Synthesis and Properties of Novel Surface Active Monomers Based on Derivatives of 4-Hydroxybutyric Acid and 6-Hydroxyhexanoic Acid

Article abstract of DOI:10.1007/s11743-014-1640-z

Novel surface active maleate and methacrylate monomers based on derivatives of ω-hydroxy carboxylic acids have been synthesized. The monomers are comprised of hydrophobic alkyl chains and hydrophilic poly(ethylene glycol), quaternary ammonium, sulfonate and carboxylic fragments. Synthesized monomers sufficiently reduce surface tension at the aqueous solution-air interface. The copolymerization of synthesized monomers with 5-tert-butylperoxy-5-methyl-2-hexene-3-yne monomer and N-vinylpyrrolidone in solvent and emulsion copolymerization of synthesized peroxide containing surface active monomer with styrene have been carried out. The synthesized surface active monomers have been shown to be suitable emulsifiers for obtaining polystyrene colloid dispersions. It has been ascertained that the surface active copolymers obtained can form stable interpolyelectrolyte complexes with oppositely charged polymers.

Full text of DOI:10.1007/s11743-014-1640-z

J Surfact Deterg
DOI 10.1007/s11743-014-1640-z
ORIGINAL ARTICLE
Synthesis and Properties of Novel Surface Active Monomers
Based on Derivatives of 4-Hydroxybutyric Acid
and 6-Hydroxyhexanoic Acid
•
Mykola Borzenkov Natalia Mitina
•
•
Volodymyr Lobaz Orest Hevus
Received: 14 May 2013 / Accepted: 25 August 2014
Ó AOCS 2014
Abstract Novel surface active maleate and methacrylate
monomers based on derivatives of x-hydroxy carboxylic
acids have been synthesized. The monomers are comprised
of hydrophobic alkyl chains and hydrophilic poly(ethylene
glycol), quaternary ammonium, sulfonate and carboxylic
fragments. Synthesized monomers sufficiently reduce sur-
face tension at the aqueous solution-air interface. The
copolymerization of synthesized monomers with 5-tert-
butylperoxy-5-methyl-2-hexene-3-yne monomer and N-vi-
nylpyrrolidone in solvent and emulsion copolymerization
of synthesized peroxide containing surface active monomer
with styrene have been carried out. The synthesized surface
active monomers have been shown to be suitable emulsi-
fiers for obtaining polystyrene colloid dispersions. It has
been ascertained that the surface active copolymers
obtained can form stable interpolyelectrolyte complexes
with oppositely charged polymers.
Introduction
The chemistry of polymeric and composite materials for
biomedical applications has been intensively developed
over the last decades [1–8]. Such materials possess
special physical, mechanical and colloidal properties,
essential for the creation of biocompatible implants [9–
11], drug delivery systems [12–18], carriers of genetic
materials [19–21] etc. In this sense, the properties of
modern polymer materials with microheterogeneous
morphology are determined not only by chemical struc-
ture of polymer but also by the nature of the interface
and by processes occurring at interface [22]. The pre-
sence of various functional groups on the surface of
polymeric particles facilitates performing varied reactions
at the interface, namely forming implanted polymeric
layers with desired properties [23], to immobilize various
biomolecules [24], drugs [25], as well as luminescent,
magnetic and other markers [26].
Keywords Synthesis Á Surface activity Á Surface active
monomers Á Surface tension Á Surface active copolymers
The efficient way of creation of polymer colloids with a
functionalized interface consists of utilizing surface active
monomers, also known as surfmers, during the polymeri-
zation of various monomers. Surface active monomers
during the preparation of emulsion of monomers in water
are located predominantly on the monomer droplet-water
interface thus acting as surfactants stabilizing the emulsion
[27]. However, in contrast to traditional surfactants, surf-
mers due to presence of polymerizable units are incorpo-
rated into polymer backbone during the polymerization.
The surfmer links due to their surface activity are located
predominantly on the surface of polymeric particles [28]
providing effective stabilization of the polymer colloid.
Such polymer dispersion is considered cleaner, than that
obtained with non polymerizable surfactants, which is
important for biomedical applications.
Abbreviations
IPEC
Interpolyelectrolyte complex
Surfmer Surface active monomer
VEP
5-tert-Butylperoxy-5-methyl-2-hexene-3-yne
M. Borzenkov (&) Á N. Mitina Á O. Hevus
Department of Organic Chemistry, Lviv Polytechnic National
University, 12 S. Bandera Str., Lviv 79013, Ukraine
e-mail: nickborzenkov@gmail.com
V. Lobaz
Institute of Particle Technology, Friedrich-Alexander University
Erlangen-Nuremberg, Cauerstrasse 4, 91058 Erlangen, Germany
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J Surfact Deterg
One of the first surveys on non-ionic polymerizable
surfactants was published by the research group of Ottewill
[29]. The authors synthesized polyethylene oxide contain-
ing macromonomer and used it for preparation of stable
polystyrene latexes. In another paper, the synthesis and
homopolymerization of polyethylene oxide containing
macromonomers in water and toluene were reported [30].
