life of rosocyanin in basic environment.
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Expected Results
Rosocyanine is a complex created by the reaction between boric acid and
curcumin. This complex is according to the literature more stable than curcumin
because there is no longer any keto-enol tautomerism in the center. Because of the
complex curcumin decomposes at 250 degrees Celsius. The is not stable in basic
environment, nor is it 100% stable in acidic environment,
it would have a dark green color. In acid it would be red
and in base it would be temporarily blue. Whether the
acetylation has an effect on the stability in the basic
medium will depend on whether the stability depends on
the alcohol groups that are protected. These groups
are the reason that the reaction starts during autoxidation.
Literature
Jeena John et al; Kinetics and Mechanism of the Thermal and Hydrolytic
Decomposition Reaction of Rosocyanin; Wiley Periodicals, Inc. Int J Chem Kinet 50;
(2018) 164–177
12

Synthesising curcumin ester derivates via a ‘green’
Steglich esterification as a new yellow biobased
colorant
Aukje Laurijssen
Keywords: Curcumin, Steglich esterification, CUR-KZ ester derivates, biobased colorant
Abstract
The Centre of Expertise is currently investigating using
curcumin as a natural dye for bioplastics. Unfortunately
curcumin is light sensitive and loses its yellow color rapidly.
To improve the UV-stability of curcumin research is being
made to investigate if conversion of the hydroxyl groups into
other functional groups, such as esters, lead to a more
stable product 1 .
Photo
The goal is to synthesize curcumin-t-cinnamic acid ester
derivates via a ‘green’ Steglich esterification with a
minimum yield of 90% or higher 3456 . The hypothesis is a
more stable product with an intense yellow color which will
be suitable as a biobased colorant for bioplastics 789 .
Expected Results
Reaction mechanism
‘green’ Steglich esterification
Literature
1 Gordon et al. The J. of bio. chem. 2015;290(8):4817-4828. 2. Kolonko et al. Bioorg. & Med. Chem. 2018;26(19):5291-
5298. 3. Srivastava et al. J. Mol. Struc, 2016;1117:173-180 4. Srivastava. et al. J. Mol. struc. 2017;1141:678-686. 5.
Srivastava et al. J. mol. struc. 2015;1109:58-66. 6. Dicks AP. J. Chem. Edu. 2004; 81:1488-1491 7. Holser R J. Am. Oil
Chem. Soc. 2008; 85(3):221-225 9. Rojsitthisak P et al. Molecules 2011; 16(2):1888-1900
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32SPOC02
Betty Oostenbrink
Foto
Docent
“If someone doesn't value evidence, what
evidence are you going to provide to prove
that they should value it? If someone doesn’t
value logic, what logical argument could you
provide to show the importance of logic?” –
Sam Harris
~ Betty Oostenbrink
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32SPOC03
Betty Oostenbrink
The influence of chain length on the
viscosity of poly vinylacetate
Ilse Joosen
The Effects of Molecular Weight on
Polymer Properties
Thomas de Crom
The influence of chain length on the
Weissenberg effect of poly methyl
methacrylate
Romy van Dongen
Ring-opening polymerisation of -
Caprolactone
Fabian van Acker
The effect of the chain length of
polymers and their properties
Christiaan Verdonk
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18

The influence of chain length on the viscosity of
polyvinyl acetate
Ilse Joosen
Keywords: Emulsion polymerisation, chain length, viscosity, poly vinylacetate
Abstract
Many properties of polymers depend on the chain length.
Many students are not aware of this. In order to make this
connection visible to students, Avans University of Applied
Sciences asked to make a chemical experiment, by which
students can see the connection between different
properties and the different chain lengths. The aim of this
research is to measure various properties, such as Tg, Mn,
Mw, viscosity, film formation and tensile strength relative to
the chain length of the polymer polyvinyl acetate. The
polymer will be synthesized by emulsion polymerization.
The polymerization will vary in temperature and initiator
(potassium persulfate) concentration.
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Expected Results
The polymer polyvinyl acetate is expected to be synthesized by an emulsion
polymerization. The synthesized polymer polyvinyl acetate will have a molecular
weight of about 1000 kg / mole. The Tg of polyvinyl acetate will be approximately
between 30 and 45 ° C [1]. The Tg was expected to be lower at low values and to
reach a limit value at high values. This can be explained with the Flory-Fox
equation [2]. When the molecular weight increases film formation will form more
easily and tensile strength and viscosity will increase as well. Finally, it is
expected that after the 20 experimental days a chemical experiment can be set up
by which the relationship between different properties and the chain length of the
synthesized polymer can be clearly shown.
Literature
[1] CAMEO. (2016, May 10).CAMEO. http://cameo.mfa.org/wiki/Polyvinyl_acetate
[2] Leslie H. Sperling,“Introduction to Physical Polymer Science”,Wiley,Ed. 4,
2005.
19

The Effects of Molecular Weight on Polymer
Properties
Thomas de Crom
Keywords: Polymers, Tensile strength, PBMA, Polymer films
Abstract
The properties of polymers are dependent on a broad
spectrum of parameters. One highly overlooked parameter
is the degree of polymerisation (Pn) of the polymers. The
goal of this project was to setup an undergraduate level
experiment to give insight on the effects of the molecular
weight on the (mechanical) properties of
poly(butylmethacrylate). A range of polymer
films with variable molecular weights were to
be synthesised using a variation of initiator
concentrations and different polymerisation
techniques. The polymer films were
analysed using GPC/SEC, DSC and tensile
tests.
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Expected Results
An increase in initiator concentration will lower the
kinetic chainlength based on polymer kinetics (v ∝
1 Τ [I] ). Based on the Flory-Fox equation, an
asymptotic correlation is expected between the
molecular weight of the polymer and the glass
transition temperature (Tg) (figure 1) [1] . An
asymptotic increase isalso expected for the ultimate
tensile strength (UTS)of the polymer film (figure
2) [2] .
Figure 1, Correlation Tg and Mw [1]
Figure 2, Correlation UTS and Pn [2]
Literature
[1] Hitachi (1995), DSC Measurements of Polystyrene.
[2] Nunes, R. W., Martin, J. R., & Johnson, J. F. (1982). Influence of molecular
weight and molecular weight distribution on mechanical properties of polymers.
Polymer Engineering and Science, 22(4), 205–228. doi:10.1002/pen.760220402
20

