Synthesis and Characterization of New poly β-Lactam from poly acrolein and Study Corrosion Inhibition for Stainless steel in Hydrochloric Acid Solution

 

Amaal S. Sadiq1, Entesar O. Al-Tamimi2

1Department of Chemistry, College of Science for Woman, University of Baghdad, Al-Jadiriya, Baghdad, Iraq.

2Department of Chemistry, College of Science, University of Baghdad, Al-Jadiriya, Baghdad, Iraq.

*Corresponding Author E-mail: amaalsameer74@gmail.com

 

ABSTRACT:

A new poly chain derivative of polyacrolein has been synthesized from the two basic precursors, polyacrolein and aromatic amine/substituted amine in chloroform to prepare poly Schiff base compounds (A1-A4). The novel poly subs.β-lactam derivative is obtained via coupling of poly schiff base with chloroacetyl chloride and trimethylamine (B1-B4). Newly synthesized compound was identified via spectral methods; their [13C-NMR, 1H-NMR, and FTIR] also measurement of some of its physical properties. Furthermore the inhibition effect of synthesized compounds (B1-B4) on the corrosion of stainless steel in 1N HCl was studied by wight loss method. The results of weight loss measurements showed that corrosion inhibition efficiency by increasing the concentration of organic inhibitors for stainless steel in 1M HCl solution at 30°C.

 

KEYWORDS: Polymer, β-Lactam, chloroacetyl chloride, corrosion, weight loss.

 

 

1. INTRODUCTION:

Stainless steel is widely used in different applications due to its excellent mechanical properties, availability at lowcost ease of fabrication stainless, also it is commonly used in many fields due to its excellent resistance to oxidation and its mechanical properties. Nevertheless, steel suffers from pitting corrosion in chloride-containing condition1,2. Corrosion can cause serious problem for the safe and economic operation of a wide range of industrial installtions3. The acidic conditions could have a deleterious effect on the surface and could reduce the service life of the equipment. Thus, careful control and monitoring of the corrosion processes is always necessary. In the case of closed systems, corrosion protection by the chemical inhibitor is considered to be a necessary procedure4. Most organic receptor have P, N, S, O and π electrons in their structures and can be used in acidic condition5,6.

 

Organic inhibitors form a protective layer on the surface of the steel7, black the active surface sites and reduce the corrosion rate8. Numerous attempts have been made to improve the passivity of stainless steel by applying inhibitors9 to corrosive solutions, through application of polymer coatings on the surface10. Polymer have recently attracted considerable attention as corrosion inhibitor, and their inhibiting power is structurally linked to cyclic ring and hetero-atoms which are the major active centers of adsorption.11,12.

 

The goal of this study, synthesize β-lactam ring-containing polymers and to investigation their corrosion inhibition efficiency against SS in hydrochloric solution by weight loss process. 

 

2. EXPERIMENTAL:

2.1. Materials and physical measurements:

All starting materials and solvents have been collected from Sigma-Aldrich and Fluka was used without further purification. (Melting points) were measured on Gallen Kamp capillary melting point apparatus and were uncorrected, FT-IR measurements were recorded on Shimadzu model (FTIR-8400S). (1HNMR and 13CNMR) spectra were obtained with Bruker spectrophotometer model ultra-shield at 400 MHz in DMSO solution with the TMS as internal standard.

 

2.2. Synthesis of the organic compounds:

2.2.1. Synthesis of poly subs. Schiff bases13:

The Aromatic amine/substituted amine (0.01mol) in chloroform (15ml) are mixed with (0.01mol) of polyacrolein with drops of glacial acetic acid, and the mixture is stirred for 4-6 hours for the magnetic stirrer method, removal of excess solvent by evaporation, the polymer was purified by dissolving in THF and precipitated from ethanol, extracted by filtration, and washed with ethanol. (TLC solution ethyl acetate and hexane, The physical properties of synthesized compounds (A1-A4) are given in Table 1).

