Vol.7 No.3 CHINESE JOURNAL OF POLYMER SCIENCE 1989 COORDINATION POLYMERIZATION OF BENZOTRIAZOLE ON THE SURFACE OF METALLIC COPPER XUE Gi (#° 4), DAI Qinpin ( ®% ),DING Jianfu (T#x ). and WU Peiyi (Risté ) (Department of Chemistry « Nanjing University » Nanjing, ) ABSTRACT ‘The coordination polymerization of benzotriazole with metallic copper has been investigated by infrared and X-ray photoelectron spectroscopies . We found that benzotriazole could react with cop- per (0 )under mild conditions to form bis ( benzotriazolato )copper ( Tl ) and benzotriazolato copper CT which covered the surface of copper metal in the shape of polymeric materials . Since benzotriazole is of great interest as a ligand in that its presence in many biological system with metal ions .and is considered as a corrosion inhibitor this work will be in favour of the study of protective corrosion . INTRODUCTION Benzotriazole ( BTAH hereafter ) is of considerable interest as a Ligand in that its presence in many biological systems provides a potential binding site for many metal ions. BTAH is considered as a Ligand in solution near neutrality via the unshared pair of electrons on nitrogen . In sufficient basic media the conjugate base , BTA° , is formed and may function as a ligand too . The tendency then is for forma- tion of an “inner” complex of stoichiometry M*( BTA~ ) or M*( BAT- )2» with depositive ions . These materials are usually insoluble in organic solvents and are gener- ally considered to be polymeric in nature!'~*), Copper is traditionally known as a coinage metal together with silver and gold be- cause of its stability under ordinary atmospheric conditions. We report here an unusual reaction of copper metal in a non-corrosive solution consisting of ethanol and BTAH , during which copper metal is dissolved under extreme mild con- dition , a polymeric material , bis ( benzotriazolato ) copper ( II ), is formed . BTAH is also.a well — known corrosion inhibitor . Inspite of the application of dif- ferent techniques , the mechanism by which BTAH inhibits corrosion on copper has not been completely elucidated . The consensus is that BTAH is chemisorbed on cop- per oxides surface to form an inert copper— BTAH coordination polymer film . Using ellipsometry, Mansfeld and Smith found that BTAH interacted with copper only when it was covered with oxides’! , However , unlike the reports above mentioned , we have found that BTAH could easily interact with metallic copper directly in a fast rate. EXPERIMENTAL BATH ( 99% ; Aldrich Chemical Co. , Inc. ) was dissolved in distilled water Received June 14 , 1988.240 CHINESE JOURNAL OF POLYMER SCIENCE 1989 and ethanol (1:1 ) to give a 0.2M solution at 25 C . 0.5 gram of copper powder was etched in 5% HNO, to remove the surface oxides, and rinsed by ethanol (95% ) thoroughly . 100 ml of BTAH solution was mixed with the copper powder immediate- ly after the rinsing while the powder was still wet. The system was vigorously agitated and exposed to the air at 25 C . And then gradually a suspended white solid was formed . A sample was collected after the reaction had proceeded for one day , and it was named as an “intermediate”. As the reaction proceeded for five days , all of the copper powder changed into a blue material which was supposed to be the reaction product . The intermediate and the product of the reaction were washed by ethanol , dried under vacuum, and then characterized by infrared and X~-ray photoelectron spectroscopies and elemental analysis . IR spectra were obtained using a Nicolet 170 SX Fourier transform spectrometer, and were recorded at a resolution of 4cm™'.A minimum of 100 scans were coadded for each spectrum . Photoelectron spectra were obtained by ESCA LAD MK-—2 spectrometer with Mg k,,, as the radiation source (h= 1253. 