MINISTRY OF EDUCATION
AND TRAINING
VIETNAM ACADEMY
OF SCIENCE AND TECHNOLOGY
INSTITUTE FOR TROPICAL TECHNOLOGY
----------***----------
DAM XUAN THANG
STUDY ON SYNTHESIS AND CURING
acrylated black seed oil
MAYJOR: organic chemitry
code
: 62 44 01 14
Summary of doctoral thesis
Ha Noi - 2014
The work has completed at Institute of Tropical Technology – Vietnam
Academy of Science and Technology
Supervisor 1: Assoc.Pro.Dr. Le Xuan Hien
Supervisor 2: Assoc.Pro.Dr. Nguyen Thi Viet Trieu
Referee 1: Assoc.Pro.Dr. Tran Thi Nhu Mai,
Vietnam National University, Hanoi - University of Science
Referee 2: Assoc.Pro.Dr. Le Thi Anh Dao,
Hanoi National University of Education
Referee 3: Assoc.Pro.Dr.Bach Trong Phuc,
Hanoi University of Science and Technology
The thesis will be defended in front of doctoral thesis judgement, held at
Institute for Tropical Technology - Vietnam Academy of Science and
Technology at 9 AM, 10th November, 2014.
The thesis can be found at:
- Library of Institute for Tropical Technology.
- Vietnam National Library.
- Website of Institute for Tropical Technology: http://itt.ac.vn
1
INTRODUCTION
1. The urgency of the thesis
Metal and non-metal materials play an important role in production and the lives. Degrading
metal and non-metal materials by environmental conditions are enormous causes economic
damage. Vietnam stays in tropical zone and has long coastline, approximately 3000km and thus
speed of corrosion in Vietnam is near five-times higher than other climate areas. Damages of
corrosion, degradation and ageing metal materials combining with costs of protection materials in
Vietnam are estimated round one billion USD per year. Depending on properties of materials and
factor causes corrosion and degradation, there are many methods against corrosion and
degradation materials such as: electrochemical, inhibitor, protective coating… Today, protected
material, especially UV-curing paints becomes more popular.
Besides, the demand of preparation of high quality and friendly environmental materials
significantly increase due to global climate change and pollution becoming serious. One of the
protected and high quality decorative materials having attracted the attention of researchers and
producers is materials containing acrylate groups because these materials have advantaged
features such as weather resistance, chemical resistance, abrasion resistance and good biological
interactions. Currently, protective and decorative materials based on acrylated vegetable oil
have been interested because it combines the advantages of acrylate compounds and vegetable
oil as well as taking advantage of natural resources: available, inexpensive and environmentally
friendly. Research, development and application materials based on acrylated vegetable oils not
only help to overcome some disadvantages of low molecular weight acrylate compounds such
as dermatitis, skin allergies, but also contribute in the development of advanced processing
methods. Vegetable oils are abundant and renewable material. Particularly, vegetable oils
containing high chemical activity epoxy groups (synthetic or natural) can be used directly or
modified by acrylated to preparation higher quality and diverse products.
The demand for high quality protected and decorative materials is gigantic in Vietnam
which is in harsh climate zone. With abundant vegetable oil, especially black seed oil which
contains natural epoxy groups in Northwest of Vietnam has been little attraction in research and
thus researching protective and decorative coating based on generally acrylated vegetable oil,
particularly acrylated black seed oil, is essential.
Thesis: “Study on synthesis and curing acrylated black seed oil” has been done to solve
above problems.
2. The objectives of the thesis
- Determine optimal condition for acrylating black seed oil and crosslinking of photo-systems
based on acrylated black seed oil produces good quality films.
- Evaluate the possibility of using acrylated black seed oil to produce high quality protective
and decorative materials.
3. Significance
- Identified some rules and relationships of the chemical nature of the agent, reaction
conditions and kinetics, structure and nature of the acrylated black seed oil and photocrosslinking systems based on acrylated black seed oil.
2
- Evaluation and selection of conditions for acrylated black seed oil reaction and photocrosslinking of systems based on acrylated black seed oil to create protective, decorative
coatings meets some practical demands.
- Exploitation and efficient using vegetable oil.
4. Structure of the thesis
Thesis includes three parts: Main content (139 pages); References (11 pages); Appendix
(57 pages): Namely:
- Main content: Introduction (3 pages); Chapter 1. Literature review (37 pages); Chapter 2:
Experimental (8 pages); Chapter 3: Results and discussion (87 pages); Conclusion (2 pages);
the list of author’s research (1 page).
- References: 111 documentations consist of: 28 Vietnamese documentations; 72 English
documentations and 1 Russian documentation.
- Appendix: IR, UV-Vis,
spectroscopies.
1
HNMR,
13
CNMR; DEPT; HSQC; HMBC and MS
Chapter 1. BACKGROUND OVERVIEWS
The literature presents an overview of the history of research, development, using the
compounds containing acrylate and protective, decorative materials in the world and Vietnam.
The latest data on the production and consumption of organic protected, decorative materials
shows the distribution of the quantity, types and values as well as their properties are diverse
and increasing in recent years. Due to the increasing demand for quality and environmental
materials, the trends of research and development of protective and decorative materials not
only changes in the structure and categories but also use a variety of modern methods such as:
electrophoretic paint, photo-crosslinking, ... Protective, decorative materials based on acrylated
vegetable oil usually have good mechanical properties by combining the advantages of flexible
vegetable oil and the hard acrylic component have attracted the attention of researchers,
producers in the world and domestic. The situation of synthesis, manufacture and application of
acrylated vegetable oil is fully updated. The analysis of the synthesis, properties and abilities
crosslinking of acrylated vegetable oil showed the ability of denatured as well as the properties
of the production. Synthesized and analyzed the results of researches, application follow trend
of preparation protective and decorative materials based on acrylated vegetable oil.
