Synthesis and characterization of a novel series of cationic fumaric polymerizable emulsifiers

Article abstract of DOI:10.1007/s11743-010-1199-2

A series of novel cationic fumaric polymerizable emulsifiers (named as F series emulsifiers) were synthesized. The chemical structures of these emulsifiers were confirmed by ¹H NMR and MS and their minimal inhibitory concentrations to Escherich

Full text of DOI:10.1007/s11743-010-1199-2

J Surfact Deterg (2011) 14:37–41
DOI 10.1007/s11743-010-1199-2
ORIGINAL ARTICLE
Synthesis and Characterization of a Novel Series of Cationic
Fumaric Polymerizable Emulsifiers
•
Weihong Qiao Cui Cao Yingli Sun
•
•
•
Hongzhu Liu Xingshun Zhao Xinmei Fu
•
Received: 18 September 2009 / Accepted: 2 April 2010 / Published online: 29 April 2010
Ó AOCS 2010
Abstract A series of novel cationic fumaric polymerizable
emulsifiers (named as F series emulsifiers) were synthe-
sized. The chemical structures of these emulsifiers were
confirmed by 1H NMR and MS and their minimal inhibitory
concentrations to Escherichia coli were determined. Anti-
bacterial tests of latex films showed that [2-(N-benzyl-N,
N-dimethylamino)ethyl]dodecyl fumaric ammonium bro-
mide, [2-(N-benzyl-N,N-dimethylamino)ethyl]decyl fumaric
ammonium chloride and [2-(N-benzyl-N,N-dimethylamino)
ethyl]dodecyl fumaric ammonium chloride can possibly be
used as a polymerizable bactericides.
of latex particles by physical adsorption. The weak phys-
ical adsorption of traditional emulsifiers may cause the
destabilization of the latex and water sensitivity of the film.
However, polymerizable emulsifiers can improve the sta-
bility of the lattices against electrolytes [1, 2], shear forces
[3] and freezing/thawing [4], as well as affecting the water
sensitivity of the film formed [2, 5–7].
The polymer emulsion which is polymerized by an
antimicrobial cationic emulsifier has antibacterial proper-
ties, and it can overcome the shortcoming of high toxicity
and poor security of the low molecular weight antimicro-
bial agent [8–15]. When this polymer emulsion is applied
to the preparation of coatings, the coatings have lasting
antibacterial properties, and other additive antibacterial
agents are not needed.
Keywords Cationic fumaric polymerizable emulsifiers ꢀ
Synthesis ꢀ Characterization ꢀ Minimal inhibitory
concentrations
Usually anionic and non-ionic emulsifiers are used in the
preparation of coatings, while cationic emulsifiers are sel-
dom used in the preparation of coatings. In this paper, a
series of fumaric cationic polymerizable emulsifiers(Fseries
emulsifiers) were synthesized and used in the emulsion
polymerization of vinyl acetate–butyl acrylate–vinyl
versatate–hexafluorobutyl methacrylate, the antimicrobial
activity of F series emulsifiers and the latex film was
tested. The results indicate an excellent degree of anti-
microbial activity and good application prospects of the
F series polymerizable emulsifiers.
Abbreviations
MIC
Minimal inhibitory concentration
CTAB Cetyl or hexadecyltrimethyl ammonium bromide
Introduction
Emulsifiers play important roles in emulsion polymeriza-
tion. Traditional emulsifiers are adsorbed onto the surface
W. Qiao (&) ꢀ C. Cao ꢀ Y. Sun ꢀ X. Fu
Experimental
State Key Laboratory of Fine Chemicals, School of Chemical
Engineering, Dalian University of Technology, 158 Zhongshan
Road, Dalian 116012, People Republic of China
e-mail: qiaoweihong2001@sina.com
Materials
Maleic anhydride (analytical grade, Tianjin Fuyu Fine
Chemical Co. Ltd), n-decanol, n-dodecanol and n-tetra-
decyl alcohol (analytical grade, Tianjin Damao Chemical
H. Liu ꢀ X. Zhao
Dalian Zebon Fluorocarbon Paint Stock Co. Ltd.,
Yingtai Road, Dalian 116036, People Republic of China
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J Surfact Deterg (2011) 14:37–41
Reagent Factory), phosphorus trichloride (analytical grade,
Tianji No. 1 Chemical Reagent Factory), dimethyletha-
nolamine (analytical grade, Feixiang Chemicals Co. Ltd),
benzyl chloride (analytical grade, Beijing Xingjin Chemi-
cal Factory), benzyl bromide (analytical grade, Shanghai
Nuotai Chem Co. Ltd), Hexadecyltrimethyl ammonium
bromide (CTAB, analytical grade, Xiamen Pioneer Tech-
nology Co. Ltd).