Colloidal properties of surface active monomers as in
the case of traditional surfactants depend on the length and
origin of lipophilic and hydrophilic fragments. Variation of
length and origin of lipophilic and hydrophilic fragments
allows one to tailor the hydrophilic-lipophilic balance of
the surfmer and its preferential location in the colloid
system [31]. The nature of lipophilic fragment of the
surfmer provides the affinity to different surfaces. Syn-
thesized surface active monomers contain fragments of
aliphatic alcohols or higher carboxylic acids as hydropho-
bic fragments and poly(ethylene glycol), carboxylate, sul-
fonate, phosphate and quaternary ammonium fragments as
hydrophilic moieties.
[55]. Moreover, cationic oligomers based on the above-
mentioned surfmers perform efficient protein binding and
can be used as carriers for nucleic acids, polypeptides, as
well as some pharmaceutical substances [56]. For this
purpose the synthesis of new cationic surfmers with qua-
ternary ammonium fragment seems to be the prospective
way for creation of polymers for efficient binding of neg-
atively charged biomolecules. Surface active monomers
with carboxylic groups are known to be prospective com-
pounds for creation of anionic surface active copolymers
applied for drug delivery as well as for binding of peptides
and amino acids [57]. Incorporation in the surfmer struc-
ture of more hydrophilic anionic fragments such as a sul-
fonate group should improve the stability of complexes of
copolymers containing links of the surfmer with positively
charged centers of biomolecules.
Surface active copolymers with side peroxide links were
applied as macroinitiators for the creation of block or
branched carriers for drugs and nucleic acids during the last
few years [58]. They are obtained by copolymerization of
peroxide monomers, namely peroxide derivatives of vi-
nylacetylenic alcohol, or peroxide-containing surfmers
[59]. Utilization of peroxide-containing surfmers during
emulsion or dispersion polymerization provides the loca-
tion of peroxide groups onto the surface of polymeric
particles directly during the polymerization process. Also
this technique permits one to obtain surface active oligo-
mers with a predictable structure containing peroxide
groups as substitutes of the side chain [60, 61]. This allows
one to perform various polymer-analogous transformations
at the surface of polymeric particles by free radical reac-
tions of peroxide groups.
The polymerization capability of such compounds, as in
the case of typical monomers, is determined by the nature
of the polymerizable fragment [32]. Variation of nature of
polymerizable unit impacts on the polymerization capa-
bility of surfmers and on the microstructure of the
copolymer backbone respectively. Nowadays, a wide range
of maleate [33–37], (meth)acrylate [38–42] and styrene
[43–46] surfmers have been synthesized.
Moreover, a number of papers [47–49] published in the
1990s were devoted to the behavior of macromonomers
during copolymerization in the presence of surface active
monomers. Thus, during the copolymerization of amphi-
philic polyethylene oxide with styrene it was found that the
polymerization rate significantly increases at concentra-
tions of surface active monomer above the critical micelle
concentration (CMC) [50]. Also the rate of copolymeri-
zation increases with increasing hydrophobicity of terminal
aralkyl groups of the macromonomer due to formation of a
micellar core. This type of copolymerization is known as
micellar polymerization [51]. It was shown that during
micellar copolymerization of macromonomers with sty-
rene, hyperbranched polystyrene-grafted-polyethylene
oxide capable of formation of monomolecular nanoparti-
cles in aqueous solutions was obtained [50].
However, the application of copolymer family contain-
ing di-tert-butyl peroxide for initiation of polymerization
from the surface is limited due to high thermal stability of
the peroxide group. The surfmers with peroxyester groups
are more promising for creating surface functionalized
polymeric colloids due to their lower thermal stability.
Various surface active monomers that have a polymer-
izable group and a functional group separated from each
other by spacers of different lengths and nature are inter-
esting prospects for developing novel types of surface
active copolymers. Various fragments of bifunctional
compounds (diols, dicarboxylic acids, diamines, etc.) that
are used as spacers could be incorporated into the surfmer
structure via successive interaction due to their functional
groups. However, selective transformation of one of the
two equally reactive functional groups is quite problematic.
As a result, the final product contains impurities of
bifunctional derivatives which is a serious issue in mono-
mer synthesis.
Additionally the surface active monomers contain vari-
ous functional groups in their structure [52–54] providing
the reactivity towards desired molecules or surfaces.
Copolymerization of functional surfmers results in surface
active copolymers which could be applied as efficient
interface modifiers or carriers of biomolecules.
The surfmers containing a quaternary ammonium frag-
ment or zwitterionic function are the promising reagents
for creation of modifiers of negatively charged surfaces
Such problems can be avoided by using various het-
erocyclic reagents (oxiranes, lactones, sultones, etc.) since
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J Surfact Deterg
they are known to selectively form monosubstituted
derivatives in ring opening reactions under mild conditions
[62]. Lactones of corresponding carboxylic acids are par-
ticularly promising reagents for the incorporation of
hydrophobic spacers. The utilization of lactones of differ-
ent carboxylic acids and with various ring sizes allows
varying hydrophilic-lipophilic balance and the position of
polymerizable fragment relative to the other functional
groups in molecule of surfmer.
with 1-hexadecanol according to the described technique in
[68].