6 eV ). The pressure during measurements was less than 10-7 torr. The samples were spread thinly on scotch double— coated tape which was attached to an aluminium sample holder. The C,, line ( BE = 284.4 eV ) from residual pump-line oil contamination was used internal standard for binding energy calibration . Possible changes in the compounds under X —ray action were monitored by repeating scans , but no significant changes in the spectra were observed . Measurements of the average of three different values from different samples have been considered accurate to + 0.2 eV . A Dupont 310 curve resolver was used for peak deconvolution with a Gaussian fit . RESULTS AND DISCUSSIONS Spectra in the middle infrared re- gion are shown in Figure !. In the solid i : state, BTAH is associated by means ee of hydrogen bonds involving the N— H | group. IR spectrum of BTAH shows i strong and broad absorptions in the re- N93 735, gion 3600 — 2500 cm~' . The spectrum p——w} i of the reaction product from metallic Wen | So and BTAH is. very. different ‘ek i) 824 from the spectrum of solid BTAH . The i209 complete absence of the N-H bond mt stretching absorption near 3000cm™', site the N-H_ bending frequency at Wavenumbersicm ') 1524cm™', and the N—H out-of Fig .1 IR spectra of benzotriazole ( lower ) and the — plane bending frequency indicate the reaction product of benzotriazole with copper absence of the imino hydrogen in the metal (upper ) reaction product . The analytical results of the elemental analysis are given in Table 1 .Vol.7No.3 COORDINATION POLYMER OF BENZOTRIAZOLE ON COPPER SURFACE 241 Table 1 Elemental analysis data Samples % | H% | _N% | RatioC:H:N BTAH Calculated | 60.5 | 4.2 | 35.3 | 6:53 Found 60.2 | 45 | 35.4 BTAH Caulated | 39.3 | 2.7 | 30.0 | 6:5:3 Ci'(O ) Found 38.8 27 29.7 Catculated | 48.0 | 2.6 | 28.0 | 64:3 CHBTA? Found | 47.7. | 2.5 | 27-7 For BTAH the number ratio of atoms C : H: N should be 6: 5: 3, while for the re- action product the ratio is 6: 4: 3. The change shows the deprotonation during the reaction. Figure 2 shows the spectra in the far infrared region . BTAH spectrum lattice vi- bration mode is at 132cm7' and benzene — ring torsion is at 285 cm~' . The reaction in- rw VW termediate shows broad absorption band near 173cm™' which will be discussed in latter section. There is a new broad band near 292cm™! which could be assigned TN pe as Cu(+ 2 )—N stretching mode in the spec- trum of the reaction product!®!. The disap- pearance of N—H stretching and the forma- 132 tion of Cu( + 2 )—N bond indicate that the / 132 285 reaction product is probably copper " benzotriazolate. a0 0350250200150 BTAH possesses the property of, Wavenumberstem™!) basicity , intermediate between that of satu- — Fig.2 Far IR spectra of benzotriazole ( upper ). rated amines such as R,NH and aromatic the intermediate ( middle ). and the amines such as pyridine. In addition to its product (lower ) basic properties , BTAH is also a weak acid. : 3 NN a Ni, an N+ Ht L_.- = O Ni nN H Metallic copper has not been considered to be active enough to substitute for the pyrrole proton from BTAH solution at room temperature . Metal benzotriazolates were ususlly prepared by boiling sufficient basic solution of BTAH and metal ions!) The formation of copper benzotriazolate form BTAH and metallic copper in neutral solution seems to follow a new reaction scheme . XPS studies of the model compounds and the samples from the reaction system of BTAH and metallic copper gave more information of the reaction procedure. Bis ( benzotriazolato ) copper ( [] ) and benzotriazlato copper ( | ) model complexes were prepared according to the method outlined by Goodgame and Cotton'"! . Their photoelectron spectra are given in Figure 3. The analysis of Cu,, peaks of the242 CHINESE JOURNAL OF POLYMER SCIENCE 1989 complex from cuprous ion and BTAH shows two binding energy values, 932.9 and 935.1 eV. The first value coincides with the value of Cu (+1), and the second with Cu (+ 2). This peak gives evidence for the partial oxidaton of benzotriazolato copper (I )prior to the XPS measurement. The XPS spectrum of bis( benzotriazolato ) copper(I] ) shows binding value of Cu,, 935.1 eV. Jn Figure 4 the Cu,, photoelectron peak of the reaction intermediate shows mainly binding energy 932. 2 eV , which coincides with the copper at zero oxidation state. The spectrum of the reaction product shows binding energy value 935. 1 eV which co- incides with the model complex bis ( benzotriazolato ) copper ( II ). The sample col- lected from the system after the reaction had proceeded for three days seems mainly the mixture of the intermediate and the product. Based on IR and XPS studies it seems reasonable to conclude that the final product is bis (benzotriazolato ) copper ( II ). 