study on synthesis and curing acrylated black seed oil

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, 10 th 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 suc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.   uring       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 photo- crosslinking systems based on acrylated black seed oil. 2 - Evaluation and selection of conditions for acrylated black seed oil reaction and photo- crosslinking 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);  - References: 111 documentations consist of: 28 Vietnamese documentations; 72 English documentations and 1 Russian documentation. - Appendix: IR, UV-Vis, 1 HNMR, 13 CNMR; DEPT; HSQC; HMBC and MS spectroscopies. 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..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  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 50 0 C 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 80 o C. Sample, which was taken after certain time, was neutralized by Na 2 CO 3 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 -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 Functional group IR UV-Vis (nm) 1 HNMR (ppm) Wave (cm -1 ) Characteristic Absorption 3470 1163 Valence fluctuation of O-H with H-bond Valence fluctuation of C-O in alcohol - Hydroxyl 3008 1654 Valence fluctuation of C-H olefin. Valence fluctuation of double bond in CIS 5,30 - 5,53 (-CH=CH-) 2926 1378 Valence fluctuation non-symmetry of C- H in -CH 3 Symmetric deformed oscillator of C-H in -CH 3 0,87 - 0,92 (CH 3 -) 2926; 2855 1461 721 Valence fluctuation Symmetry and non- symmetry CH trong nhóm -CH 2 - Non-symmetric deformed oscillator of C- H trong -CH 2 - Pendulum oscillation of -CH 2 - 1,25 - 1,61 (-CH 2 -) 1745 1237; 1101 Valence fluctuation of carbonyl in ester. Valence fluctuation of C-O in ester. 225nm: transformation  * in ester - (-COO-) 1725 Valence fluctuation of general carbonyl 273nm: transformation   * in general carbonyl - General carbonyl 1260 851 824 Valence fluctuation non-symmetry of C  O in epoxy ring Valence fluctuation non-symmetry of epoxy. Deformed oscillator of epoxy. 2,76 - 2,93 Epoxy group 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. - 1 H-NMR spectra of black seed oil Table 3.2. Comparison of data 1 H-NMR spectra of black seed oil and Vernonia Type proton Chemical shifts (δ, ppm) Black seed oil Vernonia oil Proton hydroxyl (OH) - - Proton olefin (CH=CH) 5,30 - 5,53 5,22 - 5,56 Proton glyxerin (CH) 5,25 5,22 -5,56 Proton glyxerin (CH 2 ) 4,12 - 4,31 4,02 - 4,34 Proton epoxy (OCH) 2,76 - 2,93 2,71 - 2,98 Methylene (CH 2 -CH=CH-CH 2 ) 2,05  2,40 1,94- 2,42 Methylene (CH 2 ) n 1,25  1,61 1,18 - 1,68 Methyl (CH 3 ) 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. 1 H-NMR spectra of black seed oil Table 3.3. Chemical shifts in the H-NMR spectra of proton of black seed oil Proton Chemical shifts ( , ppm) Proton Chemical shifts ( , ppm) A 4,12 (m, 2H) 4,31 (m, 2H) 9 5,53 (t) B 5,25 (t, 1H) 10 5,30 (t) 1 - 11 2,20 (m) 2,40 (m) 2 2,20 (m) 12 2,93 (t, 3H) 3 1,61 (d) 13 2,76 (t, 3H) 4 1,25 - 1,35 (complex) 14 1,52 (m) 5 1,25 - 1,35 (complex) 15 1,25 - 1,35 (complex) 6 1,25 - 1,35 (complex) 16 1,25 - 1,35 (complex) 7 1,25 - 1,35 (complex) 17 1,25 - 1,35 (complex) 8 2,05 (m) 18 0,87 - 0,92 (complex) G 6 - 13 C-NMR and DEPT spectra of black seed oil. Table 3.4. Comparison 13 C-NMR between black seed oil and Vernonia oil. Type of carbon Chemical shift (δ, ppm) Black seed oil Vernonia oil Carbon carbonyl (C=O) 173,21 173,27 Carbon olefin (CH=CH) 123,94 - 132,58 123,86 - 132,53 Carbon glycerin (CH) 68,93 68,88 Carbon glycerin (CH 2 ) 62,08 62,01 - 64,90 Carbon epoxy (OCH) 56,54 - 57,20 56,41 - 57,16 Carbon methylene (CH 2 ) n 24,78 - 34,14 22,55 - 33,88 Carbon methyl (CH 3 ) 14,01 13,96 The results of analysis 13 C-NMR spectra of black seed oil were presented in table 3.5 Table 3.5. Chemical shifts in the 13 C-NMR of the carbons in black seed oil Carbon Chemical shift ( , ppm) Carbon Chemical shift ( , ppm) A 62,08 9 132,58 B 68,93 10 123,94 1 173,21 11 26,22 2 34,14 12 57,20 3 24,80 13 56,54 4 28,99 14 27,14 5 29,06 15 27,38 6 29,28 16 31,88 7 29,31 17 24,78 8 25,61 18 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       reactive diluent in the system and varnish, paint non-solvent, in the photo- 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. 