(2E)-alkyl-(dimethylaminoethyl) butenedionate 2-(dimeth-
ylamino)ethyl alkyl ester (4). Dimethyl-ethanolamine
(0.05 mol), K2CO3 (0.05 mol) and butanone in sequence
were placed in a three-necked flask. Then compound 2 was
added dropwise to the reaction mixture and stirred for
2 to 4 h at 70 to 80 °C. The solution was filtered when it
had cooled to room temperature and then washed with
acetone. Compound 3 was obtained by drying in a vacuum
for 4 h. Compound 3 was dissolved in water, using sodium
hydroxide solution to control the pH of the solution to
weak alkaline, and compound 4 was extracted using
chloroform.
Synthesis of Polymerizable Emulsifiers
The series of polymerizable emulsifiers, with the length of
the carbon chain 10, 12, or 14, were synthesized according
to the reaction scheme shown in Fig. 1.
[2-(N-benzyl-N,N-dimethylamino)ethyl]alkyl fumaric
quaternary ammonium salt (5). The compound
4
Synthesis of 1 was carried out according to reference
[16].
(0.05 mol), benzyl chloride (or benzyl bromide; 0.05 mol)
and butanone were placed in a reactor and stirred for
16 to 24 h at 60 to 70 °C. Removing solvent butanone by
Alkyloxyacrylyl chloride-2-butenoic acid alkyl ester (2).
Compound 1 (0.05 mol) was placed in a three-necked flask,
stirred and heated. When the solid had turned to liquid,
PCl3 (0.025 mol) was added dropwise, then allowed to
react for 2 h at 60 °C. After standing at ambient temper-
ature for 2 h, the surplus PCl3 was removed by vacuum
distillation. The crude product was obtained by filtering to
remove H3PO3, which was used in the following reaction
without purification.
1
rotary evaporator, compound 5 was obtained. A typical H
NMR (CD3OD, 400 MHz) for F series product: d 0.86–
0.90 (t, 3H, CH2–CH3), 1.26–1.35 (m, 18H, –(CH2)9–),
1.65–1.70 (m, 2H, –(CH2)9–CH2–CH2–), 3.16–3.27 (s, 6H,
–N(CH3)2–), 3.84–3.91 (t, 2H, –(CH2)9–CH2–CH2–O–),
4.15–4.20 (t, 2H, –O–CH2–CH2–N(CH3)2–), 4.68–4.76 (t,
2H, –CH2–CH2–N(CH3)2–), 4.76–4.86 (s, 2H, –N(CH3)2–
CH2–C6H5–), 6.85–6.90 (s, 2H, –CO–CH=CH–CO–),
Fig. 1 Synthesis of fumaric
cationic polymerizable
emulsifiers
O
O
O
OR
OR
OH
PCl3
R-OH
O
Cl
O
O
1
2
O
OH
N
K2CO3 , butanone
O
O
OR
OR
pH=8.5
chloroform
O
O
HCl· N
N
O
O
3
4
CH2Br or
CH2Cl
butanone
O
F1: R1=C10H21 X1=Br
F2: R2=C12H25 X1=Br
F3: R3=C14H29 X1=Br
OR
H3C
CH2
H3C
O
F4: R1=C10H21 X2=Cl
N
X
F5: R2=C12 25
H
X2=Cl
X2=Cl
O
F6: R3=C14 29
H
5
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J Surfact Deterg (2011) 14:37–41
39
7.61–7.63 (m, 5H, –CH2–C6H5–). MSD: F1: m/z 418.3
(M?–Br-). F2: m/z 446.3 (M?–Br-). F3: m/z 474.3 (M?–
Br-). F4: m/z 418.3 (M?–Cl -). F5: m/z 446.3 (M?–Cl-).
F6: m/z 474.3 (M?–Cl-).
Latex films were prepared by placing the required
amount of latexes on polyester sheets and then drying them
at 30 °C under static air in a temperature-controlled
chamber for 24 h. After the film formation, a representative
and uniform piece (3 cm 9 3 cm) was cut from each sheet,
and the square samples were prepared and dried at 40 °C in
vacuo for another 24 h.
Measurement of Minimal Inhibitory Concentration
(MIC)
(1) A suspension of Escherichia coli with a concentration
range of 5.0 9 105 to 10.0 9 106 cfu/mL was
prepared.
Antibacterial Test of Latex Film
The antibacterial activity of the synthesized latex film
was evaluated according to the method of viable plate
count against Escherichia coli BL21(DE3) [17–20]. A
certain amount of the bacterial suspension was inoculated
to negative control samples, blank control sample and
latex film samples. This was done five times at the same
time on 3 different samples. When the humidity was
greater than 90%, these 3 kinds of samples were covered
with a cover glass and cultured for 24 h at 37 °C in
sterilized petri dishes by the sticking membrane method.
