Elizabeth Dafoe Document Delivery RE 7101031 ORPS DAFOE 2NDFLR -- saved Portland State University Library - Interlibrary Loan 951 SW Hall Avenue Portland, OR 97201 USA SUBMITTED: 2008-10-21 15:59:54 PRINTED: 2008-10-22 14:04:28 REQUEST NO.: REG-47101031 SENT VIA: ocLe EXPIRY DATE: 2008-10-30 OcLe No.: 47339140 REG Regular copy JOURNAL NEED BEFORE: 2008-11-20 TITLE: TRIBOTEST. PUBLISHER/PLACE: John Wiley & Sons Chichester, UK VOLUME /ISSUE/PAGES : 949 4 317 - 332 DATE: June 2003 AUTHOR OF ARTICLE: V. Bansal, A. Chopra, M. I. S. Sastry, V. Kagdiyal, A. S. Sarpal: Detailed characterisation of sulphur and nitrogen comp OTHER NUMBERS/LETTERS: Canadiana: 129792271 SOURCE: ocLe MAX COS: $20.00 IFM COPYRIGHT COMP. : ceL. NOTES: From OCLC:0RZ Delivery Info.: ARIEL,ORBIS COURIER, FAX, LIBRARY RATE FEIN #93-6001786 FAX/ARIEL: (503) 725-4527 ARIEL:ariel.lib.pdz.edu or 131.252.180.29 EMAIL: ILL@pdz.edu BILL TO: came REQUESTER INFO: Totten, Gearge DELIVERY: Ariel: 131.252.180.29 REPLY: E-mail: ILL@pdx.edu This document contains 16 pages. You will be invoiced for $10.00. This is NOT an invoice. If payment is required send remittance and invoice copy. Visa/Mastercard payment accepted. Phone: 204-474-9873; Fax: 204-474-7577 Document Delivery, E. Dafoe Library. 25 Chancellors Circle, University of Manitoba, Wpg. MB R3T2N2 University of Manitoba LibrariesLeaf Coppin 317 Detailed Characterisation of Sulphur and Nitrogen Components in a Multifunctional, Ashless Lubricant Additive by Spectroscopic and Chromatographic Techniques V. Bansal, A. Chopra, M.S. Sastry, V. Kagdiyal, and A.S. Sarpal Indian Oil Corporation Limited, Research and Development Centre, Faridabad, India Abstract ‘The work reported here used infrared (IR), multinuclear nuclear magnetic resonance (NMR), and chromatographic techniques to identify and characterise a commercial sulphur- and nitrogen-containing ashless multifunctional additive, The proper assign- ment of signals in the 1H/3C NMR and IR spectra of the sample has facilitated the identification of different types of sulphur- and nitrogen-containing components. The methodology involves investigation by NMR and IR spectroscopies, thin-layer chroma- tography (TLC) and high-performance liquid chromatogaphy (HPLC) techniques to elucidate the types of components present. This requires the generation of NMR and IR spectral data for standard compounds of alkyl sulphides with different sulphur content and alkyl chain, and nitrogen and sulphur components such as thiadiazole, iniidazoline, triazole, etc., and spectral comparison with the spectra of the unknown sample. Further, these components have been separated by silica/alumina column chromatographic and preparative TLC techniques and subsequently analysed for their exact chemical struc- lure by spectroscopic techniques. The combined spectroscopic and chromatographic analyses have yielded the presence of four types of components: di-t-octyl polysulphide, di-t-octyl thiadiazole, a component containing amine ether functionality, and alkyl antine salts of mono/dialkyl phosphoric acid. Keywords ashless multifunctional additive, nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, high-performance liquid chromatography (HPLC), "thin-layer chromatography (TLC) Tribotest journal 9-4, June 2003. (9) 317 ISSN 1354-4063 $10.00 + $10.00 (2186/0603)318, Bansal, Chopra, Sastry, Kagdiyal, and Sarpal INTRODUCTION Lubricants today are treated with a variety of multicomponent additives to achieve the required overall performance levels. Demands on the performance of lubricating oils are increasing and diversifying, and because of the require- ments for higher performance in machine systems, or in order to be of use in novel systems, the applications of multifunctional additives are increasing. Sulphur-based additives are mainly used as antiwear (AW) and extreme- pressure (EP) agents, which include sulphurised olefins (sulphurised isobutyl- ene), sulphurised fats or