Chapter 2. EXPERIMENTAL
2.1. Materials
Black seed oil in Muong Ang, Tuan Giao (Dien Bien) and Thuan Chau (Son La) containing
quantity of epoxy groups from 0.87 mol epoxy/mol oil đến 2.36 mol epoxy/mol oil was expeller
pressed or extracted in Department of Rubber and Natural resins materials, Institute of Tropical
technology. Monomer acrylate Hexanediol Diacrylate (HDDA); Bisphenol A diglycidyl ether
dimetacrylate (DGEDM); Bisphenol A diglycidyl ether diacrylate (DGEDA); Mixture monomer
and oligomer acrylate H4.12.2 including DGEDM and HDDA with weigh ratio: 25/15; Irgacure
184; Solvents and other pure chemicals: acid acrylic; acid metacrylic, toluene, acetone, ether
petro; chloroform…
3
2.2 Isolation black seed oil
Fresh black fruit was purchased in Muong Ang, Tuan Giao (Dien Bien) and Thuan Chau
(Son La). Fresh fruit was peeled soft coat by hand, and then it was dried or dried at 500C in an
oven which was followed by hard coat was smashed by hammer and peeled by hand. Black
kernels obtained.
2.3. Acrylated black seed oil by acid acrylic or acid metacrylic
Black seed oil was dissolved in toluene with concentration 50% in three-neck flask. Acid
acrylic or metacrylic was added with ratio (mol) acrylic/epoxy = 20/1. The solution was stirred
and kept at 35, 60 or 80oC. Sample, which was taken after certain time, was neutralized by
Na2CO3 5%, and then the organic layer was isolated by separatory funnel and washed by distill
water, dried at ambient in vacuum oven.
2.4. Preparation of sample
- The sample was prepared by mixing the components.
- Films were cast either on a KBr crystal for infrared spectroscopy analysis with 20 m
thickness, or on a glass plate for hardness measurements, or on steel and copper plates for
determination of other physico-mechanical properties with 30 m thickness.
2.5. Characteristic analysis
- Chemical and physical chemistry analysis: The titration; Elemental analysis (EA 1112,
USA); IR-analysis (NEXUS 670, USA); UV-Vis analysis (CINTRA 40, GBC, USA); Analysis of
nuclear magnetic resonance (Avance 500, Brucker, Germany); MS analysis (Waters-API-ESI,
USA).
- Determination of the physico-mechanical properties: Gel fraction and the swelling degree;
hardness (according standard PERSOZ (NFT 30 – 016)); Resistance impact (according standard
ISO 6272); Flexibility (according standard ГOCT 6806-03); Pencil hardness (according standard
ASTM D3363-05); Adhesion (according standard ISO 2409).
Chapter 3. RESULTS AND DISCUSSIONS
3.1. Study on black seed oil
3.1.1. Study on composition and structure of black seed oil
Acid index
Identified acid index of new separation black seed oil by chemical titration was 3.27 mg
KOH/g
Epoxy group content
Determining epoxy group content by titration methods based on color indicator and voltage
measurements showed that the epoxy group content of black seed oil changed over time, venue
procurement from about 0.87 to 2.36 moles of epoxy/moles of oil.
Elemental analysis
According the results of elemental analysis, the black seed oil contained 14.96% oxygen.
Analysis IR, UV-Vis, NMR spectra.
4
IR, UV-Vis, NMR spectra of black seed oil have very similar spectral shape Vernonia oil. The
absorption, resonance signals characteristic of the groups of atoms in black seed oil on the types of
spectra studied are presented in Table 3.1
Table 3.1. The absorption, resonance signals characteristic of the groups of atoms in black
seed oil on the types of spectra studied
Analysis
IR
Wave
(cm-1)
3470
1163
3008
1654
2926
1378
2926; 2855
1461
721
1745
1237; 1101
1725
1260
851
824
Characteristic Absorption
UV-Vis
(nm)
1
HNMR
(ppm)
Functional group
Valence fluctuation of O-H with H-bond
Valence fluctuation of C-O in alcohol
Valence fluctuation of C-H olefin.
Valence fluctuation of double bond in
CIS
Valence fluctuation non-symmetry of CH in -CH3
Symmetric deformed oscillator of C-H in
-CH3
Valence fluctuation Symmetry and nonsymmetry CH trong nhóm -CH2Non-symmetric deformed oscillator of CH trong -CH2Pendulum oscillation of -CH2Valence fluctuation of carbonyl in ester.
225nm:
transformation
Valence fluctuation of C-O in ester.
n →π* in ester
Valence fluctuation of general carbonyl
273nm:
transformation
n →π* in
general
carbonyl
Valence fluctuation non-symmetry of C –
O in epoxy ring
Valence fluctuation non-symmetry of
epoxy.
Deformed oscillator of epoxy.
-
Hydroxyl
5,30 - 5,53
(-CH=CH-)
0,87 - 0,92
(CH3-)
1,25 - 1,61
(-CH2-)
-
(-COO-)
-
General carbonyl
Epoxy group
2,76 - 2,93
The analysis results obtained showed that black seed oil has similar functional group like
ester, epoxy, double bone olefin and molecular weight Vernonia oil. As a result, the black seed
oil has similar structure Vernonia oil with follow structural formula:
5
Thesis will analyses the NMR spectra of black seed oil.