Synthesis of tert-Butylperoxy-6-hydroxyhexanoate 3
First, 0.0098 mol (1.12 g) of e-caprolactone 1b and
0.068 mol (6.17 g) of tert-butyl hydroperoxide were mixed
and a droplet of BF3Á(C2H5O)2 was added. The mixture
was stirred for 12 h at 50–55 °C and filtered through a thin
layer of aluminium oxide. The excess tert-butyl hydro-
peroxide was removed under reduced pressure. The crude
product was chromatographed on a silica gel column and
eluted with a hexane–ethyl acetate gradient. The solvents
were removed under reduced pressure to give 1.4 g (70 %)
of pure peroxide 3. d240 1.0182; nD20 1.4552; MR: 53.56; MR
(calculated): 53.55. Found, %: C 58.59; H 9.4. Calculated,
In this study we report the synthesis of novel surface
active monomers containing poly(ethylene glycol), car-
boxylic, sulfonate, quaternary ammonium hydrophilic
fragments and tert-butylperoxy groups utilizing lactones of
6-hydroxyhexanoic acid and 4-hydroxybutanoic acid as
initial materials.
1
%: C 58.82; H 9.8. H NMR (DMSO-d6), d, ppm: 3.64 (t;
J = 6.46 Hz; 2H); 2.32 (t; J = 7.8 Hz; 2H); 1.64 (m;
Experimental
J = 7.61 Hz; 4H); 1.4 (t; J = 8.16; 2H); 1.28 (s; 9H).
Initial Materials
Synthesis of 6-tert-Butylperoxy-6-oxohexylmaleinate 4
Maleic anhydride, triethylamine, methacryloyl chloride
were purchased from Merck and additionally purified by
distillation. Phosphorus trichloride, 1,3-propane sultone,
1-hexadecanol were also purchased from Merck and used
without further purification. e-Caprolactone, c-butyrolac-
tone, N,N-dimethylaminoethanol, styrene, N-vinylpyrroli-
done were obtained commercially from Sigma–Aldrich and
were additionally purified by distillation. Poly(ethylene
glycol) monomethyl ether 550 with average molecular
weight of 550 g/mol was also commercially available from
Sigma–Aldrich and used without additional purification.
tert-Butyl hydroperoxide was additionally purified by
vacuum distillation. VEP was synthesized from 2-methyl-
hex-5-en-3-yn-2-ol and tert-butyl hydroperoxide according
to a known technique [63] and purified by vacuum distil-
lation. All solvents (hexane, dichloromethane, ethyl ace-
tate, 2-butanone) were purchased form Sigma–Aldrich and
purified according to known techniques [64] prior to use.
To a solution of 0.01 mol (1 g) of maleic anhydride in 5 ml
of dichloromethane 0.01 mol (2 g) of compound 3 and
0.0007 mol (0.1 ml) of triethylamine were added conse-
quently. The mixture was stirred for 24 h at 40 °C. The
compound 4 was further used for in situ synthesis of target
surfmers and, therefore, was not identified.
Synthesis of 4-(Hexadecyloxy)-N-(2-hydroxyethyl)-N,N-
dimethyl-4-oxobutan-1-aminium bromide 10
To a solution of 0.01 mol (1 g) of N,N-dimethylamino-
ethanol in 10 ml of 2-butanone 0.01 mol (3.76 g) of
1-hexadecyl-4-bromobutyrate, 2 was added and the mix-
ture was heated for 15 h at 80 °C. The solvent was
removed under reduced pressure to give the compound 10
with a quantitative yield (4.76 g). m.p. 50–53 °C; Found,
%: C 60.15; H 10.57; Br 17.01; N 3.05. Calculated, %: C
60.00; H 10.42; Br 16.66; N 2.91.
Synthesis of Intermediate Compounds
The purity of the intermediate compounds was con-
firmed by thin layer chromatography and elemental
analysis.
4-Bromobutyric acid was synthesized according to the
technique described in [65]. The triethylammonium salt of
4-hydroxybutyric acid was obtained by interaction of c-
butyrolactone 1a with triethylamine in aqueous solution.