The influence of chain length on the Weissenberg
effect of poly methyl methacrylate
Romy van Dongen
Keywords: Suspension polymerisation, chain length, viscosity, PMMA
Abstract
The chain length of a polymer has a great influence on the
mechanical properties of polymers. Students are not fully
aware of this in their practical experience. The aim of the
research was to propose a chemical experiment, where
students were able to determine and discover the link
between mechanical properties and the chain length from a
polymer. The results were measured such as Mn, Mw and the
Tg. Another important part of the research was to show the
visco-elastic effects from the polymer; as the Weissenberg
effect. The polymer will be synthesized by emulsion
polymerization. The polymerization will vary in temperature
and monomer (methyl methacrylate) concentration.
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Expected Results
Poly methyl metacrylate is expected to be synthesized by an suspension
polymerization. The expected molecular weight will be about 1,000,000 g/mole at
least. The Tg of poly methyl metacrylate will be approximately around 105 ° C [1].
The Tg is expected to increase if the molecular weight (and thus chain length)
increase. The viscosity is also expected to increase with increasing molecular
weight. A higher molecular weight and viscosity are more suitable for the
Weisenberg effect. The Weissenberg effect requires a polymer with pseudoplastic
properties and shear thinning behaviour from the polymeric solution.
Literature
[1] W. Lyoo, „Preparation of High Molecular Weight Poly(methyl methacrylate)
with High Yield by Room Temperature Suspension Polymerization of Methyl
Methacrylate,” Fibers and Polymers, vol. 5, nr. 1, pp. 75-81, 2004.
21

Ring-opening polymerisation of -Caprolactone
Fabian van Acker
Keywords: Polymers, Polycaprolactone, Ring-opening polymerisation, Non-metal
Abstract
Ring-opening polymerisation is difficult to carry out, because
of the strict conditions that are required. The first goal of this
project was to aggregate knowledge about the non-metal ringopening
polymerisation of -caprolactone and practicable.
The polymers were analysed using SEC, DSC and TGA.
The second goal was to develope a practicum for second year
HBO students, which could give a better understanding of the
different phase states in which polymers can be found. These
different physical forms such as rubberphase, were illustrated
by video’s, so that it became visual.
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Figure 1. Propagation of cylcopentadienyl sodium with e-caprolactone.
Expected Results
The ring-opening polymerization of polycaprolactone is a
sensitive synthesis, requiring all steps to be anhydrous.
Due to the accuracy, the preparation took a long time.
As a result, polycaprolactone was polymerized within 60
minutes with an M w of 11.6 x 10 4 gram per mol, DPI of
1.4 and a conversion of 98%. [1] The practical proposal
that is made for the second year students has several
short experiments with poly-caprolactone. In addition,
the experiments are feasible by the student itself, which
stimulates the learning process of the phases. [2]
Figure 2. DSC & TGA of polycaprolactone.
Literature
[1] Labet, M.; Thielemans, W. Synthesis of Polycaprolactone : A Review W. 2009,
3484–3504. https://doi.org/10.1039/b820162p.
[2] Rodriguez, F. Classroom Demonstrations of Polymer Principles. No. 1, 784–788.
22

The effect of the chain length of polymers and their
properties
Christiaan Verdonk
Keywords: Polystyrene, Polymerization, Bulk polymerization, Weissenberg effects
Abstract
There are a lot of different
polymers, and even if the chain
length is different, the properties
of the polymers are not the same.
The aim of this project is to create
an experiment with different chain
lengths to investigate the physical
and mechanical differences. One
of the experiments you can
demonstrate with high molecular
weight polymers is the
Weissenberg effect, also known
as the rod climbing effect.
Photo
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Expected Results
By a bulk polymerization of polystyrene the conversion
increases by a conversion of 40%. The viscosity of the
solution increases rapidly and the solution can not lose
the formed heat so it is important to stop the reaction
after 40% conversion (figure 1). [1] After this conversion
there is a chain length of 31*10 3 monomers formed. The
second figure shows the difference between the Tg and
the chain length.
Literature
[1] Yamazoe, H.; Zetterlund, P. B.; Yamada, B.; Hill, D. J. T.; Pomery, P. J.
Free‐Radical Bulk Polymerization of Styrene: ESR and Near‐Infrared Spectroscopic
Study of the Entire Conversion Range. Macromolecular Chemistry and Physics
2001, 202, 824-829.
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24

32SPOC03
Paula Contreras Carballada
"Nicht alles, was zählt, kann
gezählt werden, und nicht alles,
was gezählt werden kann,
zählt". A. Einstein.
~Paula Contreras Carballada
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26