- 1H-NMR spectra of black seed oil
Table 3.2. Comparison of data 1H-NMR spectra of black seed oil and Vernonia
Type proton
Proton hydroxyl (OH)
Proton olefin (CH=CH)
Proton glyxerin (CH)
Proton glyxerin (CH2)
Proton epoxy (OCH)
Methylene (CH2-CH=CH-CH2)
Methylene (CH2)n
Methyl (CH3)
Chemical shifts (δ, ppm)
Black seed oil
Vernonia oil
5,30 - 5,53
5,22 - 5,56
5,25
5,22 -5,56
4,12 - 4,31
4,02 - 4,34
2,76 - 2,93
2,71 - 2,98
2,05 – 2,40
1,94- 2,42
1,25 – 1,61
1,18 - 1,68
0,87 – 0,92
0,81 - 0.91
1
H-NMR, formula, the value of situation and results of analysis H-NMR of black seed
oil was illustrated in Fig 3.1 and table 3.3.
Fig. 3.1. 1H-NMR spectra of black seed oil
Table 3.3. Chemical shifts in the H-NMR spectra of proton of black seed oil
Proton
Proton
Chemical shifts ( , ppm)
9
5,53 (t)
B
Chemical shifts ( , ppm)
4,12 (m, 2H)
4,31 (m, 2H)
5,25 (t, 1H)
10
1
-
11
2
3
4
5
6
7
8
2,20 (m)
1,61 (d)
1,25 - 1,35 (complex)
1,25 - 1,35 (complex)
1,25 - 1,35 (complex)
1,25 - 1,35 (complex)
2,05 (m)
12
13
14
15
16
17
18
5,30 (t)
2,20 (m)
2,40 (m)
2,93 (t, 3H)
2,76 (t, 3H)
1,52 (m)
1,25 - 1,35 (complex)
1,25 - 1,35 (complex)
1,25 - 1,35 (complex)
0,87 - 0,92 (complex)
A
G
6
- 13C-NMR and DEPT spectra of black seed oil.
Table 3.4. Comparison 13C-NMR between black seed oil and Vernonia oil.
Type of carbon
Carbon carbonyl (C=O)
Carbon olefin (CH=CH)
Carbon glycerin (CH)
Carbon glycerin (CH2)
Carbon epoxy (OCH)
Carbon methylene (CH2)n
Carbon methyl (CH3)
Chemical shift (δ, ppm)
Black seed oil
Vernonia oil
173,21
173,27
123,94 - 132,58
123,86 - 132,53
68,93
68,88
62,08
62,01 - 64,90
56,54 - 57,20
56,41 - 57,16
24,78 - 34,14
22,55 - 33,88
14,01
13,96
The results of analysis 13C-NMR spectra of black seed oil were presented in table 3.5
Table 3.5. Chemical shifts in the 13C-NMR of the carbons in black seed oil
Carbon
A
B
1
2
3
4
5
6
7
8
Chemical shift ( , ppm)
62,08
68,93
173,21
34,14
24,80
28,99
29,06
29,28
29,31
25,61
Carbon
9
10
11
12
13
14
15
16
17
18
Chemical shift ( , ppm)
132,58
123,94
26,22
57,20
56,54
27,14
27,38
31,88
24,78
14,01
Analysis MS spectra of black seed oil
MS high resolution spectra of black seed oil had a peak at m/z = 927 corresponding black
seed oil contenting epoxy group content 3.0 moles epoxy/mole oil and 3 double bond/mole oil.
According results of chemical analysis, elemental, physical-chemistry and comparison
structural data of Vernonia oil or epoxidized soya, thesis proposed that the structure of black
seed oil as follow:
Black seed oil has 3 epoxy groups and 3 double bonds in their molecular. It has feature as
Vernonia oil or epoxidized soya which is using directly or denaturing (acrylation,
7
hydroxylation…), as a stabilizer for chlorinated polymers, reactive diluent in the system and
varnish, paint non-solvent, in the photo-curing composite…
3.1.2. Study on change of black seed oil over harvest, storage
Based on titration method, spectral analysis has watched transformation of functional
group, especially epoxy group in black seed oil depending on time of harvest and storage.
IR and UV spectra of black seed oil in the process storage were illustrated in Fig. 3.2 and 3.3.
A-Abs
m t đô quang
150
140
(d)
130
(c)
(%)
Transmittance
(%)
Truy nnqua
(%)
Truy
qua
120
110
90
(b)
b
80
70
825.44
851.08
1098.72
1378.83
1239.66
723.46
1654.93
1165.05
10
1463.85
20
2925.89
30
1746.41
40
(a)
2854.74
50
3008.26
60
3470.57
%Transmittance
100
a
c
0
4000
3000
2000
1000
Wavenumbers (cm-1) -1
Số
Sô
ssóng
ng (cm
cm-1 )
Wavenumber
(cm-1 )
Fig 3.2. IR spectra of black seed oil pressed from
seed of: fresh (a); after 4 months storage (b), after 1
year storage (c) and after 2 years storage (d).
Fig 3.3. UV spectra of black seed oil pressed from
seed of: fresh (a); after 4 months storage (b), after 1
year storage (c).
According the results of analysis IR, UV spectra and titration, the epoxy and hydroxyl
groups of black seed oil had transformed significantly in process of storage oil and seed.
Therefore, obtaining quality black seed oil requires suitable process of extraction, separation
and storage.
There are several conclusions from the results of study on structure and transformation
black seed oil over time of harvest or storage:
Based on the results of chemical titration, elemental analysis and analysis IR, UV,
NMR, MS had determined the functional group namely ester, epoxy, double bond in molecular
as well as mass of molecular of black seed oil which is a triglyceride oil having similar structure
Vernonia oil.
According the results of change black seed oil over time storage, epoxy group content
decreased over time storage. Therefore, in the fact, we may obtain black seed oil by extraction
or mechanical press with epoxy group content from 0.87 to 2.36 moles epoxy/mole oil.