esters, polysulphides, xanthates, thiocarbonates, and dithiocarbamates.' A number of nitrogen/sulphur compounds that have been found to possess AW and load-carrying properties are benzotriazole deriva- tives, alkyl thiomethy! benzotriazole, 1,3,4-thiadiazole,? + and Schiff bases.” Researchers have been attempting to understand better the chemistry, per- formance, and mechanisms of various such additives. This understanding, in turn, can help in formulating structure-property relationships. An analytical method has thus been developed? for the estimation of the alkyl-to-aryl ratio of organo zinc dithiophosphate additives in finished lubricants based upon concentrating the active ingredients by liquid chromatography followed by infrared (IR) measurements. °!P nuclear magnetic resonance (NMR) spectros- copy has been widely used to characterise the phosphorus-containing additives used in lubricants.” Multinuclear NMR analysis, along with IR spectral data, helped in the complete identification of various phosphorus-based components in a commercial sample of phosphate amine additive.* Structure—activity corre- lations for sulphur-containing additives have been studied after synthesising a series of new sulphur compounds.” It has been established that the performance of these additives is entirely dependent upon the nature and structure of the compounds.!013 In the above context, a commercially available sulphur/nitrogen-based additive has been characterised to determine the nature of the main and other components. NMR, IR, thin-layer chromatography (TLC), high-performance liquid chromatography (HPLC), and open column chromatography techniques have been used to characterise similar types of ashless additive synthesised in the authors’ laboratory, to give some insight into the additive chemistry. In the present investigation, a scheme of analysis is described for the separation, identification, and structure elucidation of commercially available sulphur- and nitrogen-based components in a lubricant additive system by the application of NMR, IR spectroscopic, TLC, and HPLC techniques. © Tribotest journal 9-4, Junie 2003, (9) 318 ISSN 1354-4063 $10.00 + $10.00Detailed characterisation of sulphur and nitrogen components ina multifunctional, ashless 9 lubricant additive by spectroscopic and chromatographic techniques EXPERIMENTAL: Elemental analysis The nitrogen content was estimated using an Antek-N nitrogen analyser. The sulphur and phosphorus contents were determined by X-ray fluorescence. Infrared The IR spectra were recorded with the samples as thin films on KBr windows using an FT-IR instrument. Nuclear magnetic resonance The 'H, "3c, and 3'P NMR spectra were recorded using an NMR spectrometer (300 MHz) operating at 300, 75.4, and 121.3 MHz, respectively. The solutions of the samples and the column fractions were prepared in CDCI3 (20-30% w/v). A relaxation delay of 5 s and 32 scans were used for each recording of 'H NMR spectra. The SC NMR spectra were recorded in inverse-gated mode with a delay time of 4-5 s and 2000 scans using chromium acetylacetonate as the relax- ation agent and tetramethylsilane (TMS) as an internal standard. The distortionless enhancement by polarisation transfer (DEPT) experiment was carried out using the pulse sequence of Doddrell et al.'4 The 2D (homonuclear correlation spectroscopy (COSY) and heteronuclear correlation spectroscopy (HETCOR)) NMR experiments were recorded as detailed elsewhere.!516 Thin-layer chromatography The TLC experiments were carried out on precoated silica gel (60W) plates (without fluorescent indicator) using a solvent mixture of chloroform/ethyl acetate (80:20). Visualisation of the spots was carried out using palladium chloride and Dragondroff as the spraying reagents. Preparative TLC was carried out using PLC plates precoated with silica with a layer thickness of 2 mm having a concentration zone of 4 em x 20 cm (from Merck) using the same mobile phase