32SPOC03
Paula Contreras Carballada
[NiFe]-hydrogenase ligand
synthesis
Robin van Damme
Development of a [NiFe]-
hydrogenase analog for the
catalysed production of hydrogen
Lex Jelier
A sustainable synthesis of FK866
Lorenzo de Bie
Three-step synthesis of β-lactame
used in antibiotics
Matthias de Baat
A sustainable synthesis of FK866
Patrick Ippel
Synthesis of FK866 for cancer
treatment as a NAMPT inhibitor
Joyce Boudewijns
27

[NiFe]-hydrogenase ligand synthesis
Robin van Damme
Keywords; [NiFe]-hydrogenase, biohydrogen, electrocatalysis, biomimic
Abstract
To transition from fossil based fuels
to a cleaner form of energy,
biohydrogen has been a running
candidate for the past few years.
he means to produce biohydrogen
are nevertheless not very green. In recent years
scientist have looked at hydrogenase enzymes and
have found ways to mimic these enzymes. One of the
most promTising mimics is the one of [NiFe]-
hydrogenase. In this study, a ligand used for the nickelion
in the nickel-iron complex will be synthesized via
two methods: method A (thioureum) and method B
(thioacetic acid).
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Expected Results
The expected FTIR spectrum, H-NMR spectrum and yield of the overall
synthesis of hexakis(4-mercapto-3,3-methyl-2-thiabutylmethyl)benzene is
given.
FTIR:
3000-2840 cm -1 (CH alkene), 2000-1650 cm -1 (CH, aromatic), 1450 and
1375 cm -1 (CH 3 , methyl), 2600-2550 cm -1 (SH, thiol). Information from [1]
Literature
[1] Infrared Spectroscopy Absorption
Table. https://chem.libretexts.org/Bookshelves/Ancillary_Materials/Reference/Refere
nce_Tables/Spectroscopic_Parameters/Infrared_Spectroscopy_Absorption_Table
28

Development of a [NiFe]-hydrogenase analog for the
catalysed production of hydrogen
Lex Jelier
Keywords; [NiFe]-hydrogenase, hydrogen production, catalyst, clean energy
Abstract
Due to the current energy transition,
the demand for renewable energy
production is increasing, as is a way
to store this energy. One of the most
promising forms of energy storage
is hydrogen gas. However, the efficiency of hydrogen
production is still low and the use of traditional catalysts
such as platinum is not feasible on a large scale. To
solve this problem, we are looking at nature that uses
the enzyme [NiFe]-hydrogenase to produce hydrogen.
In this study, an new analog of this enzyme will be
synthesised as shown in Figure 1.
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Expected Results
The final product has been synthesized by 5 synthesis steps, with the
yield from start to end product being 56% [1].
The signals obtained from the final product should be the following:
1
H-NMR chemical shift of δ 3.73 (s, 12H, Ph-CH2-S-), 2.71 (d, 3J = 8.4
Hz, 12H, -CH2-SH), 1.62 (t, 3J = 8.4 Hz, 6H, -SH), 1.39 (s, 36H, CH3).
FTIR 3000-2800 (-CH2- and CH3, alkane), 2600-2550 (S-H, thiol), 1600-
1400 (C-C, aromatic).
Literature
[1] J. Verhagen, D. Ellis, M. Lutz, A. Spek, and E. Bouwman, “Synthesis,
characterisation and crystal structures of new nickel complexes in S4 coordination
spheres; an unprecedented rearrangement during ligand synthesis,” J. Chem. Soc.
Dalt. Trans., Mar. 2002
29

A sustainable synthesis of FK866
Lorenzo de Bie
Keywords; Energy metabolism, FK866, NAD, NAMPT inhibitor
Abstract
An anti-tumor agent FK866 is a widely described drug
that promotes inhibition of the enzyme NAMPT in the
salvage reaction pathway, thereby reducing the NAD +
level. As a result, the apoptosis (controlled cell death)
of the tumor cells will be initiated[1].
In this research the component FK866 is synthesized
with aim of optimizing
the synthesis so that the
synthesis is less harmful
to humans and the
environment.
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Expected Results
Yield: 50-90%
per reaction
step [1]
[1] [2] 1 H NMR (300 MHz) (CDCl3): d=8.72 (br s, 1-H), 8.56 (br s, 1-H),
7.76 (d, 1-H), 7.59 (d, 1-H), 7.40–7.35 (m, 5-H), 7.32–7.28 (m, 1-H), 6.46
(d, 1-H), 5.98 (br t, 1-H), 4.69 (br d, 1-H), 3.72 (br d,1-H), 3.37 (q, 2-H),
2.95 (br t, 1-H), 2.72 (br t, 1-H), 1.81 (br s, 3-H), 1.63–1.51 (m, 4-H), 1.40–
1.25 ppm (m, 4-H)
Literature
[1] U. Galli; E. Ercolano; L. Carraro; et al. Synthesis and biological evaluation of isosteric analogues
of FK866, an inhibitor of NAD salvage. ChemMedChem 2008, 3, 771-779.
[2] H. You; H. S. Youn; I. Im; et al. Design, synthesis and X-ray crystallographic study of NAmPRTase
inhibitors as anti-cancer agents. European journal of medicinal chemistry 2011, 46, 1153-1164.
30

Three-step synthesis of β-lactame used in
antibiotics
Matthias de Baat
Keywords; β-lactam, Antibiotic, Desilylation agent, Potassium superoxide
Abstract
Due to bacterial resistance against antibiotics, new
antibiotics have to be synthesized. One of the
methods is synthesizing the β-lactam by a three-step
synthesis with the desilylation by Tetra-nbutylammoniumfluoride.
The problem of this method
is the presence of water. The goal of this research is
to synthesize the β-lactam by a different desiylation
agent. The first step is synthesizing the nitrone, with a
yield of 88% and relatively pure crystalline product.
The nitrone was sillylated to form a yellow oil with a
yield of 96%. The product should be desilylated by
Potassium superoxide, which will lead to the
formation of the β-lactam.
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Expected Results
Literature
[1] Inouye, Y. et al., Bulletin of the Chemical Society of Japan, 1979, 52 (12), 3763-3764.
[2] Ahn, C. et al., Journal of Organic Chemistry, 1994, 59 (21), 6282-6286.
[3] Torisawa, Y. et al., Tetrahedron Letters, 1979, 21, 1865-1868.
31