3.2. Study on acrylated black seed oil reaction
3.2.1. Study on IR spectra of black seed oil before and after acrylation
IR spectra and the result of analysis IR spectra of black seed oil before and after 60 hours
acrylation by acid acrylic were presented in Fig. 3.4 and table 3.6.
As can be seen from table 3.6, in the process of acrylation, intensity of absorption
characteristic valence fluctuation of C-H at 2927 cm, 2855 cm was almost unchanged.
Absorption at 3467 cm characteristic valence fluctuation of hydroxyl, at 1729 cm of carbonyl
increased. Absorptions at 1636, 1619, 987 and 810 cm-1 characteristic valence fluctuation,
8
deformed oscillator of double bond acrylate dramatically grew and absorptions at 851, 825 cm-1
charateristic of epoxy group significantly after 60 hours reaction. Therefore, absorption at 2927
characteristic of C-H alkane has been selected as the internal standard to examine the change of
the content of the functional group during the process of acrylated black seed oil.
85
(a)
65
60
(b)
55
5
810.96
1060.31
10
1410.54
15
2927.91
20
1729.76
25
2854.14
30
1636.16
35
1250.04
1619.92
40
986.97
45
1096.69
50
3467.86
%Transmittance
(%)
Transmittance
Truy n qua (%)
70
851.64
1654.70
75
825.70
80
0
4000
3000
2000
1000
Wavenumbers (cm-1)
Sô s ng (cm-1(cm
) -1 )
Wavenumber
Fig. 3.4. IR spectra of black seed oil before (a) and after 60 hours acrylation by acid acrylic
at 60oC
Table 3.6. Characteristic absorption in the IR spectra of black seed oil before, after
acrylation. and transformation of them in the process.
Wave
number
(cm-1)
3467
2927
2854
1729
1636
1619
Black seed oil
Characteristic
Before
Valence fluctuation of Hydroxyl
+
Symmetric and non-symmetric valence
+
fluctuation of C-H alkane
Valence fluctuation of carbonyl
+
Valence fluctuation of double bond of
acrylate
Deformed oscillator of double bond of
1410
acrylate
Valence fluctuation of C-O in epoxy
1250
+
ring
Symmetric valence fluctuation and
851, 825
+
deformed oscillator of epoxy group
810
Deformed oscillator of double bond
Note: (+)absorption, (-) non-absorption, Increase, decrease
After
Change
+
+
→
+
+
+
-
-
+
3.2.2. The change of functional group in the process of acrylated black seed oil
The fig 3.5. showed the change of functional group content in the process of reaction of
acrylated black seed oil by acid acrylic at 60oC.
As is showed in fig 3.5, the epoxy group content sharply fell and the content of acrylate
group, hydroxyl, carbonyl dramatically increased in 36 hours reaction, before the change of
functional groups saw slow convert and almost unchanged after 60 hours.
9
0.20
D X /D 2927
D 825 /D 2927
1729 cm
1.0
-1
0.9
3467 cm-1
0.16
-1
1410 cm
0.8
0.12
0.08
cacbonyl :
●
hydroxyl :
*
acrylat
:
▲
epoxy
:
♦
0.7
0.6
0.04
825
0.5
cm-1
0.00
0.4
0
10
20
30
40
50
Thời gian phản ứng (giờ )
60
70
Time reaction (hour)
Fig 3.5. The change of functional group in the process of acrylated black seed oil at 60oC.
3.2.3. Influence of several factors on acrylated black seed oil reaction.
3.2.3.1. Influence of temperature on acrylated black seed oil reaction
The change of functional group in the process of acrylated black seed oil
Acrylated black seed oil was studied at 35, 60 and 80oC. At 80oC, acrylated black seed oil
initially occured rapidly but the reaction was gel after 3.5 hours.
The change of content of epoxy, hydroxyl and acrylate in the acrylated black seed oil at 35,
60 C was presented in the fig 3.6 and 3.7.
o
0.20
D825 /D 2927
D X /D
nh m hydroxyl:
2927
0.16
D825 /D2927
DX /D 2927
0.20
▲
0.16
3467 cm
0.16
nh m acrylat
0.12
1410 cm
nh m epoxy
0.12
●
:
3467 cm
-1
0.08
0.08
0.04
0.04
1410 cm
-1
825 cm
30
40
50
▲
nh m acrylat
:
♦
nh m epoxy
:
●
0.08
0.04
-1
0.00
20
nh m hydroxyl:
0.04
0.00
10
-1
0.12
0.08
0
-1
0.12
♦
:
0.16
60
70
Thời gian phản ứng (giờ)
Time reaction (hour)
Fig.3.6. The change of content of epoxy,
hydroxyl and acrylate in the acrylated black seed
oil at 35oC
825 cm
-1
0.00
0.00
0
10
20
30
40
50
60
70
Thời gian phản ứng (giờ)
Time reaction (hour)
Fig 3.7. The change of content of epoxy,
hydroxyl and acrylate in the acrylated
black seed oil at 60oC
As is shown from Fig 3.6 and 3.7, reaction of acrylated black seed oil at 35oC obtained
lower efficency than acrylated black seed oil at 60oC and thus not studying acrylated black seed
oil at lower temperature.
According the above results, determined the optimal condition of acrylated black seed oil
reaction being temperature at 60oC and time reaction 60 hours for further studies.
3.2.3.2. Study on influence of epoxy group content in black seed oil on acrylation
Fig 3.8 presented the change of content of epoxy group and acrylate group in acrylated
black seed oil with variety oil containing epoxy group content: 2.2; 1.8; 1.2 and 0.87 moles
epoxy/mole oil.