Then these samples and cover glass were eluted with
20 mL of washing liquid for many times. Then, 200 lL
washer liquid was taken and inoculated into the Luria–
Bertani medium. The numbers of live bacteria were
calculated after being cultured for 24–48 h in an
incubator.
(2) A culture medium was prepared containing the antibac-
terial agent: the antibacterial agent solution was doubly
diluted with distilled water to different concentrations as
the test solutions. The test solutions with different
concentrations (5 mL in each case) were added to a test-
tube which contained 5 mL Luria–Bertani medium (its
concentration two times that of the test solution).
(3) The bacterial suspension 0.1 mL was inoculated into
the above antibacterial culture medium. The concen-
tration of the Escherichia coli suspension was
3.55 9 106 cfu/mL. This group was used as experi-
mental samples.
(4) A positive control sample was prepared by inoculat-
ing the bacterial suspension into the culture medium
without any antibacterial agent by the method men-
tioned above.
(5) Negative control samples were prepared by placing
the culture medium in two test tubes.
Results and Discussion
(6) The experimental samples, positive control and
negative control were all put into an incubator for
culturing for 24 h at 37 °C.
Structural Characterization
(7) The number of living bacteria in the experimental
The trans-structure of the F series product was observed by
1
coupling constants from H-NMR. The J of the H on the
samples was calculated.
unsaturated carbon of the F series product is 15.6 Hz,
which is higher than that of the similar trans-alkene
(structure of fumaric monoester monoacidamide) 14 Hz
[19] and cis-isomer monododecyl maleate 12.8 Hz. The
fact is that J of the H on the unsaturated carbon of the
trans-alkene is higher than that of the cis-isomer.
Preparation of Latex Films
The emulsifiers and CTAB were used with the same
technique for the emulsion polymerization of vinyl ace-
tate–butyl acrylate–vinyl versatate–hexafluorobutyl meth-
acrylate, recipes were presented in Table 1.
By analyzing this five steps reaction, only the second
step reaction has the possibility to cause the isomerization.
Usually, when the temperature is higher than about 100 °C
or the existence of some acids (HCl and H3PO3 etc.), it is
easily to bring about the isomerization of the maleate [20].
During the second step reaction, H3PO3 produced as a
byproduct acid in this reaction, can catalyze the isomeri-
zation of cis-isomers to trans-isomers in the process of
acylchlorination. For other four step reactions, neither a
high temperature nor the existence of any acid can cause
the isomerization of alkene. The possible reaction mecha-
nism is shown in Fig. 2.
Table 1 Recipes for emulsion polymerization
VAc BA
VEOVA
10
HFBMMA SF V50 H2O
Charge
(g)
1.86 0.62 0.62
0.93
0.18 0.07 37.93
Feed (g) 28.14 9.38 9.38
Total (g) 30 10 10
14.07
15
2.69 0.28 42.30
2.87 0.35 80.23
Vac vinyl acetate, BA butyl acrylate, VeoVa 10 vinyl versatate,
HFBMMA hexafluorobutyl methacrylate, SF emulsifier, V50 2,
20-azobis (2-amidinopropane) hydrochloride
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J Surfact Deterg (2011) 14:37–41
Fig. 2 Mechanism of the acid
catalyzed transformation of the
hemiesters of maleic acid and
their chlorides to trans-isomers
O
O
O
O
O
O
CnH2n+1
CnH2n+1
H
CnH2n+1
CnH2n+1
O
R
O
O
O
H
R
R
R
O
O
R=Cl,OH; n=8,10,12,14,16
Table 3 The anti-bacterial test of latex films with regard to the
numbers of viable bacteria
Table 2 The minimal inhibitory concentration of the polymerizable
surfactants
Number of the
parallel experiment
Emulsifier
CTAB
Emulsifiers
CTAB F1
F2
F3
F4
F5
F6
MIC (10-5 mol/L) 2.44
4.88 2.44 625 9.77 4.88 625
F2
F3
F4
F5
F6
1
2
3
4
5
0
0
0
0
0
0
0
0
0
0
520
460
430
390
455
0
0
6
0
0
0
0
0
1
0
610
570
430
540
455
Minimal Inhibitory Concentration (MIC)
of the Polymerizable Emulsifiers
The designed quaternary ammonium salt polymerizable
emulsifiers with an ester bond and double bonds, not only
possess polymerizable ability, but also show antibacterial
properties, and they adsorb by covalent bonds to the sur-
face of latex particles during emulsion polymerization. The
latex itself has antibacterial properties after formation of
the latex film. If the latex is used in paint, the paint may be
endowed with antibacterial properties without the need of
an additional antibacterial agent. In order to test the anti-
bacterial property of the polymerizable emulsifiers syn-
thesized, it was necessary to study their MIC and
antibacterial activity of their latex film.