A sustainable synthesis of FK866
Patrick Ippel
Keywords; FK866, Synthesis, green chemistry
Abstract
FK866 is a potential anti-cancer drug and currently only
one synthesis pathway has been made to this
substance. This research will look at a greener
alternative route to this possible drug, whereby the
intermediate - (4-aminobutyl) -1-piperidinyl (phenyl)
methanone will be synthesized. This is done by
replacing various harmful substances, for example
NaN3, with another greener component. Then the
syntheses will be carried out, after each step the
product obtained is separated by column
chromatography. The current route is shown below.
The total conversion rate is estimated at 55% [1-4]
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Expected Results
Literature
[1]Galli, U., Ercolano, E., Carraro, L., Blasi Roman, C. R., Sorba, G., Canonico, P. L., ... & Billington, R. A. (2008). Synthesis and biological evaluation of isosteric
analogues of FK866, an inhibitor of NAD salvage. ChemMedChem: Chemistry Enabling Drug Discovery, 3(5), 771-779.
[2] Gillig, A., Majjigapu, S. R., Sordat, B., & Vogel, P. (2012). Synthesis of a C‐Iminoribofuranoside Analog of the Nicotinamide Phosphoribosyltransferase (NAMPT)
Inhibitor FK866. Helvetica Chimica Acta, 95(1), 34-42.
[3] Sommen, G. L., Linden, A., & Heimgartner, H. (2005). First synthesis of a selenazepane. Tetrahedron letters, 46(39), 6723-6725.
[4] Saulnier, M. G., Zimmermann, K., Struzynski, C. P., Sang, X., Velaparthi, U., Wittman, M., & Frennesson, D. B. (2004). Microwave-assisted synthesis of primary
amine HX salts from halides and 7 M ammonia in methanol. Tetrahedron letters, 45(2), 397-399.
32

Synthesis of FK866 for cancer treatment as a
NAMPT inhibitor
Joyce Boudewijns
Keywords; cancer treatment, inhibitor, FK866, NAD+
Abstract
Cancer is the second leading cause of death in the
world. It is a disease of the genetics in cells. This
causes the cells to start growing rapidly and evade
apoptosis. For the growth the cells need a lot of energy
and they provide this with glycolysis. NAD+ is needed
for this process and is provided by three biosynthesis
pathways. In one of these pathways an enzyme,
NAMPT, is overexpressed and ‘recycles’ NAD+. FK866
is possibly an inhibitor for NAMPT. In this study a
precursor, N-benzoyl-4-piperidinebutanamine, for
FK866 will be synthesized with a greener and safer
approach.
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Expected Results
For the last synthesis a yield of 75% [1] was predicted. N-benzoyl-4-
piperidinebutanamine is supposed to be a yellow oil. The predicted 1 H-
NMR is shown in Figure 1. According to literature the two hydrogen atoms
that form the primary amine have a shift of 2 ppm [2]. In the predicted
spectrum there is also a peak at about 3,2 ppm.
There were no hydrogen atoms that correspond
with this peak in the literature[2][3].There are no
predicted FT-IR spectra, but the literature says
there signals at the following wavenumbers: 3436
(broad), 2923,2853, 1601, 1447, 1124, 711 cm -1 [2].
Literature
[1] Saulnier, M. G.; Zimmermann, K.; Struzynski, C. P.; Sang, X.; Velaparthi, U.; Wittman, M.; Frennesson, D. B. Tetrahedron Lett. 2004,
45 (2), 397–399.
[2] Galli, U.; Ercolano, E.; Carraro, L.; Blasi Roman, C. R.; Sorba, G.; Canonico, P. L.; Genazzani, A. A.; Tron, G. C.; Billington, R. A.
ChemMedChem 2008, 3 (5), 771–779.
[3] Gillig, A.; Majjigapu, S. R.; Sordat, B.; Vogel, P. Helv. Chim. Acta 2012, 95 (1), 34–42.
[4] Predicted NMR data calculated using Advanced Chemistry Development, Inc. (ACD/Labs) Software
33

34

32SPOC04
Sonny van Seeters
Foto
Docent
Verandering blijkt helemaal niet zo moeilijk te zijn en creativiteit wordt
makkelijk bereikt als er een set beperkingen wordt opgelegd. Darwin
zei het al: "Het zijn niet de sterkste of slimste die overleven, maar
diegene die zich het beste aanpassen aan een veranderende
omgeving" . Blijf jezelf dus uitdagen en leg een beperking op, dan word
je creatiever en zul je sneller met meer kwaliteit jouw doel bereiken.
~ Sonny van Seeters
35

36

32SPOC04
Sonny van Seeters
A study of RAFT agents
Nard Schellekens
Polymerization and epoxidation of
cardanol
Merel Schram
Macro-RAFT emulsion polymerization
of styrene
Bas van der Linden
Design and Synthesis of RAFT
Agents used for the Polymerisation
of Styrene Analogues
Remco Neutelings
37