optimised earlier. A 20% solution of 50 mg of sample was loaded on the plate. The separated fractions were extracted with methanol, filtered, and evaporated for subsequent analysis. High-performance liquid chromatography HPLC of separated fractions was carried out using a Waters 600 HPLC unit equipped with a fixed volume loop of 20 p1l at a flow rate of 1.0 ml/min. The Tribotest journal 9-4, June 2003. (9) 319 ISSN 1354-4063 $10.00 + $10.00320 Bansal, Chopra, Sastry, Kagdiyal, and Sarpal Table 1 Fractions obtained using different separation approaches Silica column Amina column Preparative TLC Fraction Mobile phase (eluent) Fraction Mobile phase (eluent) Fraction Spots Fa Hexane FAR Hexane Lt Top 2 Hexane/CCh, (1:1) 2K Hexane/ethylacetate (19:1) 2 Middle BS cel, FSR Hexane/ethylacetate@3)—L-3_—_—Bottom Fa CHCK/CHAOH G1) FAR Ethyl acetate 5 CHCh/CH.OH (1:1) FSR Methanol mobile phase used was acetonitrile (HPLC grade). The column used for the sep- aration was C-18 (25 cm x 0.46 em, from Supelco). A UV detector at 254 nm was used for monitoring the column eluents. SEPARATION OF ADDITIVE COMPONENTS: Methanol extraction The polar components of the sample were enriched by carrying, out methanol extraction of the original additive. A known quantity of sample was extracted with methanol. The methanol layer was separated and evaporated to get the polar components for subsequent separation and identification. Chromatographic separation Open column chromatography ‘The methanol extract of the sample was subjected to open column chromatography using silica as the stationary phase with elu- ents of increasing polarity (gradient elution). Initially hexane was used to elute the less retained component from the column as fraction F-1. Subsequently, the polarity of the mobile phase was increased by mixing CCl, in hexane and frac- tion F-2 was collected. After elution of the column with CCl, (to obtain fraction F-3), the polarity of the mobile phase was enhanced with a mixture of chloro- form and methanol (3:1) for elution of fraction F-4, and lastly a 1:1 mixture of chloroform and methanol was used to elute the most polar components (frac tion F-5). Fractions F-1 to F-5 (Table 1) thus collected were analysed for their components using TLC, IR, and NMR techniques. Based on the findings for the fractions obtained from the silica open col- umn, the separation was further improved by carrying out a second column of methanol extraction using alumina/silica (1:3) as the stationary phase with a modified mobile phase of increasing polarity: elution with hexane (to obtain Tribotest journal 9-4, june 2003. (9) 320 ISSN 1354-4063 $10.00 + $10.00Delailed characterisation of sulphur and nitrogen components in a multifunctional, ashless Iubricant additive by spectroscopic and chromatographic techniques ‘Table 2 Characteristic NMR and IR frequency data for pure reference compounds Reference compounds Sulphurised isobutylene (SB) Di-t-octy! polysulphide Di octyl disulphide Di-isopropyl poly sulphide Di-isopropyl mono- sulphicle butyl polysulphide Dit-butyl monosulphide Di-t-butyl disulphide Disroetyl polysulphide Disulphide Sulphurised fat 2,5-Dialkyl-ctimercapto- 13Arthiadiazole, R= bocty! (1,1,3,34etramethyt butyl R= sroetyl Alkyl imidazoline Alkyl xanthates, R= isobutyl “e= singlet, d = doublet, m = multiplet, Q= quaternary. w THENMR (ppm 1.34, 18,25-3 4.8m) 1.08, 1.46,1.49,1.7, 173 1.03, 1.46, 1.50, 174 1.3244), 2.95(m) 1.28(4), 30 1.38, 1.4(6), 14269) 14 0,88, 1.38, 1.55, 2.5(m) 0.88, 1.38, 1.5 2.45(m) 0.9, 1.38, 1.6, 2.34, 26-30, 4.1-4.4(m) 1.04, 1.46, 1.7 29,27,1.7,1.27, 0.88 33,27, 241,20, 16, 125,088 1.0(4), 2.100), 3.4565), 43(0) BO NMR (ppm) 20.2, 24-30, 40-60, 112-116, 139-142 29.4, 299, 32.0, 328, 53.8(Q), 54.0 29.4,30.2, 32.1, 2.8, 52.6(Q), 54.0 226,414 237,335 30.6-93.8, 46.1-48.1 33.2, 46.5, 306, 46.1 14.0, 22.7, 28.9, 29.2, 29.8, 31.9, 32-39 140, 22.7, 289, 29.2, 319, 38.9 140, 22.7, 24.5, 26.7, 24.846), 31.9, 34-15 (W) 339, 61.9, 68.3, 120- 145(w), 173, 179.0 29.0, 31.8, 32.6(Q), 53.6, 35.9(Q), 174.8, 164.0, 188.0 14.0,22.7, 28.2, 29.018), 31.9. 