 

2.2.2 Synthesis of poly subs. Β- Lactam14

Chloroacetylchloride (0.01mol) was add drop wise to a magnetically stirred solution of poly schiff base (0.01mol) and ET3N in THF (15ml), at 0-5 C. The reaction mixture was stirred for 4 hours and the precipitated amine hydrochloride was washed off. The filtrate was refluxed for about 3hours and the remaining solvent was evaporated. The resulting polymer was purified by dissolving in warm THF and precipitated from ethanol (TLC solution ethyl acetate and hexane. The physical properties of synthesized compounds (B1-B4) are given in Table (1).

 

3. MATERIALS AND METHODS OF WEIGHT LOSS:

3.1. Preparation HCl solution:

The analytical level of 37% HCl with a molecular weight of 36.5g/mol was used for the preparation of an acid electrolyte. The acid was combined with double distilled water to make 1 M HCl solution. For each collection of freshly prepared tests, 1M HCl solutions were used to prevent any contamination.


 

 

Table 1: The physical properties of all compounds.

Yield%

Softing Point C0

Molecular Weight

color

Chemical formula

Structure

 

No. of compd.

 

 

82

 

 

199-225

 

 

206.24

 

 

 

Orange

 

 

C11H14N2O2

 

 

 

 

A1

 

 

 

71

 

 

154-168

 

 

 

189.30

 

 

Brown

 

 

C13H19N 

 

 

 

A2

 

 

73

 

146-166

 

195.69

 

Yellow

                          C11H14ClN

 

 

 

A3

 

 

 

80

 

               175-183

 

                    218.09

 

 

Brown

 

                          C12H14N2S

 

 

 

A4

 

 

78

 

                202-214         

 

 

282.72

 

 

 

Black

 

 

C13H15ClN2O3

 

 

 

 

 

B1

 

61

 

214-126

 

265.78

 

Deep Brown

 

C15H20ClNO

 

 

 

B2

 

 

76

 

198-213

 

272.17

 

Deep Brown

 

C13H15Cl2NO

 

 

 

 

B3

 

77

 

271-289

 

 

294.80

 

Deep Brown

                

C14H15ClN2OS

 

 

 

 

B4

 

 

 

3.2. Preparation of specimens:

The sheet of stainless steel used has the composition percentages (0.045% P, 2.00% Mn, 0.08% C, 0.03% S, 16.00-18.00% Cr, 2.00-3.00% Mo, 0.75% Si, 0.01% N, 10.00-14.00 Ni, and the remainder iron 31.004-38.005%). Specimens were cut for use as coating substrates to size (2.5cm in diameter), using a method of cutting machismo (wire cut), the open side was gridded and mechanically polished using a grinding wheel tool. All specimens were grinded and polished using a series of grits of increasing fineness ((500 to1500) to the surface finish, the specimen was degreased with acetone and washed in distilled water finally with ethanol and stored inside desiccators before being used in corrosion studies.

 

3.3. Weight loss measurements:

1.     In the case of experiment weight loss five glass containers with a capacity of 100ml  containing (1M HCl)

2.     The first beaker was functioning as blank, while each of the other four beaker contained various concentration inhibitors, all of which were placed at room temperature (about 30°C).

3.     The specimens were initially weighed in an analytical balance, then suspended and completely immersed in the experimental solutions.

4.     After every immersion of 24 hours, the specimens were removod from the container, cleaned with emery papers, washed in doubled distilled water degreased with acetone, dried and reweighed.

5.     Weight loss allowed calculation of the mean corrosion rate I (mg cm -2 h-1). The corrosion rate of mild steel was determined using the relation15.

 

         ∆m

W = –––– ………………………………..…………... (1)

           st

 

∆m: mass loss

S: the area 

t: immersion period

The percentage inhibition efficiency (IE%) was calculated using the relationship16.