A study of RAFT agents
Nard Schellekens
Keywords; RAFT, Polymerisation, Rgroups, Zgroups
Abstract
A reliable method to synthesise polymers is via RAFT
(Reversible Addition Fragmentation Chaintransfer)
polymerisation. In this review all kinds of RAFT agents will
be studied theoretically on their characteristics by
applying them to the polymerisation of biobased styrene.
Some main comparison properties are the molecular
weight distribution, the polydispersity, the time of the
polymerisation, the yield of the desired product. The
RAFT agents will have different R and Z groups, each
group has its own advantages and disadvantages. The
most important Z-groups are the dithioesters,
dithiocarbamates and the trithiocarbonates and for the R-
groups cyanide, alkanes and phenyl derivatives
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Expected Results
Table 1: The comparison of
some RAFT agents regards
the time, molecular weight
distribution and conversion
Literature
D. Keddie, G. Moad, E. Rizzardo en S. Thang, „RAFT Agent Design and
Synthesis,” Macromolecules, vol. 45, nr. 13, pp. 5321-5542, 2012.
38

Polymerization and epoxidation of cardanol
Merel Schram
Keywords; Epoxy resin, Cardanol, CSNL, Biobased
Abstract
This research investigates whether cashew nut shell
liquid or cardanol (figure 1 & 2) [1] can act as a
biobased substitute for bisphenol A in epoxy resins.
First, cardanol is epoxidized and then crosslinked/polymerized
with citric acid and triethylenamine.
The epoxidized cardanol is crosslinked with 2 agents
so that the difference in properties can be seen. The
difficult part of the research is the epoxydation of
cardanol in connection with the side reactions.
Including the acid catalysed ring opening of the formed
epoxy group that could take place. The products are
analysed with NMR, FTIR and DSC. [1]
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Expected Results
Literature
[1] Caillol, S. (2018). Cardanol: A promising building block for biobased polymers and additives. Current Opinion in
Green and Sustainable Chemistry, 14, 26–32. doi:10.1016/j.cogsc.2018.05.002
[2] Z. Liu et al, "Synthesis of Epoxidized Cardanol and Its Antioxidative Properties for Vegetable Oils and Biodiesel,"
ACS Sustainable Chemistry & Engineering, vol. 4, (3), pp. 901-906, 2016. DOI: 10.1021/acssuschemeng.5b00991
39

Macro-RAFT emulsion polymerization of styrene
Bas van der Linden
Keywords; macro-RAFT, emulsion, polymerization, styrene
Abstract
Polystyrene is a major source of plastic products in the world
due to its high durability. Out of many polymerization
techniques, emulsion is preferred for industrial use and the
ability to combine with Reversible Addition-Fragmentation
Chain Transfer (RAFT). This RAFT agent can be added to a
block polymer giving it emulsifying properties. Therefore the
purpose of the research was to synthesize and analyse a
block copolymer macro-RAFT agent from acrylic acid and
styrene in different ratios. These macro-RAFT agents will be
used to polymerize styrene in which the respective PDI and
conversion will be analysed and compared as shown below
QR-code
A major challenge is analysing the
length of the block copolymer. This
can be calculated using the intervals
of a 1 H-NMR analysis.
Expected Results
A major challenge is analysing the
length of the block copolymer. This
can be calculated using the intervals
of a 1 H-NMR analysis.
Literature
1. Wang, X., Luo, Y., Li, B., & Zhu, S. (2009b). Ab Initio Batch Emulsion RAFT
Polymerization of Styrene Mediated by Poly(acrylic acid-b-styrene) Trithiocarbonate.
Macromolecules, 42(17), 6414–6421. https://doi.org/10.1021/ma9010999
40

Design and Synthesis of RAFT Agents used for the
Polymerisation of Styrene Analogues
Remco Neutelings
Keywords; RAFT, Polymers, Styrene analogues
Abstract
Many commercially used polymers originate from oil.
These oil-based polymers have a negative effect on the
environment, making the need for bio-based alternatives
high. Bio-based styrene derived from lignin [1] is an
answer to this problem however, in order to polymerize it
and make block-co-polymers with acrylates a suitable
RAFT agent is needed. DOPAT has been used for this
purpose before, the Z-group of this RAFT agent is
modified to achieve higher yields and more conversion
within the same time. These RAFT agents are
synthesized and used in a polymerisation in order to test
their applicability to the monomers, styrene, 4-
acetoxystyrene and methylmethacrylate
Expected Results
3 different raft agent synthesized, DOPAT, CEDB and a dithiocarbamate.
Hopefully yields up to 60%. Prove the target molecule is made using NMR,
FTIR and TLC. Then test in polymerisation with controlled properties.
Polymer requires:
- Mn and Mn (calc)
are close together
- PDI <1,5
- 30 C% within 8 h.
- Mn >4000
Literature
[1] Schijndel, J. A. M., et al Preparation of bio-based styrene alternatives and their free
radical polymerization. European Polymer Journal, 125 [109534] (2020)
[2] Nabifar, A., et al Thermal polymerization of styrene in the presence of TEMPO. Chemical
Engineering Science, 64(2), 304–312. (2009)
41

42

32SPOC05
Nishant Sewgobind
Foto
Docent
“Je weet dat je van Organische Chemie
houdt als je in (Lewis)structuren denkt en je
de vrije elektronenparen ziet dansen en
springen om te reageren”
~ Nishant Sewgobind
43

44

32SPOC05
Nishant Sewgobind
Perkin synthesis of butylidene
phthalide under reduced
pressure
Lars Schrauwen
A Natural Medicine
Etienne Kant
Synthesis of different N-
carboxyanhydrides (NCAs) for
the polymerization to a
polypeptide block copolymer
Veron Verhoeven
Synthesis of L-lysine into a
gelifyer
Rick van Ham
A Gelifyer For Cosmetic Purpose
Selina Lafertin
45

