Galley Proofs, RJC-8787/2024

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ENHANCEMENT OF ANTI-CORROSIVE PERFORMANCES OF

CRESOL BASED p-TOLYL BENZOXAZINE RESIN BY
COPOLYMERIZING WITH POLYURETHANE
C. Ushaand M. Sivaraju
PG & Research Department of Chemistry, Thiruvalluvar Government Arts College
(Affiliated to Periyar University), Rasipuram, Namakkal-637401, Tamilnadu, India

Corresponding Author: tkr_jai@hotmail.com
ABSTRACT
Corrosion is a major issue in steel applications for industrial purposes and other fields. In order
to combat this, extensive research has been done on anti-corrosive materials, resulting in the
development of various types of precursors. This work presents a polyurethane-based material
that uses benzoxazine as a monomer. The synthesized monomer has been characterized
extensively and systematically using NMR, UV-visible, and FT-IR spectroscopic methods. The
monomer's electronic properties have been explained by DFT analysis, including FMO's analysis
and molecular mapping studies. Moreover, three different ratios of polyurethane precursor have
been used to create an anti-corrosive co-polymer material. The hygroscopic nature and gel
formation of the synthesized polymer have been tested, demonstrating superior results.
Additionally, the Tafel experiment was used to test the coated polymer's activity, and the results
showed that it was more active than bare mild steel.
Keywords: Benzoxazine, Polyurethane, DFT, MEP and Tafel.
RASĀYANJ. Chem., Vol. 17, No. 2, 2024
INTRODUCTION

Surface quality is a serious aspect of various materials, such as metal, stone, wood, and
polymers.1 Metal surfaces, in particular, have gained much attention due to their frequent use in
industrial sceneries like shipbuilding. Therefore, preventing rust on metal surfaces has become
an extensively researched crucial factor. Mild steel (MS) is a commonly used material for
corrosion research and has diverse applications across various sectors. The annual cost of MS
corrosion, estimated to exceed USD 1.8 trillion, has a significant impact on the economies of
industrialized countries. In biomaterials exposed to biological fluids, corrosion on MS can cause
inflammation and allergic reactions, severely impacting human health. 3,4Scientists face
significant challenges in reducing corrosion on metallic surfaces, making organic coatings a
promising research area.5-8There are lots of anti-corrosive materials for MS from rust that have
been developed where the material is made of nanomaterials, inorganic complexes, organic
molecules, and polymeric compounds.9-12 In recent years epoxy-based resin molecules have been
widely used as an anti-corrosive agent for MS due to their peculiar properties such as excellent
chemical resistance, high cross-linking density, and strong adhesion/affinity to substrates. 13-15
However, it faces some issues that could degrade its applications towards MS coating such as the
hygroscopic nature of the compound, and hydrophilicity thus creating practical applications.
Similarly, the phenolic resin could be also used as an anti-corrosive material for MS via
conventional heat treatment. This kind of polymeric material has overcome the drawbacks that
Rasayan J. Chem., 17(2), XXXX-XXXX(2024)
http://doi.org/10.31788/RJC.2024.1728787 This work is licensed under a CC BY 4.0 license.
 Galley Proofs, RJC-8787/2024

are mentioned above; thus, increases hydrophobicity and decreases its hygroscopic nature. In this
line, a new branch of thermosetting phenolic resin called polybenzoxazine displays properties
such as high char yield, great heat and chemical resistance, and a very long shelf life. 16-18Thereby,
it could have more advantages such as anti-corrosive efficiency, and brittleness. Additionally,
monomers also have been reported by a tandem reaction between primary amine, phenol, and
formaldehyde, which is called the Mannich condensation reaction. In the present work, we have
developed a new anti-corrosive agent that consists of polyurethane and benzoxazine units as
monomers. The p-tolylbenzoxazine (PTB) monomer was synthesized through a mannich
condensation reaction thus, attaining a high yield of ultra-pure monomer. Three different
polymeric materialshave been developed by changing the ratio of polyurethane content. In this,
we could increase the strength of the polymeric material.