 

              Wcorr-Wcorr(inh)

IE% = –––––––––––––––––– Χ 100………………… (2)

                     Wcorr

 

Where Wcorr and Wcorr (inh) are the corrosion rates of mild steel in the absence and presence of inhibitor

 

4. RESULTS AND DISCUSSION:

In this study, we have prepared new poly β-lactam from poly schiff base, which was a synthesis of the reaction sequences depicted in scheme (1). Initial attempts to synthesis by preparation of poly Schiff base from reaction different substituted aromatic amine and poly acroline with catalytic amounts of glacial acetic acid in refluxing chloroform furnished the polymer(A1-A4) is good yield. confirmed by FTIR and NMR measurement, FTIR spectr17 table (2), showed appearance (C=N)stretching band at (1645-1649), moreover poly β-lactam (B1-B4) was synthesis via coupling of poly schiff base with chloroacetyl chloried and triethylamine, confirmed by disappearance (C=N) and appearance (C=O)stretching band at(1718-1728) that indicated formation of azetidinone ring table (2), H1-NMR spectrum exhibited signals at δ=(3.53-3.49) ppm and (4.35-4.33) for –HC-N- and Cl-CH- respectively also C13-NMR confirm formation poly β-lactam by absorption at δ =(166.68-169.08) for (C=O),other spectral data of all compound showed in table (3).

 

Weight loss measures have been described as ideally good as other techniques for corrosion assessment of metals in an immersion18. In this investigation apparent that the rate of corrosion in (1 M HCl) solution with the addition of poly β-lactam derivatives at different concentration for 24 hours immersion at 30°C decreases as the concentration of the product studied increases18,19.

 

 

Schem1: The chemical steps for the synthesis of poly compounds (A1-A2 and B1-B2)

 

 

Table 2: FT-IR Spectral data of synthesized compounds (A1-A4 andB1-B4) in cm-1

Comp. No.

n C-H

Aromatic

n C-H

aliphatic

n C=N

           

n C=C

Aromatic

Other

 

A1

3087

2923,

2885

1649

1614,

1485

ѵ (NO2)

1528,

1350

A2

3095,

3080

2923,

2845

1649

1616,

1515

-

A3

3095,

3060

2920,

2852

1647

 

1598.

1495

ѵ (C-Cl)

1042

A4

3101,

3060

2927,

2881

1645

1600,

1448

ѵ (C-S)

1198

Comp. No.

n C-H

Aromatic

n C-H

aliphatic

n C=O

 

n C=C

Aromatic

Other

B1

3099,

3043

2920,

2852

1728

1600,

1519

ѵ (NO2)

1519,

1343

B2

3098,

3040

2925,

2852

1728

1600,

1452

-                       

B3

3105,

3028

2950,

2858

1718

1596,

1490

ѵ (C-Cl)

1093

B4

3090,

3020

2920,

2842

1726

1600,

1448

ѵ (C-S)

1192

 

 

Table (3) 1HNMR and 13CNMR data of compounds (B1 and B3) in ppm.

Compd.  No.

Compound structure

1HNMR data in ppm

 

13C-NMR data in ppm

B1

 

d1.23(t,-CH2-CH-),d1.91-2.8(m,-H2-CH-),d 3.83(t, -CH-N), d 4.35(d, -CH-Cl), d 7.21-7.96(m, 4H, ArH)

29.23-35.26(-CH2-CH-);

49.19(C-Cl); 51.32(C-N); 116.25-139.19(C-aromatic); 169.08(C=O)

 

B3

 

 

d1.21(t,-CH2-CH-),d 1.92-2.84(m,-H2-CH-), d 3.49(t, -CH-N), d 4.35(d, -CH-Cl), d 6.95-7.84 (m, 4H, ArH)

30.24-38.34(-CH2-CH-); 46.50(C-Cl); 50.66(C-N); 118.54-128.48 (C-aromatic); 166.98(C=O)

 

 

 

Figure 1: Effect of inhibitor concentration on the efficiencies of stainless steel obtained at 30oC in 1M HCl containing different concentrations of suggested inhibitors

 

These results highlight the fact that the adsorption of the stainless-steel inhibitor increases with an increase in the concentration of the inhibitor. The inhibitive activity of the inhibitor may be partly due to the presence of heteroatoms and aromatic rings in the poly β-lactam structure and the capacity to create a protective film on the metal corroding layer. As shown in Figure 1,19.