39.0, 39.4, 173.3 174.0-164.0,58.5-44.0, 319,297,227, 14.1 180, 2 810,210 weak: IR ens 3080, 1650, 1110, 900, 500 1203, 1106, 982 1203, 1106, 982 1312, 1232, 1154, 1047, 620 2, 1238, 1152, 1044, 650 131 1155, 610, 1209 1220, 1161, 567 1216, 1100, 912 1740, 1440, 1160 1250, 1200, 1110, 11050, 980, 700 1300-12000), 1120, 1050, 720 3300, 1650 Tribotest journal 9-4, June 2003, (9) 321 ISSN 1354-4063 $10.00 + $10.00 321322 Bunsal, Chopra, Sastry, Kagdiyal, and Sarpal Figure 1 1 NMR spectra: (a) original additive; (b) fraction F-5; (©) fraction F-2R (S-2); (d) fraction F-5R (S-3) — — 2R), 25% ethyl] acetate in hexane (F- R). fraction F-1R), 5% ethyl acetate in hexane 3R), ethyl acetate (F-4R), and methanol ( Preparative TLC Preparative TLC was carried out to isolate the column frac- tion F-5 into different components. The preparative isolation of components was done using a preparative silica plate 4 cm x 20 cm (from Merck). A mixture of chloroform/ethyl acetate (80:20) was employed to separate F-5 into three components. The spots collected were marked as the top spot (L-1), middle spot (L-2), and bottom spot (L-3). Silica from each spot was scratched off from the Tribotest journal 9-4, June 2003. (9) 322 ISSN 1354-4063 $10.00 + $10.00Detailed characterisation of sulphurand nitrogen components ina nuultifunetional, ashless 323 lubricant additive by spectroscopic and chromatographic techniques Figure 2 °C NMR spectra: (a) original additive; (b) fraction F-5 (inset: ampli n); (¢) fraction F-2R (S-2) (inset: amplified region); (a) fraction F-SR (S-3) (inset: amplified region) 90 80 70 60 50 40 30 20 10 ppm © (b) Be bem fe LH | Oa 00 cop (a) plate and extracted with methanol, and evaporated for further analysis by IR/ NMR. A summary of the data for the above separated fractions is compiled in Table 1 Tribotest journal 9-4, June 2003. (9) 323 ISSN 1354-4063 $10.00 + $10.00324 Bansal, Chopra, Sastry, Kagdiyal, and Sarpal RESULTS AND DISCUSSION In order to understand the NMR and IR spectral features of the N- and S- containing additives, the 'H and °C NMR and IR spectra of standard S- and N- containing EP and corrosion inhibitor compounds were recorded. The chemical shift and frequency data are given in Table 2. The spectral information thus gen- erated are used for spectral comparison in the identification of the types of S and N components present in the sample under study. The NMR spectral features of different alkyl sulphides with different alkyl chains attached to sulphur atoms are distinct and can be specific fingerprints for exact structure elucidation. For instance, the isopropyl, butyl, !-octyl, and n-octyl groups display distinct and characteristic signals in both 'H and ‘SC NMR spectra. Similarly some useful information regarding the nature of the alkyl chain can be derived from the IR spectra after critical interpretation. The !4C NMR spectral analyses can also dis- tinguish clearly mono-, di- or polysulphide linkages, as with increasing sulphur content the chemical shift of the carbon atom attached to sulphur varies largely in the range 2-8 ppm (Table 2). The S- and N-containing compounds belonging to alkyl benzotriazole, imidazoline, and thiadiazole derivatives display signals characteristic of each class, as evident from Table 2, and thus can be used as a source of identification in an unknown sample, Analysis of the original additive The 'H, SC NMR, and IR spectra of the original additive (S = 38.8, N = 0.45, and P = 0.0155% w/w) are shown in Figures 1(a), 2(a), and 3(a). The 'H NMR spec- trum clearly shows very sharp and intense signals at 1.03 (ICH), 1.5 (CH) and 1.74 ppm (CH,). These signals match with the spectral features of di-t-octyl polysulphide (Table 2). The C-S linkages, being non-protonated, do not appear in the 11 NMR spectrum. However, 3C NMR spectral analysis has confirmed the C-S linkages. Further, the *C NMR spectrum shows five sharp and intense signals at 29.4, 29.7, 31.9, 32.8, and 53.7 ppm due to CHy, CH, and quaternary carbons. The intensity and position of these signals are well matched with the 3 NMR spectrum of di-!