46

Perkin synthesis of butylidene phthalide under
reduced pressure
Lars Schrauwen
Keywords: 3-butylidene phthalide, 3-ylidene phthalides, Perkin reaction, reduced pressure
Abstract
This research was commissioned by Michel Goldbach
The purpose of my research was to synthesize and
isolate 3-butylidene phthalide from phthalic anhydride
and valeric anhydride under reduced pressure using
different kinds of solvents.
This method was used to research the possibility of
performing this synthesis of 3-butylidene phthalide
using lowered temperatures, using the solvents in an
atmosphere of reduced pressure.
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Expected Results
In this column are the expected results of the MS [2],
H-NMR [3] and FTIR [4] 3-butylidene phthalide: The
yield this reaction would be 76% [1]
Literature
[1] L. Xiu, X. Duan, X. Zhang, D. Tan, D. Zou, X. Chen en K. Wang, „Method for preparing
butyphthalide”. China Patent 107216298, 29 september 2017.
[2] N. U.S., „NIST chemistry webBook, SRD 69,” 2018. [Online]. Available:
https://webbook.nist.gov/cgi/cbook.cgi?ID=C551086&Units=SI&Mask=2380. [Geopend 24 april 2020].
47

A Natural Medicine
Etienne Kant
Keywords: N-butalidene phthalide, Perkin reaction, Grignard
Abstract
A Client of the company “Synex Synthetics (CRB
Benelux Maastricht)” has come up with the task to
develop a way to produce N-butilidene phthalide.
This will be done using the perkin condensation. The
goal is to find the best enviroment for the syntheses
and make the yield as high as possible. N-butalidene
phthalide will be synthesised from valeric anhydrid,
potassium valerate and phthalic anhydride. The
product will be analysed using FT-IR, H-NMR, GC-
MS and melting point. This will be performed in a 70
hour time period.
Photo
Expected Results
The expected yield of the synthesis is 73% 1 . This is one of the best
syntheses, the best would be a Grignard (96% 2 ) . The problem is that this
is a two-step synthesis while the perkin reaction is a one-step synthesis.
GC-MS is the main characterisation. This is because
any Impurities can be identified. The illustration show
the GC-MS spectrum of N-butilidene phthalide 3 . The
base peak is at 55 m/z. The most iconic peak lies at
148 m/z. This peak is characteristic for N-butalidene
phthalide. Any expected impurities do not contain this
m/z peak.
Literature
1
CN 2017-10606003 ; 2 CN 2006-10093403 ;
3
https://doi.org/10.1080/00032710802209243
48

Synthesis of different N-carboxyanhydrides (NCAs) for
the polymerization to a polypeptide block copolymer
Veron Verhoeven
Keywords: O/W emulsifying agent, amphiphilic molecule, carboxylic anhydrides, NCAs,
polypeptides, block polymer
Abstract
In this research, the synthesis of different carboxylic
anhydrides (NCAs) was going to be performed
following a green method with dimethyl carbonate
(DMC). The NCAs were going to be polymerized into
a block copolymer following a catalytic ring-opening
polymerization (ROP) to create an amphiphilic
molecule. The expectation is that a maximum yield of
67% will be obtained for the NCA synthesis. Another
expectation is that a narrow polydispersity index
(PDI) will be achieved for the polymerization in a
relatively short time. This synthesized amphiphilic
molecule can have many application possibilities,
such as an emulsifying agent.
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Expected Results
Expected yield NCAs synthesis: 67% [1]
1H NMR (300 MHz, DMSO-d6) δ= 1.93, 2.03 (d, J = 0.358 ppm, 2H, methylene),
2.19 (s, 2H, methylene), 4.26 (s, 1H, methyne), 5.06 (s, 2H, methylene), 7.27-7.36
(m, 5H, benzene), 8.11 (s, 1H, secondary amine);
13C{ 1H} NMR (100 MHz, DMSO-d6) δ= 29.68, 30.49, 63.34, 65.92, 128.33,
128.40, 128.75, 128.88, 136.64, 171.34, 172.09, 172.67;
Elemental Analysis calculated for C13H13NO5 (C% : 59.32%, H% : 4.94%, N% :
5.32%, O% : 30.42%), found (the amount of test: 3.508 mg, C% : 59.15%, H% :
4.81%, N% : 5.17%, O% : 30.87%). [1]
Expected conversion of the polymerization: 90% till 100% [2]
Mn obtained from 2,31 * 10 4 till 3,59 * 10 5 in 7-180 minutes [2]
PDI’s ranging from 1,04 till 1,08 (specific for living polymerization) [2]
Literature
[1] Zhang, Z., Su, K., & Li, Z. (2019). Carboxylic Anhydride Synthesis from γ-Benzyl-l-glutamate and
Dimethyl Carbonate. Organic Letters, 21(3), 749–752. https://doi.org/10.1021/acs.orglett.8b03984
[2] Zhao, W., Lv, Y., Li, J., Feng, Z., Ni, Y., & Hadjichristidis, N. (2019). Fast and selective
organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst. Nature
Communications, 10(1). https://doi.org/10.1038/s41467-019-11524-y
49

Synthesis of L-lysine into a gelifyer
Rick van Ham
Keywords: L-lysine, gelling propertie, gelling agent
Abstract
In this research the gelling properties of L-lysine
derivates will be tested. In the image below, all 4
structures are shown which I tented to synthesize, to
compare the gelling properties of these 4, and a
commercial available gelling agent, shown in the
second image. There is not such thing as the best
gelling agent, because t depents on other
compounds of a cosmetic cream. This research is
just about to get some more information about
possible gelling agents for such creams.
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Expected Results
I have no expected results, hasn’t been any research about the gelling
properties of these 4 structures.
Literature
-
50