10
D825 / D2927
D1410 / D2927
D825 / D2927
0.16
DHCĐ-2,2E
0.16
0.16
0.12
0.12
D1410 / D 2927
0.12
0.10
DHCĐ-1,8E
0.12
0.08
DHCĐ-1,2E
0.08
0.08
0.08
0.04
0.04
0.04
0.06
0.04
0.02
0.00
0.00
0
10
20
30
40
50
60
70
Thời gian phản ứng (giờ )
Time reaction (hour)
Fig 3.8. the change of content of epoxy and acrylate
group in acrylated black seed oil with variety oil
containing different epoxy group content at 60oC
0.00
0.00
0
10
20
30
40
50
60
70
Thời gian phản ứng (giờ)
Time reaction (hour)
Fig 3.9. The change of content of epoxy and
acrylate group of black seed oil acrylated by acid
acrylic (♦)and metacrylic (●)at 60oC
As is shown by fig 3.8, the epoxy group of all black seed oil fully converted, the number of
acrylate group attaching oil chain reached from 83.33 to 95.45% after 60 hours reaction. Due to
reaction of acrylated black seed oil occurred follow 2 stages: in the first stage, opening the ring
of epoxy group with high speed and completely due to proton having small size easily
protonated and opened the ring of epoxy group. In the next stage, attachment of the acylate
group in oil chain experimenced slower speed and efficiency than the previous stage.
3.2.3.3. Influence of substituents on the acrylated black seed oil reaction
Fig 3.9 shows the change of content of epoxy and acrylate group of black seed oil containing
epoxy group content 1.8 moles epoxy/mole oil acrylated by acid acrylic and acid metacrylic at 60oC.
The results of the study, again confirming acrylate chemical reaction mechanism occurs in
two stages: first stage was that ring of epoxy group opened by proton and acrylate groups
attached to the oil chain in the next stage. Thus, the speed of acrylated black seed oil has no
diffirence between acid acrylic and acid metacrylic. These results have similar previous study of
Victoria Kolot and her colleages when they studied acrylated Vernonia oil.
There are several conclusions from the results of study on acrylated black seed oil by acid
acrylic or acid metacrylic:
According the study on IR of black seed oil before and after acrylation, selected absorption
at 2927cm-1 characteristic C-H alkane as internal standard to examine the change of content of
hydroxyl at 3467 cm-1, carbonyl at 1730 cm-1, acrylate at 1410 cm-1, and epoxy at 825 cm-1 in
the reaction. The results were that the content of hydroxyl, carbonyl, and acrylate significantly
increased, but the epoxy group content fell substantially.
The optimal condition of acrylated black seed oil: temperature 60oC; the mass ratio black
seed oil/toluene = 1/1; the mole ratio acid acrylic or acid metacrylic/epoxy = 20/1; time reaction
was 60 hours. The higher content of epoxy makes reactive speed faster and reaction efficient.
Black seed oil containing acrylate and metacrylate synthesized can solve well in toluene,
HDDA and having good interoperability with photo initator and thus using in photo curing system.
11
3.3. Determine structure of acrylated black seed oil
3.3.1. IR spectra of acrylated black seed oil
Study on the IR spectra of black seed oil before and after acrylated showed that the absorption
characteristic of double bond acrylate appeared and the absorption characteristic of epoxy group
disappear after acrylation (fig 3.4 and table 3.6). This proved that the reaction occurred and acrylate
groups attached to the oil chain.
3.3.2. UV-vis spectra of acrylated black seed oil
As can be seen in UV spectra that there were two peaks in range λmax = 217 - 268 nm. In
that, the intensity of absorption at 255.6 – 268.4nm increase significantly to compare with black
seed oil before acrylation. Thus, acrylate had attached to oil chain.
3.3.3 Nuclear magnetic resonance spectra of acrylated black seed oil
The NMR spectra of acrylated black seed oil had similar shapes acrylated Vernonia oil.
Comparison of resonance signals characteristic of the proton, carbon of acrylated black seed oil
and acrylated Vernonia oil were presented in Table 3.7
Table 3.7. Comparison of data 1H-NMR, 13C-NMR between acrylated black seed oil and acrylated
Vernonia oil
Chemical shifts (δ, ppm)
Acrylated black seed oil
Acrylated Vernonia oil
Types of proton
Proton ethylene of acrylated oil
Proton of metacrylated oil
Proton neighbour acrylated và
metacrylated ester
Proton of hydroxyl group
Proton methyl of metacrylate group
Types of carbon
Carbon of acrylate ester
Carbon of metacrylate ester
6,4; 6,1; 5,8
5,56 - 6,22
6,5; 6,2; 5,8
6,05; 5,5
4,87 - 4,93
4,8 - 4,9
3,43 - 3,62
1,94 - 1,95
3,57 - 3,65
1,95
165,69
166,72
165,45
166,65
Carbon of double bond in the fisrt
chain acrylate
131,09; 128,86
130,07; 128,1
Carbon of double bond in the fisrt
chain metacrylate
136,2; 125,57
136; 125,6
The next stage will present the examation and analysis NMR spectra of acrylated black
seed oil
3.3.3.1. Resonance signal 1H-NMR
The 1H-NMR spectra, formula, the number of location and the results of analysis 1H-NMR
spectra of acrylated black seed oil were presented in the Fig 3.10 and table 3.8.
12
Fig 3.10. 1H-NMR spectra of acrylated black seed oil.
