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@PHDTHESIS{Szkudlarek:767125,
author = {Szkudlarek, Marian},
othercontributors = {Möller, Martin and Pich, Andrij},
title = {{F}unctional copolymers of maleic anhydride : synthesis and
application},
school = {RWTH Aachen University},
type = {Dissertation},
address = {Aachen},
reportid = {RWTH-2019-08579},
pages = {1 Online-Ressource (xi, 152 Seiten) : Illustrationen},
year = {2019},
note = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
University; Dissertation, RWTH Aachen University, 2019},
abstract = {This thesis deals with the synthesis, characterization and
properties of copolymers containing maleic anhydride and
fluorinated building blocks prepared by means of free
radical copolymerization. Free radical polymerization in
binary or ternary systems usually leads to a blend of
polymer chains with different composition as a consequence
of different monomer reactivity, hence the most reactive
monomers are consumed first, and consequently the polymer is
enriched in monomers of lower reactivity. This effect is
even stronger, when monomers which cannot undergo
homopolymerization are used. The preferred route to overcome
this problem is to feed continuously the reaction mixture
with monomers at the same rate at which they are consumed.
In Chapter 3 copolymerization of maleic anhydride,
butyl-methacrylate and
1H,1H,2H,2H-perfluorodecylmethacrylate is described. The
kinetics of the copolymerization of F8H2MA/MSA, BMA/MSA, and
F8H2MA/BMA have been extensively studied under well-defined
reaction conditions: the determined copolymerization
parameters were rF8H2MA = 4.9, rMSA = 0, rBMA = 8.2, rMSA =
0, and rF8H2MA = 1.02, rBMA = 0.94. The reaction rates at
chosen conditions were between Rp=0.47 $wt\%/min$ for a
monomer mixture BMA/F8H2MA/MSA = 1.75:0.75:7.5 and Rp=0.73
$wt\%/min$ for BMA/F8H2MA/MSA = 1:1:1. The determined
reaction rates and the composition of the terpolymers were
used to perform successfully continuous addition experiments
in order to produce a bigger quantity of homogenous
terpolymers. The versatility of the method has been proven
by using a different set of monomers namely dodecyl
methacrylate (DMA), 1H,1H,2H,2H-per¬fluo¬ro¬de¬cyl¬
meth¬acry¬late (F8H2MA) and maleic anhydride (MSA). The
copolymers were characterized in term of molecular weight
and thermal properties. Fluorinated terpolymers
P[RFMA-co-RHMA-co-MSA] (RH = C4H9-, C12H25-, RF- =
C10H4F19-) obtained in continuous addition experiments and
containing ca. 20 $mol\%$ fluorinated side chains can be
dissolved in semi polar solvents like tetrahydrofuran,
chloroform or ethyl acetate as well as in fluorinated
solvents like HFX and Freon 113 (Chapter 4). On
incorporation of dodecyl-side chains (RH = C12H25-) the
polymers become also soluble in alkane solvents. Up to 15-20
$mol\%$ MSA content is not sufficient to induce water
solubility, even in case of carboxylate formation by
hydrolysis of the anhydride units. Emulsification of
solutions in organic solvents of the terpolymers showed to
be unstable; they demix within days. The
P[RFMA-co-RHMA-co-MSA] terpolymers were coated on glass from
1 $wt\%$ solution in chloroform. The contact angles of water
and hexadecane as wetting liquids were measured at 20°C
prior and immediately after an annealing step (12h, 120°C)
and were found to be equal: 110 ° against water and above
70 ° for hexadecane. This means that during the film
formation process the mobility of fluorinated chains is
sufficient to ensure proper orientation of the fluorinated
side chains already at room temperature. Such behavior is
possible because of relatively low Tg of these copolymers.
The surface properties of the coatings obtained on aluminum
substrates are comparable with coatings on glass both for
water and hexadecane. The properties of the coating obtained
on paper are different and the measured values for both
wetting liquids are lower than for the other two substrates.
This phenomenon can be explained by the fact that the
terpolymer solution penetrates the paper and consequently
does not form a closed film. In summary RH, RF,
MSA-terpolymers of moderate fluorine content are versatile,
flexible to handle materials that offer wide screen of
application for surface modification. To further increase
the adhesion properties of these copolymers - especially to
metallic surfaces - phosphoric acid groups were incorporated
using ethylene glycol methacrylate phosphate (EGMP) as
comonomers (Chapter 5). An obstacle in performing continuous
addition polymerization experiments was the fact that due to
overlapping signals in the 1H NMR spectra the composition of
these copolymers could not be unequivocally determined.
However, these materials showed good solubility in aqueous
ammonia solution and appropriate surface properties due to
the presence of fluorinated building blocks. The surface
properties of different polymer composition were
investigated after coating from water based formulations on
glass substrates and annealing above the glass transition
temperature. Coatings with hydrophobicity up to 120 ° were
obtained. The relatively low thermal stability of phosphorus
containing copolymers implies limitations in an application.
The aim to create a synthetic, amphiphilic structure with
strong antimicrobial properties comparable with natural
toxins, led to copolymers of maleic anhydride with vinyl
monomers (Chapter 6). Vinyl monomers and maleic anhydride
yield alternating copolymers. This ensures a constant 1:1
ratio of the hydrophobic and cationic part similar to those
in leucine/lysine (1:1) peptides (LK-peptides). The choice
of 4-methyl-1-pentene as hydrophobic comonomer is based on
the similarity of the structure with leucine, while the
choice of maleic anhydride leaves ample of space for further
design of the cationic/hydrophilic part by means of chemical
modification. An alternating copolymer of maleic anhydride
and 4-methyl-1-pentene was synthesized by means of free
radical copolymerization in the presence of benzoyl peroxide
(BPO) as initiator. Modification of the P[MP-alt-MSA]
copolymer with diamine to
poly[(4-methyl-1-pentene)-alt-(1-(3-N,N-dimethylaminopropyl)maleimide)]
was performed as a one pot synthesis in relatively mild
conditions (DMF at 120 °C).
Poly[(4-methyl-1-pentene)-alt-(1-(3-N,N-dimethylaminopropyl)maleimide)]
was converted into a polycationic polymer by means of alkyl
iodide. The modification with methyl iodide yields a yellow
colored powder easily soluble in water and polar solvents
like DMF and DMSO but insoluble in lower alcohols and less
polar solvents. Sequential quaternization with methyl iodide
and dodecyl iodide ensures solubility in a wide variety of
polar solvents including alcohols and ketons. Modification
with dodecyl iodide only leads to polymers soluble in
non-polar solvents. Copolymers with quaternary ammonium
groups and long alkyl chains were tested for their
antimicrobial properties.},
cin = {154610 / 150000},
ddc = {540},
cid = {$I:(DE-82)154610_20140620$ / $I:(DE-82)150000_20140620$},
typ = {PUB:(DE-HGF)11},
doi = {10.18154/RWTH-2019-08579},
url = {https://publications.rwth-aachen.de/record/767125},
}
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