EXPERIMENTAL
Synthesis of the Monomer
O-cresol (1g, 6.572 mmol) and p-toludine(6.752 mmol) were the chemicals used as a reactant for
the present experiment. The aforementioned substrates were combined with paraformaldehyde
(0.414g) having 20 mL of CHCl3 and refluxed for a day in order to synthesize the benzoxazine
monomer. Thin-layer chromatography was used to monitor the development of the reaction
product. The mixture was next extracted using 150 mL of chloroform, and any contaminants that
dissolved in the aqueous phase were removed by washing it with 100 mL of water and 100 mL
of brine solution. Anhydrous sodium sulphate was used to separate and dry the organic layer
containing the pure monomer in order to eliminate any remaining water. The benzoxazine
monomer was then attained by evaporating the resulting chloroform solution at low pressure.
Using this monomer (PTB), a coating material with polyurethane as its polymeric component
was produced.
OH NH2
(CH2)nO, CHCl3 O

70oC, 24 hr. N

o-cresol p-toluidine
Scheme-1: Chemical Synthesis of p-tolylbenzoxazine Monomer

Synthesis of the p-tolylbenzoxazine (PTB) Anti-Corrosive Agent (Polymer Synthesis)19-20

The polymer synthesis is given in the supporting information.

Water Absorption Studies21

The water absorption studies are performed for this coated MS plate and the detailed procedures
are given in supporting information.

Gel Content Studies22

The gel content studies are performed for this coated MS plate and the detailed procedures are
given in supporting information.

Computational Calculations

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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024

The chemical reactivity of the synthesized monomer (PTB) has been revealed by the DFT studies
using frontiers molecular orbitals (FMO) analysis. Gaussian 09W software package was used for
the whole DFT analysis. Regards this analysis, the 3D structure of the monomer (PTB) has been
initially optimized using 3D chem draw and paste structure intoGaussian software and analyzed
using B3LYP/6.311 G basis set.23 The obtained optimized structure could be visualized using
Gauss view software and it can be further used for the various processes of analysis such as
molecular electrostatic potential and identification of electron density on the molecule.

Tafel Polarization Experiment24

The corrosion efficiency was calculated based on the Tafel Polarization experiment as given in
supporting information.

RESULTS AND DISCUSSION

Characterization of the Monomer and Co-Polymers
NMR Spectroscopy
Mostly used to examine organic compounds, nuclear magnetic resonance (NMR) can yield
reliable information about the protons, carbons, and heteroatoms that make up organic
molecules. Aside from this, its uses are widespread throughout all fields of study, including
chemical sensors and catalysis.25–27Nevertheless, only synthetic organic chemists have utilized
the various NMR approaches. Henceforth, has been employed in the current investigation to
ascertain the chemical environments of monomers (PTB) (Fig.-1). The proton NMR
spectroscopy has to show the presence of the 17-proton monomer. Seven protons in total match
the aromatic protons that are present in the aromatic area between 6.6 and 7.2 ppm. Following
integration, three protons were visible for each of the singlet peaks that were discovered in the
aliphatic area at 2.16 and 2.2 ppm. The aromatic methyl groups are represented by these peaks,
respectively. The remaining four protons, which are acquired at 4.5 and 5.3 ppm and each peak
about the two protons, are from the benzoxazole -CH2- group.

Fig.-1:1H-NMR Spectrum of Synthesized Monomer in CDCl3Solvent

FT-IR Spectroscopy
FT-IR spectroscopy was utilized to determine the presence of functional groups in the organic
components. However, since then, its application has spread to several chemistry-related fields,
such as chemical sensors, biomass, nano-chemistry, and mechanism identifications. 28-31 In the
current study, additional functional groups like ether, benzoxime, amine, amide, and halides have
been included in the monomer and its copolymers. The findings from FT-IR investigations that
looked at the monomer and generated polymers are displayed in Fig.-2. The monomer was
discovered to have two peaks at higher wavenumbers of 3019 and 2917 cm -1, which correspond
to the -CH-stretching vibration of the aromatic ring. One characteristic peak, located at 1078 cm -
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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024
1
, which was proposed as a cyclic ring in the structure, confirms the presence of nitrogen in its
tertiary form. The presence of the benzoxazine ring was confirmed by three peaks at 1254, 1226,
and 1190 cm-1, which correspond to the symmetric and asymmetric stretching vibrations of the
C-O-C bond seen in the cyclic ring. It was possible to identify the stretching vibrations of the C-
H bond in the presence of methyl groups by producing a peak at 2848 cm -1. Furthermore, a
strong and considerable peak at 1517 cm-1 was found, which strongly suggests the presence of a
benzoxazine ring with a tri-substituted benzene ring. In the polymeric materials, the peaks shown
above were seen, along with other exceptionally notable changes. Apart from that, a distinct peak
corresponding to the amide -NH- bond vibrations in the polyurethane molecule emerged at 3288
cm-1. The presence of urethane C=O has also been determined by looking for peaks in the range
of 1637-1597 cm-1 for all polymeric materials that are attributed to the amide's -C-N bond
stretching vibration.

