Hyperbranched 1,2,3-triazoleorganoethoxysiloxanes and metal embedded nanocomposite coatings based on them

1. Школа-конференция молодых ученых «бесхлорная химия силиконов»

Hyperbranched 1,2,3-triazoleorganoethoxysiloxanes and
metal embedded nanocomposite coatings based on them
Мигулин Д. А.1, Розанова Ю. В.1, Мешков И.Б. 1, Зезин А. А.1,2, Музафаров А. M.1
1 Институт Синтетических Полимерных Материалов РАН им. Н.С. Ениколопова, 117393 Москва,
ул. Профсоюзная, 70.
2Химический Факультет Московского Государственного Университета им. М.В.Ломоносова, 119234
Москва, ул. Колмогорова, 1, стр.3.
E-mail: julia.rozanova.2000@mail.ru
Москва 2021

2.

DMA-1,2,3-triazolesiloxane
f
c
g
h
a
b
e
d
f
e
a
g
d
h
b
c
20
15
10
5
0
-5
-10
-15
-20
-25
-30
-35
(ppm)
-40
-45
-50
-55
-60
-65
-70
-75
-80
-85
-90
0.9
9.0
8.5
8.0
7.5
2.0
7.0
6.5
6.0
5.5
5.0
4.5
(ppm)
3.5
4.0
5.9
3.5
3.0
2.5
2.00.2
2.0
2.1
1.5
2.0
1.0
0.5
4000
3500
3000
2500
2000
1500
4000
3500
3000
2500
2000
1500
4000
3500
3000
2500
2000
Wavenumber (cm-1)
1500
i
j
c
a
i
imp. of
THF
b
d
imp. of
THF
c
e
g
e
15
10
5
0
-5
-10
-15
-20
-25
-30
-35
-40
(ppm)
-45
-50
-55
-60
-65
-70
-75
-80
-85
-90
9.0
h
f
1.1
1.0
d
1.0
2.0
8.5
8.0
j
h
7.5
2.0
7.0
6.5
6.0
5.5
5.0
(ppm)
4.5
2.7
4.0
2.0
3.5
3.0
2.5
0.9
2.0
CH3-CH2-Oc
d
a
2.8
1.5
CH3-CH2-O-
e
a
b
f
g
2.0
1.0
0.5
e
b
c
d
a
b
1.8
20
15
10
5
0
-5
-10
-15
-20
-25
-30
-35
(ppm)
-40
-45
29Si NMR (59.6 MHz) |Solvent: CDCl3, r.t.
-50
-55
-60
-65
-70
-75
-80
-85
-90 9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
(ppm)
4.0
2.0
3.5
2.0
3.0
2.5
2.0
1.5
2.7
2.0
1.0
0.5
1H NMR (300MHz) |Solvent: CDCl3, r.t.
29Si-NMR in CDCl
3
1H-NMR in CDCl
3
FT-IR
(N3-siloxane)
Intens. [a.u.]
(N3-siloxane)
PY-1,2,3-triazole-siloxane
2264.507
1250
Mw=2381
Mw/Mn=1,1
1000
Mw = 2855 g/mol
Mw/Mn =1.2
2520.619
Mw = 1696 g/mol
Mw/Mn = 1.6
2777.726
750
1793.506
2009.425
2339.550
2447.569
1866.560
500
3033.901
250
PY-1,2,3-triazolesiloxane
0
1800
2000
2200
2400
2600
2800
3000
3200
m/z
MALDI
0
1
2
3
4
5
6
7
8
9 10 11 12 min
GPC (THF, 15kD)

3.

Counts
DMA-1,2,3-triazole siloxane/Ag-NPs
Energy (keV)
EDX elemental analysis of DMA-1,2,3-triazole-siloxane/AgNPs
3
40 min
0 min
2
10 min
20 min 30 min 40 min
Absorbance
30 min
20 min
1
10 min
0 min
0
200
400
Wavelenght (nm)
600
800
UV spectra of DMA-1,2,3-triazole-siloxane in C2H5OH

4.

(30 min, 10:1)
3
DMA-1,2,3-triazole-siloxane/AgNPs
(25:1)
PY-1,2,3-triazole-siloxane/AgNPs
(25:1)
2
Absorbance
2
0 min
10 min
30 min
40 min
2
0 min
10 min
30 min
PY-1,2,3-triazolesiloxane/Ag-NPs (10:1)
0 min
10 min
30 min
45 min
1
1
1
0
200
0
0
300
400
500
600
700
800
200
300
400
500
600
700
800
200
300
400
500
600
700
800
(10 min, 25:1)
Wavelenght (nm)
(10 min, 25:1)
(30 min, 25:1)
(30 min, 25:1)
Type of polymer
Amine(Pyridine)1,2,3-triazole polymer
functional groups/Ag+
Irradiation time
in 0,2%
ethanol solutio
n (min)
Average Size of
Ag-NP
(nm)
DMA-1,2,3triazole-siloxane
25:1
10
2,8
PY-1,2,3triazole-siloxane
25:1
10
2,1
DMA-1,2,3triazole-siloxane
25:1
30
5,1
PY-1,2,3triazole-siloxane
25:1
30
5,2
PY-1,2,3triazole-siloxane
10:1
30
8,2

5.

UV spectra of DMA-1,2,3-triazole
siloxane/Ag-NPs
in H2O
TEM of DMA-1,2,3-triazole siloxane/Ag-NPs
from H2O (left); after 1 month of storage in
water solution (right)
DMA-1,2,3-triazole siloxane/Ag-NPs
from H2O
(Water-soluble DMA-1,2,3-triazole-siloxane)
after 1 month of storage
Size distribution of DMA-1,2,3-triazole
siloxane/Ag-NPs

6.