Table 3.8. Chemical shifts in the 1H-NMR characteristic protons of acrylated black seed oil
H
A
B
1
2
3
4
5
6
7
8
9
10
Chemical shifts, δ( ppm)
H
Chemical shifts, δ( ppm)
4,12 (m, 2H)
4,31 (m, 2H)
5,33 (t, 1H)
2,20 (m)
1,61 - 1,67 (complex)
1,25 - 1,61 (complex)
1,25 - 1,61 (complex)
1,25 - 1,61 (complex)
1,25 - 1,61 (complex)
2,05 (m)
5,53 (t, 3H)
11
2,40 (m)
12
13
14
15
16
17
18
19
20a
20b
4,40 - 4,47 (t, 2H)
4,87 - 4,93 (t, 2H)
2,07 (m)
1,25 - 1,61 (complex)
1,25 - 1,61 (complex)
1,25 - 1,61 (complex)
0,86 - 0,89 (complex, 9H)
6,06 - 6,13
5,81 (m, 2H)
6,41 (m, 2H)
5,30 (t, 3H)
21
3,43 - 3,62 (s, 2H)
13
3.3.3.2. Resonance signal C-NMR
The results of analysis 13C-NMR of acrylated black seed oil by acid acrylic were showed in
the table 3.9.
13
Table 3.9. The chemicacl shifts in the 13C-NMR characteristic carbon atoms of acrylated black
seed oil
C
Chemical shifts, δ (ppm)
C
Chemical shifts, δ (ppm)
A
61,95
11
28,06
B
1
2
3
4
5
6
7
8
9
10
68,80
173,86
33,05
24,86
29,02
29,17
29,37
29,62
27,24
125,14
133,05
12
13
14
15
16
17
18
19
20
72,82
77,27
30,36
25,49
31,78
22,48
13,96
165,69
128,86
21
131,09
3.3.4 Mass spectrometry of acrylated black seed oil
High resolution MS of acrylated black seed oil had a peak ion at m/z = 1057, respectively
the mass of molecular acrylated black seed oil containing the acrylate group content 2.0
moles/mole oil and the thesis proposal the structural formula follow:
There are several conclusions from the results of analysis structure acrylated black seed
oil by acid acrylic and acid metacrylic:
Based on the the results of analysis IR, UV, NMR and MS, thesis had determined
acrylated black seed oil containing hydroxyl, acrylate and ester.
Synthesized and determined acrylated black seed oil by acid acrylic containing acrylate
group content from 0.47 to 2.0 moles acrylate/mole oil and acrylated black seed oil by acid
metacrylic having 1.0 mole and 1.6 moles metacrylic/mole oil.
Structure of acrylated black seed oil indicated that this is a highly reactive compound
and easily participates photo crosslinking. Thus, reaction of photo-crosslinking based on
acrylated black seed oil has selected for further study in thesis.
14
3.4. Study on reaction of photo-crosslinking based on acrylated black seed oil system
3.4.1. Photo systems based on acrylated black seed oil with photo initator I.184
Table 2.1. Mass ratio of the constituents in the photo systems based on crosslinking acrylated
black seed oil and photo initiator I.184
No
1
2
3
4
Constituents’ ratio (wp)
Acrylated black seed oil
DHCĐA2.0
DHCĐA1.6
DHCĐMA 1.6
DHCĐMA 1.0
I.184
3
3
3
3
3.4.1.1. Study IR of photo system before and after exposure UV.
Table 3.10. The change of absorption characteristic functional group and group atoms of photo
system based on acrylated black seed oil before and after 6 seconds exposure UV
DHCĐA2.0/I.184 =
Wave
100/3
number
Characteristic
-1
(cm )
before
after
3505
Valence fluctuation of hydroxyl group
+
+
2856
Valence fluctuation symmetry and non-symmetry of C+
+
2927
H alkane
1738
Valence fluctuation of carbonyl group
+
+
1635
Valence fluctuation of double bond acrylate
+
1410
Deformed oscillator in plane of CH2 acrylate
+
988
+
Deformed oscillator out of plane of CH2 acrylate
810
+
Ghi chú:(+) absorption, (-) non-absorption, “” unchanged, “” decrease
The
change
As can be seen from the results of analysis IR, in the process of photo-crosslinking,
intensity of absorption characteristic valence fluctuation of carbonyl at 1739 cm-1, hydroxyl at
3505cm-1 and C-H alkane at 2927cm-1 were almost unchanged. Absorption at 3467 cm
characteristic valence fluctuation of hydroxyl, at 1729 cm of carbonyl increased. Absorptions at
1636cm-1, 1411cm-1, 989cm-1 và 811cm-1 characteristic valence fluctuation, deformed oscillator
of double bond acrylate in the photo curing system dramatically fell. Therefore, absorption at
2927 characteristic of C-H alkane has been selected as the internal standard to examine the
change of the content of the acrylate group at 1411 cm-1.
3.4.1.2. Influence of several factors on the photo-crosslinking reaction
The process of photo-crosslinking depends on several factors such as: natural, the
concentration of monomers, oligomers, film thickness, intensity and wavelength… The thesis
concentrated on study on influence of content and natural acrylate group on the process of
photo-crosslinking and the physic-mechanical coating.
The change of acrylate in the process of photo-crosslinking.
Fig 3.11 presented the change of rate D1410/D2927 of photo-crosslinking system DHCĐA2.0
(●); DHCĐA1.6 (♦); DHCĐMA1.6 (▲); DHCĐMA1.0 (*) having diffirent content and natural
acrylated in the exposure.