Fig.-2: Stocked FT-IR Spectra of Synthesized Monomer and its Polymeric Material.

UV-visible Spectroscopic Studies

UV-visible spectroscopy was also carried out for the monomer (PTB) and all other various ratios
of the polymeric material as part of a comprehensive characterization investigation (Fig.-3). This
technique aids in determining the electronic structure of the material. The presence of the
benzoxazine moiety is confirmed by the monomer's two bands at 280 and 270 nm, which
correspond to the n-π* transition. In the case of the polymer, these bands are decreasing since
the polyurethane band has surpassed the monomer band. Consequently, a new, distinct band for
polyurethane was found at 265 nm. These bands were present in all polymeric materials,
indicating that co-polymer and monomer synthesis was successful. This work additionally uses
characterization methods like FT-IR and NMR to corroborate the polymer synthesis.

Fig.-3: Overlaid UV-Visible Spectra of Synthesized Monomer and its Polymeric Material

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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024

Water Absorption Studies

It is well recognized that research on water diffusion in polymeric corrosion materials is crucial
and that the polymeric materials' branching and cross-linkage densities may affect these
investigations. The density of the cross-linking or branching of polymers, which might result in
higher hydrogen bonding with the materials, determines how effective the binder is during
coating.32 Henceforth, the present study has included this study which gives more supporting data
to the polymeric materials. Figure-4 shows the water absorption capacity of the polymeric
molecules and all-synthesized monomers. According to Fig.-4, which displays the findings of
water absorption research, the monomer itself does not appear to be very hydrophilic.
Consequently, a water absorption percentage of 1.8 was attained; however, the co-polymer
production further reduced this. The amount of polyurethane that is included in the polymeric
substance determines its hydrophobicity. Eighty percent of the material has passed less than
unity and sixty percent of the polymeric substance has reached nearly unity. A very low water
absorption percentage of 0.73% has been attained by using an extreme number of polyurethane
components. These investigations show that the hydrophobicity of the monomer has been
improved by the polyurethane's progressive concentration increase.

2
% 1.8
w 1.6
a 1.4
t 1.2
e 1
r 0.8
a 0.6
b 0.4
s 0.2
0
.

Fig.-4: Data Obtained from Water Absorption Studies of Synthesized Monomer (PTB) and
itsVarious Compositions of Polyurethane Material
Gel Formation Studies
However, this study is also important in that provides gel formation capability with material
which is also a crucial property of anti-corrosive agents like hydrophobicity. In general, more gel
formation could be much more suitable for the anti-corrosive agent which also correlated with its
hydrophobic nature. It is also expected that more aqueous repulsive natural materials can able to
form more gel.33 Therefore, the ability of the gel formation of synthesized polymeric materials
has been evaluated, and obtained data are presented in Fig.-5. An excellent nature of gel
formation of the monomer (PTB) has obtained a reasonable gel formation percentage of 86.9,
however, it can be improved by the attachment of polyurethane. Thus, similar to the above
studies, here synthesized polymer has been investigated for gel formation studies and results
were compared to bare monomer. A huge hike in the gel formation has been observed by the
increasing concentration of the polyurethane content. For instance, 60 % containing material has
made better gel formation and thus keeps on enhancing up to nearly 94 % with the highest
percentage of polyurethane. This study displays the impact of polyurethane on gel formation
through the possible development of various kinds of cross-linkages thus leading to increased
hydrophobicity.

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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024

96
%
g 94
e
l 92

a 90
b
s 88
.
86

84

82

Fig.-5: Data Obtained from Gel Formation Studies of Synthesized Monomer and its Various
Composition of Polyurethane Material