Antibacterial Activity of Latex Film
The antimicrobial activity of the latex film was tested and the
antibacterial data are shown in Table 3. According to
Table 3, latex films of CTAB, F2, F4 and F5 can inhibit
Escherichia coli, latex films of F3 and F6 have a certain
germicidal action but the effect was limited. After poly-
merization, the polymerizable emulsifiers still had antibac-
terial activity and the antibacterial activity was related to the
carbon chain length. The antibacterial activity of the latex
films of the polymerizable emulsifiers with chains twelve
carbons long was better than those with chains with ten and
fourteen carbons and this was confirmed by the MIC.
The MIC values of the polymerizable emulsifiers with
regard to Escherichia coli were studied and are shown in
Table 2. The results show that the traditional cationic
emulsifier CTAB gives lower MIC values and presents
good antibacterial properties. The MIC values of F1, F2,
F4 and F5 belong to an identical concentration gradient
as CTABs, therefore F1, F2, F4 and F5 also possess
these good antibacterial properties. In contrast, the MIC
values of F3 and F6 are higher and they do not show
good antibacterial properties. When the carbon chain
length of the aliphatic group of the quaternary ammo-
nium bromide and quaternary ammonium chloride is the
same, such as in F1 and F4, F2 and F5, F3 and F6, the
MIC values of the former are lower than that of the later.
This indicates that the antibacterial effect of quaternary
ammonium bromide is better than quaternary ammonium
chloride. With both quaternary ammonium bromide or
quaternary ammonium chloride, the MIC of the com-
pounds with chains twelve carbon long is lower than
those with chains of ten and fourteen carbons. This also
shows that the length of the carbon chain has an influ-
ence on the MIC.
From Table 3, the latex film of the traditional emulsifier
CTAB also showed favorable germicidal action. This is
because CTAB, itself a favorable bactericide, remained in
the latex after emulsion polymerization and gathered on the
surface of the latex film after film formation. However, the
synthesized cationic emulsifiers, with a polymerizable
group and antibacterial properties, were bonded on the
surface of the latex particles by covalent bonds. Therefore,
the polymerizable emulsifiers cannot be washed out of the
surface of the latex film by water and could show abiding
antibacterial properties, but the traditional emulsifier
CTAB may be washed out of the surface of the latex film.
Then the latex film of CTAB was washed ultrasonically
for 24 h, then the amount which had been washed out of the
surface of the latex film was measured by titration. The
strength of ultrasonic elution was enough to isolate the
emulsifier that was not bonded to the latex film surface
completely, and the titration analysis methods were accurate
to 5 ppm. As the mass of emulsifier, latex films and
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J Surfact Deterg (2011) 14:37–41
41
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Acknowledgments We thank Professor Lingyun Jia of School of
Environmental and Biological Science and Technology in Dalian
University of Technology for supporting the testing of MIC. The
financial support granted by Dalian Science and Technology Pro-
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Author Biographies
Weihong Qiao obtained an M.Sc. in 1994 and a Ph.D. in 2000 from
Dalian University of Technology. Since 1994, she has been teaching
and working at Dalian University of Technology, and her main field
of research is the synthesis and physical chemistry of emulsifiers.
Cui Cao is a master’s student at Dalian University of Technology.
Her main field of research is synthesis and properties of emulsifiers.
Yingli Sun obtained an M.Sc. from Dalian University of Technology
in 2008. His main field of research is the synthesis and physical
chemistry of emulsifiers.
5. Asua JM, Schoonbrood HAS (1998) Reactive surfactants in
heterophase polymerization. Acta Polymerica 49:671–686
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styrene–butyl acrylate lattices using maleic or succinic surfac-
tants: mechanical properties, water rebound and grafting of the
surfactants. Polymer 41:1147–1155
7. Amalvy JI, Unzue MJ, Schoonbrood HAS, Asua JM (2002)
Reactive emulsifiers in heterophase polymerization: colloidal
properties, film-water absorption, and emulsifier exudation. J
Polym Sci Part A Polym Chem 40:2994–3000
Hongzhu Liu is a senior engineer, and his main field of research is
the exploration of waterborne fluorine-containing polymers and
waterborne coatings.
Xingshun Zhao is an engineer, and his main field of research is the
exploration of waterborne fluorine-containing polymers and water-
borne coatings.
Xinmei Fu is an engineer, and her main field of research is organic
mass spectrometry and high performance liquid chromatography.
8. Sun H, Xia Y, Chen L, Tan ZY, Meng LY (2006) Present situ-
ation and development trend of research on antibacterial agent at
home and abroad. China Plastics Industry 34:1–4
123