A Gelifyer For Cosmetic Purpose
Selina Lafertin
Keywords: Gelling agent, Green Chemistry, Fatty acid, Amino acid
Abstract
A client of the company ‘’Synex Synthetics (CRB
Benelux Maastricht)’’ has come up with the mission
to develop a gelifyer agent. An emphasis was placed
on a green chemistry synthesis. Because of this, the
aim of this project is to use a variation of different
"green" solvents in a working synthesis from previous
research, with the amino acid; L-proline and the fatty
acid; lauric acid. The products will be analysed by
FT-IR and H-NMR and all experiments will be
performed over a period of 70 hours.
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Expected Results
Research has shown that 2-propanol will produce the highest yield compared to
acetone, propanol, ethyl acetate and diethyl ether as a solvent. The figure below
shows the expected H-NMR result for the product.
Literature
Cepeda, E. A., Bravo, R., & Calvo, B. (2009). Solubilities of Lauric Acid inn-Hexane, Acetone, Propanol,
2-Propanol, 1-Bromopropane, and Trichloroethylene from (279.0 to 315.3) K. Journal of Chemical &
Engineering Data, 54(4), 1371–1374. doi:10.1021/je800739y
Kolb, D. K., & Brown, J. B. (1955). Low temperature solubilities of fatty acids in selected organic
solvents. Journal of the American Oil Chemists’ Society, 32(6), 357–361. doi:10.1007/bf02640385
51

52

32SPOC06
Jack van Schijndel
Foto
Docent
“Tijd is een kwestie van
prioriteit”
~ Jack van Schijndel
53

54

32SPOC06
Begeleider : Jack van Schijndel
Photo-catalyzed polymerization
of isobutyl vinylether in batch &
flow
Bibi Nanlohy
Synthesis Of Curcumin
Emma van Oort
Synthesis Of
Bisdemethoxycurcumin and
alkylation of the central carbon
atom
Arjan Bons
A synthesis of curcumin and
related compounds
Nora Pool
Photo-Catalyzed Flow and Batch
Polymerization of Ethyl Vinyl
Ether
Nick Romijn
55

56

“PHOTO-CATALYZED POLYMERISATION OF ISOBUTYL
VINYLETHER IN BATCH & FLOW”
Bibi Nanlohy
Keywords: photopolymerization, cationic polymerization, vinyl ethers, isobutyl vinyl ether
Abstract
Photo-initiated polymerization and flow chemistry are
developing strongly these days. A photo-initiated
polymerization takes place under mild conditions,
e.g. using light sources and metal-free
photocatalysts. The advantage of applying flow is the
reduction of reagents, a higher conversion, and so
very favorable for green chemistry. The photoinitiated
polymerization of isobutyl vinyl ether (IBVE)
will be performed using a 450 nm LED-strip, various
chain transfer agents (CTA) and a metal-free
photocatalyst (PC). The appliance of flow chemistry
will lead to the same molecular weight distribution
compared to a batch performance.
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Figure 1. Cationic polymerization of IBVE regulated with blue light.
Expected Results
Yields
Table 1. Selected results of the cationic polymerization of IBVE with CTA
S-1-isobutoxyethyl N,N-diethyl dithiocarbamate (1) and S-1-isobutoxyethylo-ethyl
xanthate (2) [1].
a
Reaction conditions: IBVE (1 eq.), 1a (0.01 mol%), and chain transfer
agent (0.02 eq.) at room temperature in
dichloromethane with blue-light-emitting
diode irradiation (450 nm) for 360 minutes
[1]. 1H NMR spectra
Literature
[1] Q. Michaudel et al., “Mechanistic Insight into the Photocontrolled Cationic
Polymerization of Vinyl Ethers,” vol. 139, no. 43, pp. 15530–15538, Nov. 2017, doi:
10.1021/jacs.7b09539.
[2] K. Van Beurden, J. Van Schijndel, ‘’ 1 H NMR spectrum CTA 2a and 2c,’’ 2020
57

Synthesis Of Curcumin
Emma van Oort
Keywords: Curcumin, Antioxidant, Curcuminoids, Synthesis
Abstract
During this project, the aim was to synthesize a
curcumin derivative from syringaldehyde and to
connect phenylacetaldehyde to this intermediate.
Curcumin is an organic molecule with a conjugated
system and has an absorption maximum between
410 and 430 nm, which reflects a yellow light. [1] This
yellow colour is present at a pH between 2.5 and 7.0
and when the pH rises, the substance turns red. [2]
The hypothesis is that there will be a colour change
from yellow to blue because the phenylacetaldehyde
causes the pH to drop. [2]
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Expected Results
Curcumin has a melting point of 183 °C and the derivative is expected to
have a higher melting point due to the additional methoxy groups on the
benzene rings. Further it is expected that a yield between 70% and 80%
can be determined. [3-5] The figure below, figure 1, show the expected
FTIR and NMR spectrum of curcumin that the spectrum of the derivative
should resemble.
Literature
[1] Sui, Z.; Salto, R.; Li, J.; Craik, C.; Ortiz de Montanellano, P.R. Inhibition of the HIV-l and HIV-2
Proteases by Curcumin and Curcumin Boron Complexes, Pergamon Press Ltd,1(6), 1993, 415-422.
[2] Lee, W.H.; Loo, C.Y.; Bebawy, M.; Luk, F.; Mason, R.S.; Rohanizadeh, R. Curcumin and its
Derivatives: Their Application in Neuropharmacology and Neuroscience in the 21st Century. Current
Neuropharmacology, 11, 2013, 338-378.
58