Electrochemical Studies
The Tafel plot presented in Fig.-6 was used to compute the corrosion potential and current of the
artificial polymeric material. By overlaying a straight line on the linear components of both the
anodic and cathodic curves, the corrosion potential was used to predict the corrosion current
density. These characteristics significantly influence the corrosion behavior of the synthesized
materials. Higher conductivity and electron density in the materials usually result in a higher
corrosion current, which accelerates corrosion. On the other hand, a larger positive corrosion
potential leads to a lower corrosion rate. As a result, materials require a higher potential to
display their conductivity.34-35Table-1 contains the data gathered from the tafel plot experiment. It
demonstrates how the co-polymer treatment dramatically changed the bare sample's larger
negative potential and greater current density. The sample with a monomer-to-polyurethane ratio
of 100: 60 likewise exhibits nearly identical outcomes to the naked sample and, as a result, does
not reveal any corrosion efficiency activity (8%). A greater percentage of polyurethane content,
on the other hand, has resulted in a significant increase in activity and a decrease in current
density (1.08 mA) and corrosion rate (12.5 x 10 -3 mm/year). Since this is over 88.0% more
efficient than the bare, it is established that the polymeric substance in polyurethane plays a
significant role in inhibiting corrosion. Consequently, the polyurethane content has been raised to
100%, significantly enhancing corrosion activity. In comparison to naked steel plates, almost the
corrosion rate has been reduced to zero, and its efficacy has been measured at 91.3 percent.
These test findings show how the co-polymer coating protects mild steel against corrosion, and
the substance that was created may turn out to be a very effective anti-corrosive in the future.

Table-1: Parameter Calculated from the Tafel Plot Experiments

Corrosion Corrosion Anodic Cathodic
Icorr Pcorr -
Compound rate (10 efficiency slope (mV/ slope (mV/
(mA) (mV) 3
(mm/year) (%) decade) decade)
(bare) 8.94 -839.4 104 0 68.8 -65
-60 8.14 -756.1 94.6 8.94 94 -79.2
-80 1.08 -629.1 12.5 87.91 76.7 -87.7
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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024

-100 0.77 -556.9 8.98 91.38 91.7 -116

Fig.-6:Tafel Plot Experiment of the Bare Sample and Sample Coated with Synthesized Co-
Polymers Containing Various Ratios of Polyurethane.

Microscopic Imaging Studies

It is possible to determine how a coated polymer prevents corrosion by analyzing optical images
which shows the effect of the concentration of the polymer material on the coating. When
exposed to light, any damage to the surface will be visible as a dark red tone. This study
examines the application of coatings on polymeric composites, which are known to have poor
and ineffective anti-corrosive abilities. The mild has degraded almost entirely despite having a
60% loaded material coating. On the other hand, it is demonstrated that even a small amount of
coating can resist corrosion as it does not turn red. Moreover, the inclusion of an additional
100% of polyurethane successfully mitigated the corrosion. Consequently, the color of the
minimally affected surfaces remained unaltered.

DFT Studies
Computational methodologies also greatly influence analysis in modern chemistry research.
Therefore, research has advanced to a new level of quality and analysis thanks to the integrated
analysis of the computational and experimental data. 36In terms of theory, analysis using density
functional theory (DFT) is an important technique made up of numerous quanta mechanical
operations. Specifically, its applications span a wide number of scientific domains, including
biology, chemistry, physics, and mathematics.37Notably, chemistry has received increased
support and can therefore be used in a variety of chemistry-related research fields, including
pharmacology, chemical sensors, solar cells, catalysis, drug design, and electro-optic studies. 38-
42
The frontier orbital analysis, which is a preliminary analysis of DFT results, is a very
significant study. FMO consists of higher occupied molecular orbital (HOMO) and lower
unoccupied molecular orbitals (LUMO); the latter possessing a higher energy level whereas the
previous one is used to obtain in lower energy level. As a result, this study could provide the
electron distribution of the molecule, electron transition of the molecule, and chemical
reactivity.This study analyzed a newly synthesized monomer and found that the Frontier
Molecular Orbital (FMO) of the molecule is displayed in Fig.-7. The Highest Occupied
Molecular Orbital (HOMO) of the molecule is composed of the whole oxazole and N-aryl ring,
with a portion of the electron density moving throughout the entire molecule and decreasing in
electron density at the LUMO level. This is due to the molecule's highly polar nature, causing
electronic charge to transfer into the oxazole ring, thus acting as a bridge. The energy level
values of FMOs were obtained and used to calculate various parameters to explain the molecule's
reactivity and chemical properties, such as chemical potential, global softness, global hardness,
electrophilicity index, and energy band gap.Table-2 contains a tabulation of the computed
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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024