723.46 825.44 851.08 1098.72 1165.05 1239.66 1378.83 1463.85 1654.93 1746.41 2854.74 2925.89 3008.26 3470.57 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 %Transmittance 1000 2000 3000 4000 Wavenumbers (cm-1) (a) (b) (d) (c) Sông cm -1 n qua (%)  sóng (cm -1 )  qua (%) Wavenumber (cm -1 ) Transmittance (%) a c b A- t ôquang Abs 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. 825.70 851.64 1096.69 1250.04 1654.70 810.96 986.97 1060.31 1410.54 1619.92 1636.16 1729.76 2854.14 2927.91 3467.86 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 %Transmittance 1000 2000 3000 4000 Wavenumbers (cm-1) (b) (a) Sông (cm -1 ) n qua (%) Wavenumber (cm -1 ) Transmittance (%) Fig. 3.4. IR spectra of black seed oil before (a) and after 60 hours acrylation by acid acrylic at 60 o C 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 ) Characteristic Black seed oil Change Before After 3467 Valence fluctuation of Hydroxyl + +  2927 2854 Symmetric and non-symmetric valence fluctuation of C-H alkane + +  1729 Valence fluctuation of carbonyl + +  1636 1619 Valence fluctuation of double bond of acrylate - +  1410 Deformed oscillator of double bond of acrylate - +  1250 Valence fluctuation of C-O in epoxy ring + -  851, 825 Symmetric valence fluctuation and deformed oscillator of epoxy group + -  810 Deformed oscillator of double bond - +  Note: (+)absorption, (-) non-absorption,  Increase,  decrease 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 60 o C. 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. [...]... 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... 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... 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... Vernonia oil The content of epoxy and hydroxyl can change over time of harvest, storage seed and oil 3 Studied on acrylated black seed oil reaction and determined the optimal conditions to acrylated black seed oil: mass ratio DHCĐ/toluen = 1/1, mole ratio acid acrylic/epoxy or acid metacrylic/epoxy = 20/1, temperature 60oC, time of reaction 60 hours The acrylated black seed oil by acid acrylic containing... 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... 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... 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. .. 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... DHCĐA2.0/H4.12.2 on the change of relative in exposure UV The results of conversion total acrylate content and some properties of photo-crosslinking coating based on acrylated black seed oil, monomer/oligomer acrylate and I.184 were showed in table 3.11 Table 3.11 The conversion of acrylate and some properties photo-crosslinking coating based on acrylated black seed oil, monomer/oligomer acrylate and I.184... 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 . and nature of the acrylated black seed oil and photo- crosslinking systems based on acrylated black seed oil. 2 - Evaluation and selection of conditions for acrylated black seed oil reaction. 13 C-NMR and DEPT spectra of black seed oil. Table 3.4. Comparison 13 C-NMR between black seed oil and Vernonia oil. Type of carbon Chemical shift (δ, ppm) Black seed oil Vernonia oil Carbon. 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