1-Hexadecyl maleate was synthesized as it was reported in
[66]. Chloroanhydride of 1-hexadecyl maleate 7 and
chloroanhydride of 4-bromobutyric acid were synthesized
via interaction of corresponding compounds with phos-
phorus trichloride according to the described method in
[67]. 1-Hexadecyl-4-bromobutyrate 2 was synthesized by
the reaction of chloroanhydride of 4-bromobutyric acid
Synthesis of Surface Active Monomers
Synthesis of Triethylammonium 3-[(Z)-4-(6-tert-
butylperoxy-6-oxohexyloxy)-4-oxobut-2-enoyloxy]-1-
propanesulfonate 5
To a solution of 0.0066 mol (2 g) of compound 4 in 6 ml
of dichloromethane, 0.0066 mol (0.8 g) of 1,3-propane
sultone and 0.0066 mol (0.67 g) of triethylamine were
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Synthesis of N-(2-{[2Z]-3-carboxyprop-2enoyl]oxy}ethyl)-
4-hexadecyloxy-N,N-dimethyl-4-oxobutan-1-aminium
bromide 11
added consequently. The reaction mixture was stirred for
24 h at ambient temperature. After the evaporation of the
solvent, the monomer 5 was obtained with a quantitative
yield (3.47 g) as slightly yellow viscous liquid. 1H
NMR(DMSO-d6), d, ppm: 9.47 (s; 1H); 6.33 (d;
J = 12.3 Hz; 1H, = CH2); 6.22 (d; J = 12.3 Hz;
1H, = CH); 4.29 (t; J = 6.38 Hz; 2H); 4.16 (t;
J = 6.69 Hz; 2H); 3.16 (q; J = 6.69 Hz; 6H); 2.73 (t;
J = 5.44 Hz; 2H); 2.33 (m; J = 7.12 Hz; 2H); 2.16 (m;
J = 6.9 Hz; 2H); 1.63 (m; J = 7.72 Hz; 2H); 1.33 (m;
11H); 1.28 (s; 9H) [69].
To a solution of 0.0043 mol (0.42 g) of maleic anhydride
in 5 ml of dichloromethane, a solution of 0.0043 mol (2 g)
of compound 10 and 0.0007 mol (0.1 ml) of triethylamine
in 5 ml of dichloromethane were added. The mixture was
stirred at 40 °C for 24 h. The solvent was removed under
reduced pressure to give 2.27 g (94 %) of monomer 11.
Synthesis of 4-(Hexadecyloxy)-N-(2-
(methacryloyloxy)ethyl)-N,N-dimethyl-4-oxobutan-1-
aminium bromide 12
Synthesis of (6-tert-Butylperoxy-6-oxohexyloxy)(methoxy
polyethylene glycol-550)maleinate 6
To a solution of 0.0043 mol (2 g) of compound 10 and
0.0043 mol (0.43 g) of triethylamine in 10 ml of dichlo-
romethane, 0.0043 mol (0.44 g) of methacryloyl chloride
solution in 5 ml of dichloromethane was added dropwise at
5–10 °C. The mixture was stirred for 6 h at 5–10 °C. The
precipitate was filtered off and the solvent was removed
under reduced pressure to give 2.3 g (90 %) of monomer
12.
To a solution of 0.0066 mol (2 g) of compound 4 and
0.0066 mol (0.66 g) of triethylamine in 6 ml of dichlo-
romethane, 0.0033 mol (0.45 g) of phosphorus trichloride
was added dropwise. The reaction mixture was stirred for
6 h at 40 °C. The resulting solution was decanted and was
added dropwise at 10 °C under stirring to a solution of
0.0066 mol (3.8 g) of polyethylene glycol monoethyl
ester and 0.0066 mol (0.7 g) of triethylamine in 10 ml of
hexane. The mixture was stirred for 20 h at 15 °C and
then filtered through a thin layer of aluminium oxide. The
solvent was removed under reduced pressure. The yield of
monomer 6 was 85 % (4.6 g) 1H NMR(DMSO-d6), d,
ppm: 6.23 (d; 2H); 4.61 (t; 2H); 4.18 (t; 2H); 3.78 (t; 2H);
3.61 (m; 47H); 3.53 (t; 2H); 3.34 (s; 3H); 2.31 (t; 3H)
CH2C(O)OO; 1.61 (m; 4H); 1.36 (t; 2H); 1.28 (s; 9H)
[69].
Polymerization Technique
Copolymerization reactions were carried out in ethyl ace-
tate as a solvent under an argon atmosphere in soldered
dilatometers with volumes from 15 to 50 ml and with
0.05 ml as the scaling factor. Concentration of monomers
was varied in range from 1 to 4 mol/L. Azobisisobutyro-
nitrile at concentration 5 9 10-2 mol/L was used as the
initiator of polymerization. The copolymers obtained were
isolated and purified by repeated precipitation by adding an
excess of poor solvent (hexane) to a solution of copolymer
in ethyl acetate. Isolated copolymers were dried under
vacuum at ambient temperature to constant weight.
Emulsion polymerization was performed in thermostati-
cally controlled reactor equipped with a stirrer and con-
denser under an argon atmosphere. The conversion rate of
monomers was determined by a gravimetric technique [70].