parameters. The molecule's stability has been bolstered by its increased negative energy value,
and its LUMO value was likewise obtained at a negative energy level. The stability parameter is
further helped by the marginally greater energy band gap value. While the value of
electrophilicity illustrates the molecule's electro-withdrawing nature, the chemical potential value
unmistakably demonstrates that molecules become less reactive. This might result in a robust
interaction with polyurethane, so generating a co-polymer that is more cross-linked. As a result,
the produced monomer has emerged as a highly significant molecule for use in chemical
applications, such as corrosion research.
Compo LUM Global
HOMO Band gap Chemical Global Electrophilicit
und O hardnes
(eV) (E) potential softness y index
name (eV) s
-
Mono -5.1943 0.039 5.1546 -2.6170 -2.5773 -0.1939 1.32869
7
Table-2: Parameters Calculated from DFT Studies
Molecular Electrostatic Potential Studies (MEP)
Several trustworthy quantum chemistry techniques were employed to obtain information about
molecular electrostatic potential. In terms of its application to understanding and forecasting
molecules' chemical reactivity, this study has enormous promise. 43Through the use of this
method, the compound's three-dimensional configuration has been clarified through the analysis
of the distribution of electrical charges. As such, it would be useful to examine the charges that
cover the entire molecule. This analysis uses color representations to help visualize the
molecule's surface or electron sink.44Three different colors are usually used to represent the
compound's surface electrical density. Strong red coloration indicates an increased electron
density, whereas green coloration indicates more positively charged areas, which indicates an
electron deficit. The color blue indicates the neutral charge of the compounds, making it easier to
comprehend how the electrical charge is distributed throughout the surface.

Fig.-7: Frontier Molecular Orbital (FMO) Analysis of Synthesized Monomer (PTB) and its
Optimized Structure Obtained by the DFT Studies

As a result, this method makes it possible to make well-informed decisions on the molecules'
reactivity. The optimized structure obtained from the DFT analysis was also used in the DFT and
MEP experiments that followed.The entire molecule exhibits yellowish color mapping in Fig.-8,
which indicates a faint presence of electron density. Because of the presence of a free lone pair,
which causes the oxygen atom to become a more electron-rich portion of the molecule, a reddish
hue was specifically seen in the oxygen region. Although benzoxazole nitrogen also possesses a
single electron, it is used to resonate with the benzene ring, which results in a decrease in
electron density and a yellow hue. Aside from this, the green color indicates the presence of
hydrogen in the benzene ring, indicating that all hydrogen atoms were in a neutral charge.

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ANTI-CORROSIVE PERFORMANCE OF BENZOXAZINE RESINC. USHAand M. Sivaraju
 Galley Proofs, RJC-8787/2024

Fig.-8: Molecular Electrostatic Mapping Analysis of Synthesized Monomer and Structure

Derived from DFT Studies

CONCLUSION
A new type of monomer has been synthesized using o-cresol and p-toluidine as the basic
building blocks. The chemical structure of this monomer has been confirmed using FT-IR, NMR,
and UV-visible spectroscopy techniques. The monomer's ability to prevent corrosion has been
tested by synthesizing polymeric composites using polyurethane. Three different ratios of
monomer and polyurethane composites have been tested using FT-IR and UV-visible
spectroscopy. The results show that materials containing higher amounts of polyurethane have
been effective in resisting corrosion compared to other materials.The resistance of polymers to
corrosion is due to their ability to absorb water and the presence of a significant amount of gel
components. Optical microscopic imaging studies have shown the positive effects of polymer
coating on steel, which strongly supports the results of Tafel experiments. The monomer's
chemical reactivity has also been demonstrated through various DFT studies, including
Mullikan's charge distribution analysis, MEP, and FMO analysis.All of the examinations
revealed that monomers and the polymeric composites theyproduce have a big impact on mild
steel corrosion research.

ACKNOWLEDGMENTS
I would like to use this opportunity to express my heartfelt appreciation and thanks to the
administration of PG & Research Department of Chemistry, Thiruvalluvar Government Arts
College (Affiliated to Periyar University), Rasipuram, Namakkal.

CONFLICT OF INTERESTS
The authors declare that there is no conflict of interest.

AUTHOR CONTRIBUTIONS
All the authors contributed significantly to this manuscript, participated in reviewing/editing, and
approved the final draft for publication. The research profile of the authors can be verified from
their ORCID IDs, given below:
C.Usha https://orcid.org/0009-0000-5385-5449
M.Sivaraju https://orcid.org/0000-0001-8502-5458
Open Access: This article is distributed under the terms of the Creative Commons Attribution 4.0
International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use,
distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s)
and the source, provide a link to the Creative Commons license, and indicate if changes were made.
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[RJC- 8787/2024]

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