SUPPLEMENTARY INFORMATION Synergistic effects of linseed oil ...
SUPPLEMENTARY INFORMATION
Synergistic effects of linseed oil based waterborne alkyd and 3-isocynatopropyl triethoxysilane: Highly Transparent, Mechanically robust, thermally stable, hydrophobic, anticorrosive coatings Shabnam Pathan and Sharif Ahmad* Materials research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi110025
Preparation of linseed oil monoglyceride (LM) LM was prepared by following the same procedure as reported earlier 1. Initially, LO and glycerol were taken in a three necked flat bottomed flask equipped with a magnetic stirrer, thermometer, cold water condenser and nitrogen gas inlet. The NaOH (0.5 wt% of oil), used as a catalyst, was added to the reaction mixture and then heated upto 180-190 ˚C under continuous stirring for 1hr. The progress of the reaction was periodically monitored by taking FT-IR spectra at regular intervals of time, given in Figure S1) and by measuring the extent of solubility of the reaction product in methanol (monoglyceride: methanol=1:3 v/v).
Figure S1 FT-IR spectra of LO and LM
Preparation of neopentyl glycol modified waterborne linseed alkyd (NLA) Neopentyl glycol modified waterborne linseed alkyd was synthesized by polycondensation reaction. LM and phthalic anhydride (in molar ratio 1:0.75) were taken into round-bottomed glass equipped with digital stirrer and dean-stark apparatus to collect the condensation product. The neopentyl glycol was added slowly to the above reaction mixture after achieving the acid value 60 and the progress of the reaction was again monitored by acid value. The unreacted terminal carboxyl groups were neutralized by triethylamine upon achieving the desired acid value followed by the addition of water ethanol blend (80:20) 2. Scheme S1 represents the flowchart for the synthesis of NLA and the 1HNMR spectra of the same is given in supporting information (Figure S4).
Scheme S1 flowchart of the synthesis of NLA
Figure S2. 1H NMR spectrum of NLA 1
HNMR: (300 MHz, DMSO-d6, Me4Si) 0.84–0.93 (3H, t,–CH3), 1.03–1.10 (m, internal –CH2
group next to terminal methyl group), 7.62–7.73 (4H, d, Ph), 3.50 (1H, m,–CH–), 4.53 (2H, m, CH=CH–), 1.21-1.48 (-C=C-C-H, 4.02-4.28 (-CH2-O-C=O)2. Preparation of organic inorganic hybrid (NLA-IPTES) coating material NLA-IPTES was prepared via the sol-gel process by adding different weight percent (40%, 50% and 60%) of IPTES in NLA matrix. The coating became brittle in nature as the loading of IPTES was increased beyond 60wt%. Hence, the loading beyond 60wt% was not carried out. The nanocomposite hybrid coatings were coded as NLA-IPTES-I, NLA-IPTES-II and NLA-IPTESIII, where suffix represent the wt% of IPTES with respect to alkyd. The coating material was applied on carbon steel (CS) by brush technique.
Figure S3 DSC curves of different ratios of NLA-IPTES coatings
Figure S4 Fitted EIS circuit
Resin Code
Scratch Hardness (kg)
NLA-IPTES-I
5.9
Impact resistance Bending 1/8inch Cross (150lb/in) hatch test Pass
Pass
5B
NLA-IPTES5-II 6.7 Pass Pass NLA-IPTES-III 8.1 Pass Pass Table S1: Physico-mechanical test of hybrid nanocomposite coatings
5B 5B
References: 1.
Pathan, S.; Ahmad, S. Synthesis, characterization and the effect of the s-triazine ring on physico-mechanical and electrochemical corrosion resistance performance of waterborne castor oil alkyd. J. Mater. Chem. A. 2013, 1 (45), 14227-14238.
2.
Pathan, S.; Ahmad, S. s-Triazine ring-modified waterborne alkyd: synthesis, characterization, antibacterial, and electrochemical corrosion studies, ACS Sustainable Chem. Eng. 2013, 1 (10), 1246–1257.
3.
Siyanbola, T. O. Anti-microbial and anti-corrosive poly (ester amide urethane) siloxane modified ZnO hybrid coatings from Thevetia peruviana seed oil. J Mater Sci. 2013, 48 (23), 8215–8227.
4.
Jena, K. K et al. Novel hyperbranched waterborne polyurethane-urea/silica hybrid coatings and their characterizations, Polym. Int., 2011, 60 (10), 1504-1513.