Size distribution of Ag-NPs
DMA-1,2,3-triazole-siloxane/Ag-NPs
Stöber silica modified with DMA-1,2,3-triazole-siloxane/Ag-NPs
2
Absorbance
Stöber silica
40
30
20
10
0
-10
-20
-30
-40
-50
-60
-70
-80
-90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190 -200 -210 -220 -230 -240
f1 (мд)
TEM images of Stöber silica
modified with DMA-1,2,3-triazolesiloxane/Ag-NPs
1
Size distribution of Stöber silica in H2O
(DLS data)
0
40
200
400
Wavelenght (nm) 600
UV-Vis spectra
800
30
20
10
0
-10
-20
-30
-40
-50
-60
-70
-80
-90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190 -200 -210 -220 -230 -240
f1 (мд)
29Si MAS NMR Spectra of
SiO2 before modification
(bottom) and after modification with DMA-1,2,3-triazolesiloxane/Ag-NPs (top)
Size distribution of Stöber silica
modified with DMA-1,2,3-triazole-siloxane/Ag-NPs
(DLS data)

7.

Thank you for
attention!
Работа была выполнена при поддержке гранта РНФ № 21-13-00437.

8.

2
1
0
200
400
600
800

9.

Absorbance
4
1
3
2
1
0
0
200
200
400
400
600
600
Wavelength (nm)
5
4
0 min
Mig165(1:25)
10 min
3
30 min
40 min
2
3
1
2
0
200
400
1
0
200
300
400
500
600
700

10.

DMA-1,2,3-triazole-siloxane
PY-1,2,3-triazole-siloxane
(10 min)
(10 min)
Mig165 (30 min, 1/6)
TEM
2
3
0 min
10 min
30 min
45 min
1
0,0
0
300
400
500
600
700
800
Absorbance
Absorbance
0 min
10 min
30 min
0,5
200
DMA-1,2,3-triazole-siloxane/Ag+
(25:1)
DMA-1,2,3-triazole-siloxane
(1:10)
DMA-1,2,3-triazole-siloxane
(1:6)
1,0
2
0 min
10 min
30 min
PY-1,2,3-triazole-siloxane
DMA-1,2,3-triazole-siloxane
(30 min)
(30 min)
1
0
200
400
Wavelenght (nm)
600
800 200
300
400
500
600
700
800
Wavelenght (nm)
Wavelenght (nm)
5
5
4
PY-1,2,3-triazole-siloxane (1:25)
PY-1,2,3-triazole-siloxane (1:10)
PY-1,2,3-triazole-siloxane (1:6)
4
4
3
1
0
200
300
400
500
Wavelenght (nm)
600
700
Absorbance
2
Absorbance
0 min
10 min
30 min
45 min
0 min
10 min
30 min
45 min
2
1
800
0
200
0 min
10 min
30 min
40 min
3
3
Absorbance
Absorbance
1,5
2
TEM
1
0
300
400
500
Wavelenght (nm)
600
700
800 200
400
600
Wavelenght (nm)
800

11.

Intens. [a.u.]
Mig 165 (MALDI)
Mw = 1696 g/mol
Mw/Mn = 1.6
2264.507
1250
1000
2520.619
2777.726
750
1793.506
2009.425
2339.550
2447.569
1866.560
0
500
1
2
3
4
5
6
3033.901
7
8
9
10
11
12 min
GPC (THF, 15kD)
250
0
1800
2000
2200
2400
2600
2800
3000
3200
f
m/z
Mn=2348
Mw=2381
Mw/Mn=1,0141
II
I
III
II
I
a
c
g
h
b
e
d
f
e
a
g
d
III
c
15
10
5
0
-5
-10
-15
-20
-25
-30
-35
(ppm)
-40
-45
-50
-55
-60
-65
-70
-75
-80
-85
-90
9.0
7.5
8.0
8.5
2.5
j
imp. of
THF
b
d
imp. of
THF
c
e
e
III
10
5
0
-5
-10
-15
-20
-25
-30
-35
-40
(ppm)
-45
-50
-55
I
-60
0.5
1.0
1.5
c
a
i
g
15
2.0
2.1
2.00.2
2.0
i
II
I
3.0
3.5
4.0
4.5
(ppm)
5.0
5.5
6.0
6.5
7.0
5.9
3.5
2.0
0.9
20
h
b
-65
-70
-75
-80
-85
-90
II
9.0
d
1.0
2.0
8.5
8.0
j
h
h
f
1.1
1.0
7.5
7.0
g
(ppm)
4.5
2.0
2.7
2.0
5.0
5.5
6.0
6.5
a
b
f
3.0
3.5
4.0
2.5
2.0
2.0
2.8
0.9
0.5
1.0
1.5
e
a
b
e
c
d
III
c
d
a
b
15
10
5
0
-5
-10
-15
-20
-25
-30
-35
(ppm)
-40
-45
29Si NMR (59.6 MHz) |Solvent: CDCl3, r.t.
29Si-NMR
-50
-55
-60
-65
-70
-75
-80
-85
-90
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
(ppm)
4.0
1H NMR (300MHz) |Solvent: CDCl3, r.t.
1H-NMR
2.0
2.0
1.8
20
3.5
3.0
2.5
2.0
1.5
2.7
1.0
2.0
0.5
4500
4000
3500
3000
2500
2000
1500
Wavenumber (cm-1)

12.

3
Absorbance
2
1
0
200
300
400
500
600
700
800
Wavelength (nm)
Absorbance
2
Mig171 (30 min, 1/10)
1
0
200
400
600
Wavelenght (nm)
800
UV spectra of DMA-1,2,3-triazole-siloxane
in H2O
1000
4000
3500
3000
2500
2000
1500
Wavenumber (cm-1)