Synthesis Of Bisdemethoxycurcumin and alkylation
of the central carbon atom
Arjan Bons
Keywords: Curcumine, synthese, absorption maximum, green chemistry.
Abstract
This research focusses on two separate syntheses:
The synthesis of bisdemethoxycurcumin using p-
hydroxybenzaldehyde and acetylaceton catalysed by
boric anhydride and n-butylamine. In order to find a
more sustainable combination of chemicals for this
reaction boric acid will be used instead of boric
anhydride and ammoniumcarbonate instead of n-
butylamine. The next step is the synthesis of a
curcuminderivative by addition of
phenylaceetaldehyde on the central carbonatom of
curcumin catalysed by piperidine. The purpose of this
step is the increase of absorption maximum of
curcumine to become blue. The products are
measured using HPLC-UV/VIS and H-NMR. Step 1
yielded 60% and step 2 yielded 81%.
Photo
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Expected Results
Expected H-NMR of Curcumin [1]
Literature
[1] E. V. Rao en S. P., „Revisiting curcumin chemistry part I: a new strategy for the
synthesis of curcuminoids.,” Indian J Pharm Sci., vol. Vol. 73, nr. Nr. 3, pp. 262-270,
2011.
59

A synthesis of curcumin and related compounds
Nora Pool
Keywords: synthesis, curcumin, phenylacetaldehyde, acetylacetone, Green Chemistry
Abstract
This research is a combined research all related to
making curcumin and related compounds. The first
research is based on protocol [1] and aims to form
curcumin from vanillin and acetylacetone. Using
HPLC, NMR, FTIR and TLC will be concluded if the
desired curcumin has been formed.
The second researches [2] goal is to link
phenylacetaldehyde to acetylacetone. Using HPLC,
NMR, FTIR and TLC it can be concluded if the
desired link between acetylacetone and
phenylacetaldehyde has been formed.
The third researches [3] aim is to link
phenylacetaldehyde to the synthesized curcumin.
This reaction will be monitored with FTIR and NMR.
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Expected Results
For the first research the expected NMR spectrum and FTIR spectrum of
curcumin is given in the image below.
For the third research the expected NMR
spectrum is given in the image below.
Literature
[1] H. Pabon, „A synthesis of curcumin and related compounds,” Receil, 1964.
[2] A. Kamal, „One-pot, three component approach to the synthesis of 3,4,5-
trisubsituted pyrazoles,” The journal of organic chemistry, nr. april 2015, 2015.
60

Photo-Catalyzed Flow and Batch Polymerization of
Ethyl Vinyl Ether
Nick Romijn
Keywords: photo-controlled, chain-transfer agent, ethyl vinyl ether, metal-free photocatalyst
Abstract
The usage of photo-catalyzed polymerizations
becomes more ordinary nowadays. Gaining control
over chain growth makes it possible to facilitate more
designs of complex structures. The mechanism of
photocontrolled cationic polymerization of vinylethers
can be carried out by using this type of
polymerization. This polymerization proceeds by
using a metal-free photocatalyst, chain-transfer agent
(CTA) and irradiation by blue colored light in flow or
batch. These conditions allow for good control over
molecular weight and polydispersity. Following the
photocontrolled cationic polymerization mechanism,
poly(vinyl-ethers) e.g. poly(ethyl-vinyl-ether) (EVE)
can be formed. Photoreversible cation formation
enables control over polymer chain growth by
adjusting specific wavelengths of light. [1]
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Expected Results
The monomer is ethyl-vinyl-ether (EVE). The chain-transfer agent (CTA) are S-1-
isobutoxyethyl-N,N-diethyl dithiocarbamate (2a) and S-1-isobutoxyethyl O-ethyl
xanthate (2c).
Graphs:
When light is deactivated, the conversion does not increase, but when the light is
activated, the conversion of poly(EVE) does increase. Light intensity has effect on
the initial reaction rate. If the light intensity increases, the transmission increases
and the initial reaction rate too. [2]
Literature
[1] Micheaudel, Q. Mechanistic Insight into the photocontrolled cationic
polymerization of vinyl ethers. 2017, 139.
[2] Kottisch, V. Cationic Polymeriztion of Vinyl ethers controlled by visible light. 2016.
61

Epilogue
The book of abstracts of the SPOC 1920 is a special
one. This book of abstracts would not have been
possible without the help of the following people.
We want to thank Paula Contreras Carballada for
the organisation and control during this book of
abstracts. Next, we want to thank all the project
leaders: Betty Oostenbrink, Kees Kruithof, Nishant
Sewgobind, Paula Contreras Carballada, Jack van
Schijndel and Sonny van Seeters, for their support
during the SPOC project. We would also like to
thank the technical staff at ATGM for their support
and input. In addition, we want to thank the
company’s, Synex, University of Leiden and CoE
BBE, for their projects we could investigate. In the
next place we want to thank all the students for
their submitted part for completing this book of
abstracts. Last but not least we want to give a
special thanks to Nard Schellekens for inspiration
of the background pictures that made this book of
abstracts different to the previous ones.
The Book of Abstracts Commission: Nora Pool, Ilse
Joosen and Christiaan Verdonk
62

Authors Book of Abstract
SPOC 2019-2010
Vaak ben je te bang
~ Nora Pool
Chemistry is like cooking
(just don’t lick the spoon)
~ Christiaan Verdonk
Als je minder denkt, kan er
meer dan je dacht
~ Ilse Joosen
63