-octy! polysulphide. Subsequently, the identities of signals with regard to carbon multiplicities (CH,,, 1 = 0-3) were established by a DEPT-135 spectral editing experiment. Generally the quaternary carbons of t-octyl attached to mono- or disulphide give signals at 45.5-46.6 ppm. Since, in the present case, the C-S signal appears quite downfield at 53.7 ppm, this indic- ates the presence of more than two sulphur atoms in the structure, probably four sulphur atoms as estimated on the basis of the sulphur content of the sample. ‘The 9C NMR spectrum also indicates only one type of C-S signal at 53.7 ppm. This confirms the absence of mono- and disulphide compounds. Gel Tribotest journal 9-4, june 2003. (9) 324 ISSN 1354-4063 $10.00 + $10.00Detailed characterisation of sulphur and nitrogen components ita multifunctional, ashless 325 lubricant additive by spectroscopic and chromatographic techniques Figure 3 IR spectra: (a) original additive; (b) fraction F-5 4000 ‘3000 ‘2000 1500) 1000) 500 Wavenumber (or Absorbance permeation chromatographic (GPC) analysis also shows the very narrow peak distribution of sulphur compounds in the sample (dp = 1.0). The IR spectrum shows strong bands at 1104, 1300, 1345, 1383, and 1384 cm and bands of med: um intensity at 520, 650, 717, and 981 cm”, The nature of these bands is similar to those appearing in the IR spectra of di-t-octylated polysulphide (Table 2). 31P NMR spectral analysis of the original additive sample indicates signals at 0-1 and ~11.5 ppm, which have been assigned to alkyl phosphate/phosphoric acid-type components.’ The presence of a very small amount of P (0.0155%) necessitated recording the spectra with an increased number of scans. The additive sample when subjected to TLC analysis was found to contain two types of S components. One spot only showed the presence of S species and no N component, whereas the other spot showed the presence of both S and N components. The $ component was found to be identical to di-t-octyl poly- sulphide (standard reference) in terms of both Ry value and colour of the spot. Tribotest journal 9-4, June 2003. (9) 325 ISSN 1354-4063 $10.00 + $10.00326 Bansal, Chopra, Sastry, Kagdiyal, and Sarpal Figure 4 HPLC chromatographs: (a) original additive; (b) fraction F-5; () fraction F-2R (5-2); (d) fraction F-5R (5-3) a 1 = Time a Further, reverse-phase HPLC (Figure 4(a)) was also used to resolve the components and identify them. It appears from the above preliminary investigations of the sample by ele- mental, TLC, HPLC, GPC, IR, and 'H and SC NMR analyses that di-(1,1,3,3- tetramethyl! butyl) polysulphide, having structure $-1 (Table 3), is present as the major constituent. The 'H and !8C NMR spectra also show signals of very weak intensity, be- sides the intense signals due to di-t-octy! polysulphide. The weak signals at 3.4 and 3.6 ppm in the 'H NMR spectrum may be due to polar functionality (N = 0.45%). The very weak resonances at 11.0, 14.0, and 22.7 ppm in the "C NMR spectrum are due to the 2-ethy! hexyl group of a component present. A similar observation has been made in the IR spectrum of the sample, where bands of very weak intensity are visible at 714, 1057, 1201, and 1250 cm !. These bands are assigned to nitrogen functionality, possibly C=N linkages of imidazoline- or thiadiazole-type components. The exact nature of the nitrogen- containing com- ponents could not be ascertained due to the small amount in the sample. Analysis of methanol extract (ME) The TLC analysis of the ME shows the presence of S and N components. The 'H NMR analysis of the ME shows signals of enhanced intensities at 3.4 and Tribotest journal 9-4, June 2003. (9) 326 ISSN 1354-4063 $10.00 + $10.00Detailed characterisation of sulphur and nitrogen components ina multifunctional, ashless 327 lubricaut additive by spectroscopic and chromategraphic techniques Table 3 Structures of components present s1 [(CH_)g0-CH-C(CHa)g-le-Sy = 4.0 (S = 38.8%) Di-(1,1.3,3-totramethy| buty)) polysulphide (major) 82 N N | I | cL Le rss@ s© SSR A=-C(CHs)e-CHy-C-(CHols Di-tocty! dimercaptothiadiazole (minor) $3 ~OCH;-CH(O)}-CH,0- Ether-type polar component (minor) s4 RO. ° RO. ° NF NF ven Bier RO on RO ORHSA Alky| phosphate or the amine salt (minor) 3.6 ppm, besides the signals due to dialkyl polysulphide. However, the 'C NMR spectrum clearly shows downfield sharp signals between 160 and 175 ppm and reasonably good intensity signals in the region 10-80 ppm com- pared to the spectrum of the original sample. The signals at 11.0, 14.0, 22.8, 23.6, 30.0, 37.8, 39.2, 53.8, 55.8, 69.2, 73.0, and 74.2 ppm and the weak signals between 160 and 175 ppm are of reasonable intensity compared to the ™C NMR spec- trum of the original sample. The assignment of these signals has been established by DEPT-135 spectral editing experiments. The ~CHs signals at 11.0 and 14.0 ppm, the CHy signals at 22.8, 23.6, 28-30, and 37.8 ppm, and the CH signal at 39.2 ppm are assigned to a 2-ethyl hexyl moiety attached to an N/S/O atom through a CH group. The weak signals at 55.8 and 160-175 ppm are due to quaternary carbon atoms. The signals at 55.8 and 175.0 ppm may be a result of C-S and C=N quaternary carbons, respectively, of an alkyl thiadiazole func- tional group, as confirmed from the reference Spectra (Table 2). The intense signals at 160.0-170.0 and 68.0-74.0 ppm and the 2-ethyl hexyl moiety may be due to amino ether-type polar functionality. The IR spectrum of the ME also shows bands due to dialkyl polysulphide. The presence of alkyl thiadiazole-type components has also been confirmed by IR spectral analyses, which clearly indicate C-N linkages at 1057, 1105, 1202, and 1238-1250 cm" similar to those found in the standard reference spectra (Table 2). The *!P NMR spectral analysis of the ME (P = 0.0455%) shows signals at 0-1 and 11.5 ppm, which might be due to alkyl phosphates or their amine salts. Tribotest journal 9-4, June 2003. (9) 327 ISSN 1354-4063 $10.00 + $10.00228 Bansal, Chopra, Sastry, Kagdiyal, and Sarpal The assignments were made by comparing with standard reference spectra and are mentioned elsewhere.* As discussed earlier, the Ry values and the intensity /colour of the TLC spots, as well as the data generated by NMR and IR of the sample under study, indicate the presence of the following four components: di-t-octyl polysulphide (S-1, major) di-t-octyl dimercaptothiadiazole (S-2, minor) component with ether-type polar functionality (S-3, minor) alkyl phosphate or the amine salt (S-4, minor). As discussed, the ME still contained a higher proportion of dialkyl polysulphide (80%) besides thiadiazole and amino ether-type polar components. These polar components were separated from the polysulphide by silica open column. chromatography. Analysis of chromatographic fractions The hexane and CCl eluted fractions (F-1 to F-3) were found to contain pure di-t-octyl polysulphide, confirmed by TLC, NMR, and IR analyses. The CHCh;/ CH3OH (3:1) mixture (fraction F-4) did not elute any further component. Elution with CHCI;/CH OH (1:1) helped elute the remaining 20% of the com- ponents of the ME from the column (fraction F-5). The 1H, 13 NMR, and IR (Figures 1(b), 2(b), and (3b)) analyses of the F-5 fraction confirm both thia- diazole (S-2) and alkyl amino ether (S-3) components along witha small amount of polysulphide component. The TLC analyses also show the presence of small amounts of dialkyl polysulphide and S- and N-containing components. The signals at 29.80 (CH), 31.8 (CHy), 32.6 (-C-), 53.8 (CH), 55.8 (C-S), and 175.0 ppm (C in the 'SC NMR spectrum have been assigned to the di-t-octyl- 2,5-dimercapto-1,3,4-thiadiazole