Synthesis of Triethylamino-3-[(Z)-4-hexadecyloxy-4-oxo-2-
butenoyloxy-4-oxobutyloxanoate] 8
To a solution of 0.01 mol (2 g) of triethylammonium salt
of 4-hydroxybutyric acid and 0.01 mol (1 g) of triethyl-
amine in 10 ml of dichloromethane, 0.01 mol (3.6 g) of
chloroanhydride of 1-hexadecyl maleate in 10 ml of
dichloromethane was added dropwise at 5–10 °C. The
reaction mixture was stirred for 6 h at 10–15 °C. The
precipitate of triethylammonium hydrochloride was filtered
off and the solvent was removed to give 4.83 g (92 %) of
compound 8.
Analysis
The individuality of the obtained compounds was con-
firmed by thin layer chromatography using Silica gel 60
F
254 (Merck) sheets. The solvents hexane and ethyl acetate
Synthesis of Triethylamino-3-[(Z)-4-hexadecyloxy-4-oxo-2-
mixed in ratios of 2:1, 1:1, 1:2 were used as eluent and the
length of the solvent front was 100 mm. Iodine vapors
were used as the general unspecific color reagent. Specific
color reagents were used for discovering peroxide and
carbonyl groups (N,N-dimethyl-1,4-phenylenediamine and
2,4-dinitrophenylhydrazine, respectively). IR spectra were
butenoyloxy]-1-propanesulfonate 9
This surface active monomer was synthesized with quan-
titative yield (2.84 g) from surfmer 8. The technique was
identical to the synthesis of surfmer 5.
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J Surfact Deterg
recorded using a Spectrod M80 spectrometer in a thin film
(for liquid compounds) or in Vaseline oil (for crystalline
of corresponding derivatives of x-hydroxy carboxylic acids
is shown on Scheme 1:
1
substances). H-NMR spectra were recorded on a Bruker
Peroxyester of 6-hydroxy hexanoic acid 3 was synthe-
sized by reaction of e-caprolactone 1b with sevenfold
molar excess of tert-butyl hydroperoxide in the presence of
boron trifluoride as a catalyst and at 50–55 °C.
150 spectrometer at a working frequency of 300 MHz in
DMSO-d6 (substance concentrations of 5–10 %, internal
standard—hexamethyldisiloxane). The purity of synthe-
sized compounds was additionally confirmed by elemental
analysis.
Cetyl ester of 4-bromobutyric acid 2 was obtained in
three stages. Firstly 4-bromobutyric acid was synthesized
by interaction of c-butyrolactone 1a with hydrogen bro-
mide in the presence of sulphuric acid. The reaction of
resulted acid with phosphorus trichloride led to formation
of chloroanhydride of 4-bromo butyric acid. The desired
ester 2 with 90 % yield was obtained by interaction of the
corresponding chloroanhydride with 1-hexadecanol. The
reaction was carried out in dichloromethane at 10–15 °C
and in the presence of triethylamine as the acceptor of
hydrogen chloride.
Surface Tension
The characterization of the surface activity of the synthe-
sized monomers and copolymers was characterized by
surface tension measurements. These measurements were
performed with a Du Nou¨y ring tensiometer at 20 °C. The
CMC values of the monomers as well as surface tension
above CMC were determined from the inflection points on
the surface tension isotherms.
Peroxide containing maleate 4 was synthesized by
acylation of peroxyester 3 with maleic anhydride. The
acylation was performed at equimolar ratios of reagents in
dichloromethane at 40 °C. A small amount of triethyl-
amine was used as the catalyst. The synthesis of corre-
sponding surfmers 5 and 6 is shown on Scheme 2:
The sulfonate surfmer 5 was synthesized by reaction of
maleate 4 with 1,3-propane sultone. Sulfoalkylation was
performed in dichloromethane at ambient temperature and
in the presence of triethylamine (the molar ratio of the
reagents was 1:1:1). Peroxide containing maleate 4 was
also used for synthesis of non-ionic surfmer 6. Thus,
maleate 4 was converted to chloroanhydride by the inter-
action with phosphorus trichloride. Subsequent acylation of
poly(ethylene glycol) monomethyl ether with correspond-
ing chloroanhydride in the presence of triethylamine led to
the formation of the target monomer 6.
Interpolyelectrolyte Complexes (IEC) Formation
The formation of interpolyelectrolyte complexes was
studied with conductometric titration. To the aqueous
solution of ionic copolymer poly(vinyl acetate-co-maleic
anhydride) with the number-average molecular weight
7,500 g/mol with hydrolyzed anhydride chains or
poly(butyl acrylate-co-dimethylaminoethyl methacrylate)
with the number-average molecular weight 12,000 g/mol
the aqueous solution (1 % by weight) of synthesized
copolymer containing units of the oppositely charged
surfmer was added dropwise. Electrical conductivity was
measured with a CON 2700 conductivity meter.
Particle Size Measurement
Synthesized surfmers 5 and 6 have relatively short
hydrophobic fragments. Therefore, surfmers containing
longer alkyl chains were obtained from 1-hexadecyl
maleate and the cetyl ester of 4-bromobutyric acid 2.