932.9 30.0 982.5 985.0 90,0 —-985.0 Binding energy (eV) Binding energy(eV) Fig .3 XPS spectra of model complexes Fig .4_ XPS spectra of the samples from the reaction system upper :the model complex from upper : the reaction product ; Cu(+1 )and BTAH solution ; middle : the sample collected afier immersion lower : the model complex from for three days ; Cu(+2)and BTAH solution . lower : the sample after immersion for one day . This reaction could take place in many kinds of solvents. As using predried solvent and reactants, a minimum quantity of water was detected after the reaction. If the oxygen was removed from the system by bubbling with prepurified nitrogen , the re- action could not carry out to the end. We proposed the scheme as follows : (below ) The first step of the reaction seems to be the formation of Cu(0)-BTAH complex , an intermediate , by ligation of N—3 of BTAH with metallic copper . This assumption is supported by far infrared and XPS studies. N—Cu( 0 ) stretching mode shows absorption band near 173cm~! in Figure 2, which is lower than N-Cu( +2) stretching mode in frequency due to the probable difference in force constants . On the other hand, the binding energy of Cu,, for the intermediate is 932. 2 eV which coin- cides with the copper at zero oxidation state. The intermediate is unstable. It canVol7 No.3 COORDINATION POLYMER OF BENZOTRIAZOLE ON COPPER SURFACE 243 teturn to Cu(0)and BTAH by acid or be oxidized to copper benzotriazolate by oxygen in air. BTAH contains three nitrogen atoms, one is the so-called pyrrole nitrogen( N—1), and the others are the pyridine nitrogen. The deprotonated benzotriazole anion possessed two equivalent sites of nitrogen for coordination. While each cupric cation can coordinate with four nitrogen ligands. It is reasonable to suppose the structure of copper benzotriazolate to be that of an infinite polymer net work with benzotriazolato anions acting as bridging ligands. In fact it was reported that bis( imidazolato) copper( I] ) prepared from the boiling solution of imidazole and cupric cation was a polymeric material!" BTAH — ethanol mixture could react with cop- per metal rather than powder form. When a piece of copper plate was immersed in 2%BTAH — ethanol solution without agitation, a +10 «ayeur) compact polymeric film has been formed in a few ' minutes. Reflection absorption IR and XPS studies FBTANS OF show that the film is bis( benzotriazolato) copper (I ). This pretreated copper plate could be used as an electrode in an acetate buffer( pH =6. 0), and cyclic voltammetry was performed. The cyclic voltammetry of this copper electrode is illustrated in Cute 2) Figure 5.Since a compact film presents on the cop- a per surface, the initial two cycles do not show \& anodic oxide peaks and cathodic reduction peaks , " and the current is little . As increased the scans , the intensities of the oxidation and the reduction peaks increase gradually. After tenth cycling, the voltammogram reaches constant . It takes high positive potential and long time to destroy the compact film ."This compact film has a strong ability in inhibition of undesirable reactions on copper surface . CONCLUSIONS We have shown that BTAH can react with copper metal other than copper cations or oxides in extremely mild conditions. The reaction product is mainly bis( benzotriazolato ) copper( II ), which covers the surface in the shape of a polymeric material .244 CHINESE JOURNAL OF POLYMER SCIENCE 1989 oa ¥0.40 9.00 0.40 =9.80 potentiakV - vs - SCE) Fig.5. Effect of BTAH on cyclic voltammetry of copper — prior immersion in BTAH ~ ethanol solution. Keywords: Benzotriazole ; Metallic copper ; Coordination polymerization on surface; Infrared ; X—ray photoelectron spectroscopy. REFERENCES (1) Walker.R.. J Chemical Education 1980 .57( 11). 789. {2) Wall. K .H. and Davies .1.J. Appl Chem.» 1965.15 .389. 13] Cotton. J. B-and Scholes «I. R . Brit -Corros .J -1967..2.1. [4] Roberts .R.F.. J Electron Spectrsc . Related Phenom. 1974.4 .273 . {5] Yoshida .S .and Ishida .H'.. J. Materials Sci. . 1984. 19.2323 . [6] lto.M.and Takahashi .M . + Surface Sci. . 1985 . 158 .609 [7] Mansfeld .F .and Smith .T . . Corrosion .1973 .29 .457 [8] Sullivan.D.G.O-J.Chem. Soc . + 1960 . 3653 . [9] Cordes.M.M.and Walter .J.L.. Spectrochimica Acta +1968 .24A .1421 . [ 10] Goodgame . M . and Cotton .F.A.. J. Am.Chem. Soc. 1962 84.1543. [11] Brown. G.P. and Aftergut.S.. J. Polym. Sci. Part A. 1964 .2.1983.