 

Adsorption isotherm is very useful in determining the properties of an inhibitor of adsorption. Values of the surface coverage measured by weight loss scales have been used to fit the Langmuir isothermal curves. The properties of the Langmuir isothermal adsorption isotherm are expressed in the equation (3)20.

 

C/Ɵ = 1/Kads + C…………………………...(3)

 

Kads: is the equilibrium constant of the adsorption process.

 

The degree of (surface coverage Ө) at different inhibitor concertation at (1M HCl) was measured by measurement of weight loss (Ө =lE/100) see table 4) at 30 C0 and checked with Langmuir isotherm relationship. By the Langmuir isotherm values of the (Kads) can be determined from the intercepts of the straight line of plotting (C/Ө) against (C) see figure (2,3), Kads is correlated with the standard free energy of adsorption(∆Gads), with the following equation:

 

                1           -∆Gads

Kads = –––– exp –––––– …..………………(4)

            55.5             RT

 

 

Table (4) show the values of free energy of adsorption is negative to indicate that the adsorption mechanisms of all inhibitors (B1-B4) are spontaneous processes on the stainless steel after 24 hours and that makes sense for a remarkable relationship between the proposed inhibitors and the metal surface. Here the adsorbed atom travels closer to the surface of the metal, allowing electrons overlap with the surface elements that cause physisorption for the suggested inhibitors21,22.

 

Table 4: Corrosion rate, inhibition efficiency, surface coverage (θ) and standard free energy of adsorption for mild steel in 1M HCl by using weight loss measurements   

Concentration (M)

Corrosion rate (mgcm-2 h-1)

IE%

θ

∆G°ads (kJ mol-1)

Blank

0.004

-

-

-

(B1)

 

 

 

 

10-2

0.0006

83.3

0.833

-37.95

(R2=0.9994)

 

 

10-3

0.0011

75.0

0.750

10-4

0.0013

68.3

0.683

10-5

0.0016

60.0 

0.600

(B2)

 

 

 

 

10-2

0.0010

74.6

0.746

-47.78

(R2=0.9994)

 

 

10-3

0.0012

70.0

0.700

10-4

0.0015

61.6

0.616

10-5

0.0018

55.0 

0.550

(B3)

 

 

 

-47.01

(R2=0.9995)

 

 

10-2

0.0011

75.0

0750

10-3

0.0016

60.0

0.600

10-4

0.0021

47.5

0.475

10-5

0.0025

37.5

0.375

(B4)

 

 

 

 

10-2

0.0004

90.0

0.900

 

-23.89

(R2=1)

 

10-3

0.00046

88.3

0.883

10-4

0.0014

63.3

0.633

10-5

0.0023

42.5

0.425

 

 

Figure 2: Langmuir adsorption isotherm plot for mild steel in (1M HCl) solution in the presence of various concentrations of inhibitor (B3)

 

 

Figure 3: Langmuir adsorption isotherm plot for mild steel in(1M HCl) solution in the presence of various concentrations of inhibitor (B4)

 

5. CONCLUSION:

The following findings can be deduced from the cumulative experimental results, all weight loss measurements show inhibition efficiency in at all inhibitor concentrations. Maximum inhibition efficiency is approximately 90.0 at 0.01N concentration for compound B4, The adsorption of poly β-lactom on the surface of stainless steel in 1N HCl solution meets the Langmiur isotherm. In the end adsorption free energy values showed the physisorption effect (B1-B4) and provided useful information to describe the interaction between the metal surface and the organic molecules.

 

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Received on 30.12.2019           Modified on 12.05.2020

Accepted on 05.10.2020         © RJPT All right reserved

Research J. Pharm. and Tech. 2021; 14(6):3039-3944.

DOI: 10.52711/0974-360X.2021.00531