Thus, the carboxyl monomer 8 was synthesized by
reaction of chloroanhydride 7 obtained from 1-hexadecyl
maleate with a stoichiometric amount of triethylammonium
salt of 4-hydroxybutyric acid in dichloromethane. Per-
forming this reaction with 2 mol of triethylamine per 1 mol
of chloroanhydride 7 the corresponding monomer was
obtained in the form of the triethylammonium salt. The
sulfonate surfmer 9 was synthesized via the reaction of an
equimolar amount of monomer 8, 1,3-propane sultone and
triethylamine at ambient temperature after 24 h. The syn-
thesis of surfmers 8 and 9 is shown on Scheme 3:
Methacrylate and maleate cationic surface active
monomers 11 and 12 containing fragments of quaternized
N,N-dimethylaminoethanol were synthesized according to
Scheme 4:
Particle size during IPEC formation and emulsion poly-
merization was determined using a light-scattering tech-
nique [71] in a plane-parallel cuvette in the wavelength range
from 420 to 620 nm on a photocolorimeter LMF-72 M.
Results and Discussion
Synthesis of Surfmers
Novel anionic, cationic and non-ionic maleate or methac-
rylate surface active monomers containing fragments of
tert-butylperoxy esters or higher alkyl esters of x-hydroxy
carboxylic acids as the hydrophobic moiety were synthe-
sized as follows.
The derivatives of x-hydroxy carboxylic acids and x-
bromo carboxylic acids obtained from corresponding lac-
tones 1a,b were used as initial compounds. The synthesis
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J Surfact Deterg
Scheme 1 Synthesis of corresponding derivatives of x-hydroxy carboxylic acids
Scheme 2 Synthesis of surfmers 5 and 6
The structure of monomers was also confirmed by IR
and 1H-NMR spectroscopy. Maleate fragments in the
obtained maleate monomers are defined by absorbance
bands at 1,090–1,240 cm-1 (tC–O), 1,635–1,640 cm-1
(tC = C), 1,728–1,740 cm-1 (tC = O). Absorbance
bands at 1,035–1,220 cm-1 (tC–O), 1,640 cm-1
(tC = C), 1,724 cm-1 (tC = O) are assigned to methac-
rylate fragments in monomer 12. In the 1H-NMR spectrum
of surfmer 12 two signals with chemical shifts of 5.55 ppm
(s.,1H, CH2=) and 6.09 ppm (s., 1H, CH2=) correspond to
protons of a methylene group. This can be explained by the
cis or trans positions of the mentioned protons relative to
the carbonyl group. The signal of methylene cis-proton is
shifted downfield. The proton peak of the methacrylate
methyl group is located at 1,95 ppm (s., 3H, CH3–C=).
The presence of a tert-butylperoxy ester fragment in
monomers 5 and 6 was confirmed by presence of absor-
bance bands at 1,250–1,192 cm-1 defining the vibrations
of C(CH3)3 fragment and by the presence of a band with a
Scheme 3 Synthesis of surfmers 8 and 9
For this purpose the quaternization of N,N-dimethyl-
aminoethanol with hexadecyl 4-bromobutyrate was carried
out. The reaction was performed during heating of equi-
molar amounts of ester 2 and N,N-dimethylaminoethanol in
2-butanone at 80 °C over 15 h. Acylation of the resulting
compound 10 with maleic anhydride in dichloromethane at
40 °C in the presence of triethylamine led to the formation
of maleate surfmer 11. Surface active monomer 12 was
synthesized by acylation of 10 with methacryloyl chloride.
The reaction was performed at equimolar ratios of reagents
in the presence of triethylamine and at 10–15 °C.
1
maximum at 852 cm-1 (tO–O) [72]. In H-NMR spectra
Characteristics of synthesized surface active monomers
of peroxide containing monomers 5 and 6, the signal of
tert-butyl fragment with chemical shift 1.28 ppm (s., 9H)
and their elemental composition are shown in Table 1.
Scheme 4 Synthesis of surfmers 11 and 12
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J Surfact Deterg
Table 1 Characteristics of
synthesized surfmers and their
elemental composition
Surfmer Yield (%)
m.p. (°C) Elemental analysis (found/calculated) (%)
C
H
N
S
Br
5
Quantitative 1.4682a
52.47/52.37 8.36/8.49 2.66/2.69 6.08/6.03
56.87/56.54 8.87/8.69
6
85
92
1.4410a
8
34
67.75/67.60 9.71/9.86
9
Quantitative 28–30
60.90/61.11 9.75/9.57 2.03/2.16 5.11/4.93
58.37/58.13 8.75/8.99 2.10/2.42
61.65/61.42 9.49/9.69 2.37/2.56
11
12
94
90
45–48
34–36
13.51/13.84
14.27/14.62
m.p. melting point
a
Refractive index
Fig. 1 The surface tension isotherms for the aqueous solution-air
interface of surfmers 5 and 6
Fig. 2 The surface tension isotherms for the aqueous solution–air
interface of surfmers 8 and 9
was observed. Absorbance bands at 1,240–1,050 cm-1
corresponding to propylsulfonate fragment were observed
in IR spectra of monomers 5 and 9. In 1H-NMR spectra of
monomers 5 and 9 protons of propylsulfonate fragment are
characterized by signals with the following chemical
shifts—2.21 ppm (m., 2H), 2.94 ppm (t., 2H) and
4.33 ppm (t., 2H). The signal with chemical shift at
10.44 ppm corresponds to ammonium group (s., HN?).