Synergistic effects of linseed oil based waterborne alkyd and 3-isocynatopropyl triethoxysilane: Highly Transparent, Mechanically robust, thermally stable, hydrophobic, anticorrosive coatings Shabnam Pathan and Sharif Ahmad* Materials research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi110025
Preparation of linseed oil monoglyceride (LM) LM was prepared by following the same procedure as reported earlier 1. Initially, LO and glycerol were taken in a three necked flat bottomed flask equipped with a magnetic stirrer, thermometer, cold water condenser and nitrogen gas inlet. The NaOH (0.5 wt% of oil), used as a catalyst, was added to the reaction mixture and then heated upto 180-190 ˚C under continuous stirring for 1hr. The progress of the reaction was periodically monitored by taking FT-IR spectra at regular intervals of time, given in Figure S1) and by measuring the extent of solubility of the reaction product in methanol (monoglyceride: methanol=1:3 v/v).
Figure S1 FT-IR spectra of LO and LM
Preparation of neopentyl glycol modified waterborne linseed alkyd (NLA) Neopentyl glycol modified waterborne linseed alkyd was synthesized by polycondensation reaction. LM and phthalic anhydride (in molar ratio 1:0.75) were taken into round-bottomed glass equipped with digital stirrer and dean-stark apparatus to collect the condensation product. The neopentyl glycol was added slowly to the above reaction mixture after achieving the acid value 60 and the progress of the reaction was again monitored by acid value. The unreacted terminal carboxyl groups were neutralized by triethylamine upon achieving the desired acid value followed by the addition of water ethanol blend (80:20) 2. Scheme S1 represents the flowchart for the synthesis of NLA and the 1HNMR spectra of the same is given in supporting information (Figure S4).
Scheme S1 flowchart of the synthesis of NLA
Figure S2. 1H NMR spectrum of NLA 1
HNMR: (300 MHz, DMSO-d6, Me4Si) 0.84–0.93 (3H, t,–CH3), 1.03–1.10 (m, internal –CH2
group next to terminal methyl group), 7.62–7.73 (4H, d, Ph), 3.50 (1H, m,–CH–), 4.53 (2H, m, CH=CH–), 1.21-1.48 (-C=C-C-H, 4.02-4.28 (-CH2-O-C=O)2. Preparation of organic inorganic hybrid (NLA-IPTES) coating material NLA-IPTES was prepared via the sol-gel process by adding different weight percent (40%, 50% and 60%) of IPTES in NLA matrix. The coating became brittle in nature as the loading of IPTES was increased beyond 60wt%. Hence, the loading beyond 60wt% was not carried out. The nanocomposite hybrid coatings were coded as NLA-IPTES-I, NLA-IPTES-II and NLA-IPTESIII, where suffix represent the wt% of IPTES with respect to alkyd. The coating material was applied on carbon steel (CS) by brush technique.
Figure S3 DSC curves of different ratios of NLA-IPTES coatings
Figure S4 Fitted EIS circuit
Resin Code
Scratch Hardness (kg)
NLA-IPTES-I
5.9
Impact resistance Bending 1/8inch Cross (150lb/in) hatch test Pass
Pass
5B
NLA-IPTES5-II 6.7 Pass Pass NLA-IPTES-III 8.1 Pass Pass Table S1: Physico-mechanical test of hybrid nanocomposite coatings
5B 5B
References: 1.
Pathan, S.; Ahmad, S. Synthesis, characterization and the effect of the s-triazine ring on physico-mechanical and electrochemical corrosion resistance performance of waterborne castor oil alkyd. J. Mater. Chem. A. 2013, 1 (45), 14227-14238.
2.
Pathan, S.; Ahmad, S. s-Triazine ring-modified waterborne alkyd: synthesis, characterization, antibacterial, and electrochemical corrosion studies, ACS Sustainable Chem. Eng. 2013, 1 (10), 1246–1257.
3.
Siyanbola, T. O. Anti-microbial and anti-corrosive poly (ester amide urethane) siloxane modified ZnO hybrid coatings from Thevetia peruviana seed oil. J Mater Sci. 2013, 48 (23), 8215–8227.
4.
Jena, K. K et al. Novel hyperbranched waterborne polyurethane-urea/silica hybrid coatings and their characterizations, Polym. Int., 2011, 60 (10), 1504-1513.