As can be seen from fig 3.11, acrylate in all systems converted rapidly in the first 1.2
seconds exposure UV, before converting slow and almost being unchanged after 6 seconds
exposure UV, reaching acrylate convertion 99; 96; 96; and 95%, respectively photo-
15
crosslinking systems DHCĐA2.0; DHCĐA1.6; DHCĐMA1.6; DHCĐMA1.0. As is seen,
higher level of acrylated black seed oil made speed of reaction faster and acrylate experienced
higher conversion than metacrylate. The conversion of acrylate group in the photo-crosslinking
systems can be arranged follow order: DHCĐA2.0 > DHCĐA1.6 > DHCĐMA1.6 >
DHCĐMA1.0
D 1410 / D2927
0.20
DHCĐA2.0/I.184 = 100/3
:
●
DHCĐA1.6/I.184 = 100/3
:
♦
0.15
0.10
DHCĐMA1.6/I.184 = 100/3 :
▲
DHCĐMA1.0/I.184 = 100/3 :
*
0.05
0.00
0
1
2
3
4
5
6
7
Thời gian chiếu tia tử ngoại (giây)
Time of exposure UV (second)
Fig. 3.11. The change of rate D1410/D2927 of photo-crosslinking having diffirent
content and natural acrylate in the process of exposure UV.
Gel fraction and Swelling degree
Fig 3.12. presented the change of gel fraction and swelling degree of DHCĐA2.0(●);
DHCĐA1.6 (♦); DHCĐMA1.6 (▲); DHCĐMA1.0 (*) having diffirent content and natural acrylate
in the exposure UV.
Gel fraction (%)
Swelling degree (%)
Phần gel (% )
100
DHCĐA2,0/I.184 = 100/3
DHCĐMA1,6/I.184 = 100/3
Độ trương (% )
1000
● DHCĐA1,6/I.184 = 100/3
▲ DHCĐMA1,0/I.184 = 100/3
♦
*
80
800
60
600
40
400
20
200
0
0
0
1
2
3
4
5
6
7
Thời gian chiếu tia tử ngoại (giây )
Time of exposure UV (second)
Fig 3.12. The change of gel fraction and swelling degree of systems having diffirent
content and natural acrylate in the exposure UV.
As can be seen from fig. 3.12, before exposure UV, all of samples completely dissolve in
choloroform; that means the gel fraction of system equal 0%, but the gel fraction of DHCĐA2.0
increased to 29%, DHCĐA1.6 grew to 25%, DHCMĐA1.6 rose to 24%, DHCĐMA1.0
increased to 22% after 0.15s exposure UV. After 3.6s exposure UV, the gel fraction rose slowly
and after 6s exposure the the gel fraction reached 74; 70.5; 64.5; 62.5%, respectively. The
swelling degree of coating also showed the respective rule. After 6s exposure, the swelling
degree of
–
–
Thus, after 6s exposure UV, the photo-crosslinking systems based on acrylated black seed oil
have crosslinked, creating a three-dimensional network and becoming mulch solid reviews. It is
seen from the results of studies, the system having higher acrylate group content makes the
16
density of crosslinking coating increase and the cured acrylate system was closer than the cured
metacrylate leading to increasing gel fraction and reducing swelling degree.
Relative hardness
The results of examine the change of hardness of DHCĐA2.0(●); DHCĐA1.6 (♦);
DHCĐMA1.6 (▲); DHCĐMA1.0 (*) having the diffirent content and natural acrylate in the
exposure UV were presented in the Fig 3.13.
Relative hardness
Độ cứng tương đối
0.4
0.3
0.2
DHCĐA2,0
DHCĐMA1,6
●
▲
DHCĐA1,6
♦
DHCĐMA1,0 *
0.1
0
1
2
3
4
5
6
7
Thời gian chiếu tia tử ngoại (giây )
Time of exposure UV (second)
Fig 3.13. The change of relative hardness of systems having diffirent
content and natural acrylate in the exposure UV
As can be seen from 3.13, after 6s exposure UV, the coatings were studied from liquid
stage transferring to solid with high relative hardness 0.36;0.32;0.31;0.28, respectively. Thus,
coating having higher acrylate content could create hardly 3D network to compare with coating
having lower acrylate content. The metacrylate coatings did not cure as closely as their
counterpart. The change of relative hardness accordance with the results of determining gel
fraction, swelling degree and the change of acrylate of the studied samples in the exposure UV.
There are several conclusions from the results of studies on influence of the content and
natural acrylate on photo-crosslinking of acrylated black seed oil and I.184:
Due to reactive acrylate and metacrylate, the reaction of photo-crosslinking occurred
rapidly with almost complete convertsion of acrylate group and determining the time reaction
was after 3.6s exposure UV.
When exposure UV, the acrylate group converted rapidly, reaching 95 – 99% after 6s
exposure UV and the speed of convertsion arranged follow rule: DHCĐA2.0 > DHCĐA1.6 >
DHCĐMA1.6 > DHCĐMA1.0
The process of photo-crosslinking leaded to the change of physic-mechanical
properties of coating. When increasing the content of acrylate or metacrylate, the density of
crosslinking raised leading to growth of gel fraction, relative hardness, decrease of swelling
degree. The density of crosslinking and the physic-mechanical properties of metacrylate coating
saw lower than acrylate coating due to effect of space of methyl.
3.4.2. Photo-crosslinking systems based on acrylaed black seed oil, monomer, oligomers
acrylate and I.184
Table 2.2. The mass of constituents ratio in the photo-crosslinking based on acrylated black
seed oil, monomer, oligomer and I.184
No
DHCĐA2.0
5
80
Monomer, oligomer acrylat
HDDA
DGEDA
H4.12.2
20
0
0
I.184
3
17
6
7
8
9
10
11
12
13
60
40
80
60
40
80
60
40
40
60
0
0
0
0
0
0
0
0
20
40
60
0
0
0
0
0
0
0
0
20
40
60
3
3
3
3
3
3
3
3
3.4.2.1. Study on IR spectra and evolution of the change of functional group in the photocrosslinking
As can be seen from the results of analysis IR, in the process of photo-crosslinking,
intensity of absorption 1636, 1410, 982, 810cm-1 characteristic valence fluctuation and
deformed oscillator of double bond acrylate and sum of acrylate in the photo-crosslinking
dramatically reduced. Absorptions characteristic valence fluctuations of carbonyl, hydroxyl and
C-H alkane at 2927 cm-1 were unchanged. Therefore, absorption at 2927 characteristic of C-H
alkane has been selected as the internal standard to examine the change of the content of the
acrylate group at 1411 cm-1.