Absorbance band at 1,104 cm-1 assigned to poly(ethylene
glycol) fragment (tC–O) was observed in IR spectra of
non-ionic monomer 6.
Surface Activity of the Synthesized Monomers
The synthesized monomers are typical surfactants, since
they reduce the surface tension at the aqueous solution–air
interface. Therefore, the values of surface tension of
aqueous solutions of the synthesized surface active
monomers were measured and their CMC and the surface
tensions above the CMC were determined. The surface
tension isotherms of synthesized surfmers are shown on
Figs. 1, 2 and 3. The CMC values and the values of surface
tension above CMC are shown in Table 2.
Fig. 3 The surface tension isotherms for the aqueous solution–air
interface of surfmers 11 and 12
Relatively high values of CMC for surfmers 5 and 6
could be explained by the presence of a relatively short
hydrophobic tert-butylperoxyacyl fragment and a strong
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J Surfact Deterg
Table 2 The value of CMC and surface tension above CMC of the
synthesized surfmers
Surfmer
CMC (wt%)
Surface tension (mN/m)
5
2.5
31.2
34.6
43.17
36.7
41.2
38.1
6
3.7
8
0.01
0.1
9
Scheme 5 General structure of synthesized surface active
copolymers
11
12
0.03
0.06
hydrophilic sulfonate group or
a long hydrophilic
poly(ethylene glycol) chain. This promotes real solubility
of monomers in water up to higher concentrations com-
pared to the other surfmers.
Lower values of CMC of surfmers 8 and 9 are caused by
a long cetyl chain which increases the hydrophobic char-
acter of the molecule and reduces the solubility of the
monomer in water [73]. The higher value of the CMC of
surfmer 9 is explained by the presence of a strong hydro-
philic sulfonate group.
Monomers 11 and 12 contain hydrophilic quaternary
ammonium fragments. The presence of a long hydrophobic
chain promotes the poor solubility of the obtained cationic
monomers. Therefore the corresponding monomers form
micelles at low concentrations. The value of the CMC of
surfmer 12 is slightly higher due to presence of carboxylic
groups.
Fig. 4 The surface tension isotherms at the aqueous solution–air
interface of synthesized copolymers
As it can be concluded, the introduction of hydrophilic
groups of various natures and hydrophobic chains of dif-
ferent lengths gives an opportunity to vary the surface
active properties of the synthesized surfmers over a wide
range. It is worth mentioning that values of CMC reported
in the literature for various types of surfmers vary over a
wide range [27, 28, 33, 34, 40, 42]. Such values are sig-
nificant for an insight into the interfacial behavior of am-
phiphiles according to previously published papers.
Synthesized anionic and cationic surfmers were utilized
for obtaining surface active copolymers.
The incorporation of units of surface active monomers
into the copolymer structure increases their surface activity
in comparison to binary copolymer VEP–N-vinylpyrroli-
done as can be seen in Fig. 4. The presence of inflexion
points on the surface tension isotherms verifies the capa-
bility of the synthesized copolymers for association into
supramolecular structures, similar to micelles of low
molecular weight surfactants.
In contrast to low molecular surfactants, where micelle
formation takes place as a phase transition at a certain
discrete concentration, with the aggregation number
approximately constant, the polymers are polydisperse with
a varying number of functional groups per macromolecule.
Therefore, the formation of micelles involves also the
conformational changes and exchange of macromolecules
between the solution and the micelles or interface, in order
to reach packing with the minimum energy under given
conditions. Though a fast decrease in surface tension below
the CMC is explained by equilibrium adsorption at the
water–air interface, similar to low molecular surfactants, a
Copolymerization of Synthesized Surfmers with Vinyl
Monomers
The solution copolymerization of synthesized surfmers
with peroxide containing monomer VEP and N-vinylpyrr-
olidone was carried out. The general structure of the syn-
thesized surface active copolymers is shown on Scheme 5:
The resulting copolymers are water soluble and reduce
the surface tension at the aqueous solution–air interface.
The surface tension isotherms of synthesized copolymers
are shown on Fig. 4.