3.4.2.2. Study on influence of natural and ratio black seed oil, monomer/oligomer acrylate on
photo-crosslinking
Study on the change of total content acrylate
The change of total acrylate in the system with diffirent ratio DHCĐA2.0/HDDA,
DHCĐA2.0/DGEDM và DHCĐA2.0/H4.12.2 when exposure UV were presented in the fig.
3.14 – 3.16
D1410 / D 2927
D1410 / D 2927
0.25
0.40
DHCĐA2.0/HDDA: 80/20: ♦
60/40: ●
Tỉ lệ DHCĐA2.0/DGEDM:
40/60: ▲
60/40 ●
80/20 ♦
0.20
0.30
0.15
0.20
0.10
0.10
0.05
0.00
0
1
2
3
4
5
6
0.00
7
0
Thời gian chiếu tia tử ngoại (giây )
1
2
4
5
6
7
Time of exposure UV (second)
Fig 3.14. Influence of ratio DHCĐA2.0/HDDA on
the convertsion total acrylate in the exporuse UV
D 1410 / D
Fig 3.15. Influence of ratio DHCĐA2.0/ DGEDM on
the convertsion total acrylate in the exporuse UV
2927
0.6
DHCĐA2.0/H4.12.2:
80/20
♦
60/40 ●
40/60 ▲
0.5
0.4
0.3
0.2
0.1
0.0
0
3
Thời gian chiếu tia tử ngoại (giây )
Time of exposure UV (second)
1
2
3
4
5
Thời gian chiếu tia tử ngoại (giây )
6
Time of exposure UV (second)
7
18
Fig 3.15. Influence of ratio DHCĐA2.0/H4.12.2 on the convertsion total acrylate in the exporuse UV
As can be seen from Fig 3.14 – 3.16, in the first 1.2s exposure UV the total content of
acrylate converted rapidly, then it saw slower convertsion and after 6s exposure UV the
performance of convertsion reached 99 (sample number 5) 98% (sample number 6), 94%
(sample number 7), 92% (sample number 8), 81% (sample number 9), 87% (sample number 11),
85% (sample number 12) và 84% (sample number 13).
The results of the change of acrylate group content of monomers/oligomers or mixture
monomer and oligomer showed that chemical structure, rate of monomer/oligomer acrylate had
effect on the convertsion of acrylate in the photo-crosslinking. These results were explained
that: in the first stage, the compability of monomer/oligomer acrylate with acrylated black seed
oil responsed capability as well as the convertsion of total acrylate group. Due to monomer
HDDA, mixture of monomer and oligomer H4.12.2 had good compability with DHCĐA2.0 and
beter mobility than DGEDM, photo-crosslinking containing monomer HDDA, mixture of
monomer and oligomer H4.12.2 will have better capability and the faster convertsion of
acrylate group in comparison with system containing DGEDM. In the next stage, when the
network of polymer created, the capability as well as the conversion depends on the compability
of the part of chain in the spacy network. Due to the part of chain established from monomer
HDDA was more flexible and capable than that built from oligomer DGEDM or mixture of
monomer, oligomer H4.12.2, photo-crosslinking system containing HDDA will having the
higher conversion. The compabilities of monomers/oligomers acrylate were arranged the rule:
HDDA > H4.12.2 > DGEDM.
Study on the change of gel fraction, swelling degree and physic-mechanical properties
The results of the change gel fraction, swelling degree of sample 5 – 13 were showed in the
Fig 3.17 – 3.19.
Gel fraction (%)
100
Swelling degree
(%)
Độ trương (% )
Phần gel (% )
Gel fraction (%)
1000
80
800
60
600
40
400
20
200
DHCĐA2.0/HDDA:
80/20: ♦
60/40: ●
Swelling
degree (%)
Độ trương (% )
Phần gel (% )
100
1000
80
800
60
600
40
400
DHCĐA2.0/DGEDM:
20
80/20: ♦
60/40:
●
5
6
200
40/60: ▲
0
0
0
1
2
3
4
5
Thời gian chiếu tia tử ngoại (giây )
6
Time of exposure UV (second)
7
0
0
0
1
2
3
4
Thời gian chiếu tia tử ngoại (giây )
7
Time of exposure UV (second)
Fig 3.17. Influence of rate of DHCĐA2.0/HDDA
Fig 3.18. Influence of rate of DHCĐA2.0/
on the change of gel fraction and swelling degree in
DGEDM on the change of gel fraction and
the process of exposure UV
swelling degree in the process of exposure UV
Fig 3.17 – 3.19 showed that after 0.6s exposure UV, the gel fraction of coating increased
rapidly, and then it had a little change. After 6s exposure UV, the coating DHCĐA2.0/HDDA =
80/20, 60/40, 40/60 having gel fraction reached 75; 86; and 81%; the coating
DHCĐA2.0/DGEDM = 80/20, 60/40, having gel fraction reached 79; and 71%; the coating
DHCĐA2.0/ H4.12.2
74,7%. The change of swelling degree also showed the corresponding rule. After 6s exposure
UV, the swelling degree of sample 5 reduced from 846% to 423%, sample 6 fell from 897% to
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