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J Surfact Deterg
Fig. 6 The dependence of IPEC particles size on the added amount
of 1 % aqueous solutions of oppositely charged copolymers. Curve 1
corresponds to poly(maleic anhydride-co-vinyl acetate) with N-
vinylpyrrolidone–VEP–surfmer 12. Curve 2 corresponds to poly(-
butyl acrylate-co-dimethylaminoethyl methacrylate) with N-vinyl-
pyrrolidone–VEP–surfmer 9
Fig. 5 The dependence of conductivity of ionic copolymer solution
on the added amounts of 1 % solutions of oppositely charged
copolymers. Curve 1 corresponds to the solution of anionic copoly-
mer poly(maleic anhydride-co-vinyl acetate) when adding the solu-
tion of VEP–N-vinylpyrrolidone—surfmer 12. Curve 2 corresponds to
the solution of cationic copolymer poly(butyl acrylate-co-dimethyl-
aminoethyl methacrylate) when adding the solution of VEP–N-
vinylpyrrolidone—surfmer 9
As can be seen from Fig. 5, the conductivity of the
solution decreases during the interaction of oppositely
charged oligoelectrolytes. The inflection was observed at
equimolar ratio of copolymers.
further decrease in the surface tension above the CMC is
caused by further reorganization of the molecules.
Incorporation of units of ionic surfmers into the struc-
ture of VEP–N-vinylpyrrolidone macromolecules provides
the polyelectrolyte properties, namely the capability to
form IPEC with oppositely charged polymers.
Also, the size of colloid particles changes during addi-
tion of the oppositely charged copolymer as shown in
Fig. 6.
The size of particles during the addition of oppositely
charged copolymer increased at first. When a certain
amount of oligoelectrolyte was added, the particle size
remained practically unchanged.
Anionic copolymer poly(maleic anhydride-co-vinyl
acetate) with hydrolyzed anhydride fragments and cationic
copolymer poly(butyl acrylate-co-dimethylaminoethyl
methacrylate) are used as models of anionic and cationic
biopolymers [74]. Therefore, the study of IPEC formation
between model copolymers and synthesized copolymers
with surfmers fragments is an effective technique for the
estimation of their ability to bind biopolymers, particularly
nucleic acids.
The results obtained indicate the formation of stable
IPEC during the interaction of the model and synthesized
polyelectrolytes.
The formation of IPEC can be explained in nucleation
and growth terms. On first addition of the countercharged
electrolyte, the nucleation of IPEC takes place, but, since
one of the polyelectrolytes is in excess, the IPEC are rich in
this component, which still have vacant charged groups.
Further addition of countercharged polymer leads to a
saturation of IPEC and, a decrease in its charge to a value
when nucleation of a new IPEC is favored. From this it can
be concluded, that IPEC can be characterized with a certain
finite aggregation number. The constant size above
0.040 % represents a certain steady state, when previously
formed IPEC coexist with growing ones. Moreover, as it
can seen from Fig. 5 the conductivity constantly decreases
above 0.040. Only at around 0.01, does the conductivity
reach a plateau, witnessing the termination of both nucle-
ation and growth of IPEC. The fact, that the IPEC size does
not increase dramatically after 0.01 % says, that already at
0.004, the size distribution is dominated with ‘‘passive’’
IPEC, having only a small, not detectable by light scat-
tering, fraction of growing IPEC.
During IPEC formation, the electrical conductivity of
polyelectrolyte solution decreases due to the formation of
insoluble pairs of oppositely charged ions attached to a
polymer chain and therefore a decrease in the overall ion
concentration.
The IPEC formation between anionic copolymer
poly(maleic anhydride-co-vinyl acetate) with hydrolyzed
anhydride fragments and synthesized cationic oligoelec-
trolyte VEP–N-vinylpyrrolidone—surfmer 12 as well as
between cationic copolymer poly(butyl acrylate-co-
dimethylaminoethyl methacrylate) (it is a cationic polymer
in protic solvents, since ammonia groups act like Brønsted
base, become protonated [75] ) and synthesized anionic
copolymer VEP–N-vinylpyrrolidone—surfmer
9
was
studied with conductometric titration.
The dependence of conductivity of aqueous solutions of
model copolymers on adding amounts of aqueous solutions
of copolymers with surfmers units is shown on Fig. 5.
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J Surfact Deterg
4-hydroxybutyric acid and 6-hydroxyhexanoic acid was
proposed and developed. The incorporation of various
hydrophilic and hydrophobic groups tailors the surfactant
properties of synthesized surfmers over a wide range. The
copolymerization of the resulting surfmers with other
monomers led to the formation of surface-active copoly-
mers. Synthesized copolymers containing the units of ionic
surfmers were shown to be capable of forming stable IPEC
with oppositely charged copolymers. The synthesized
peroxide-containing surfmer during emulsion polymeriza-
tion acted as an effective surfactant initiator as well as the
comonomer providing stable surfactant-free polymer
dispersions.
Fig. 7 The dependence of styrene conversion during self-initiated
aqueous emulsion copolymerization of a mixture of styrene—surfmer
6 at 85 °C. The surfmer content in the monomer mixture was 10
(curve 1), 15 (curve 2) and 25 (curve 3) % (mol)
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present he has been working at Lviv Polytechnic National University.
His research field is the synthesis of functional surface active
peroxides and monomers.
123