component. The less intense signals at 11.0, 14.0, 22.8, 23.6, 29.8, 30.5, 37.8, 39.2, 69.5, 74.2, and 73.6 ppm have been assigned to the 2-ethyl hexyl amine ether-type polar component. The nitrogen and sul- phur content in the F-5 fraction increased to 3.5 and 40.9% w/w compared to 0.45 and 38.5% w/w, respectively, in the original additive. As fraction F-5 was found by NMR/ IR analyses to contain a mixture of components, preparative TLC of fraction F-5 was carried out, as explained above (p. 319). The NMR and IR analyses indicated that the upper spot (L-1) contained only an S component, alkyl polysulphide. N-containing species were found to be absent in this L-1 spot, but were found to be present in the L-2 spot. The NMR and IR analyses of the spot at the bottom of the TLC plate (L-3) showed a different nature, not matching with any of the spectral features of N- and S-containing compounds mentioned in Table 2. The nature of the signals in Tribotest journal 9-4, June 2003, (9) 328 ISSN 1354-4063 $10.00 + $10.00Detailed characterisation of sulphurand nitrogen components ina multifunctional, asiless 329 lubricant additive by spectroscopic and chromatographic techniques: 90 80 70 60 60 40 30 20 10 both 'H and 8C NMR spectra (Figures 1(d) and (2d)) appears similar to com- pounds having ether-type functionality. The signals in the 'H NMR spectrum at 3.4 and 3.6 ppm and downfield signais at 69.5 (CH), 73.0 (CHa), and 74.2 ppm (CH) in the 83C NMR spectrum are assigned to ether functionality. The other signals in the 'H NMR spectrum at 0.8-2.0 ppm and the "°C NMR spectrum be- tween 11.0 and 40.0 ppm are due to the 2-ethyl hexyl group, which is quite evident from the NMR spectral feature of the ether condensate product of glycerol and 2-ethyl hexanol. The middle spot (L-2) was found to contain a 1:1 mole ratio of thiadiazole derivative and a component having ether-type polar functionality. The complete separation of the alkyl thiadiazole component (S-2) was achieved through alumina/silica column chromatographic separation, as de- scribed above (p. 320f.). The eluents of fraction F-2R collected from the hexane/ ethyl acetate (19:1) solvent system were found to contain pure alkyl thiadiazole (S-2) and a very small amount of ether-type component as confirmed by IR, 'H, ‘SC NMR, and HPLC analyses (Figures 1(c), 2(c),and (4¢)). Fractions F-3R and FR did not elute any component. So the polarity of the solvent system was enhanced in the last eluents of the column using methanol (F-5R), which was identified as having ether-type polar functionality and a phosphorus-contain- ing component. Further, the confirmation and purity of each separated fraction Tribotest journal 9-4, June 2003. (9) 329 ISSN 1354-4063 $10.00 + $10.00330 Bansal, Chopra, Sastry, Kagdiyal, ard Sarpat was carried out by comparative HPLC analysis of the separated fractions with the reference compounds and original sample. As discussed earlier, the sample was found to contain a very small amount of phosphorus-containing components. The °'P NMR analysis of fraction F-5R (P = 0.6%) also showed it to contain phosphorus-containing components (S-4), the nature of which was the same as discussed earlier in this section. However, their concentration was very small compared to other components. ‘The IR, 'H, and °C NMR spectral features of the bottom spot (L-3) of pre- parative TLC and eluents of the silica/alumina column (F-5R) showed entirely distinct features, which were not found to match with the S- and N-containing compounds given in Table 2. The °C NMR spectrum of this fraction did not yield any signals due to C=N functionality in the range 160.0-176.0 ppm. The 1H NMR spectrum shows signals between 3.2 and 4.3 ppm and between 0.6 and 2.0 ppm. The signals between 3.2 and 4.3 ppm and the corresponding signals be- tween 68.0 and 74.0 ppm in the C NMR spectrum have been assigned to ether- type polar functionality. These observations were further confirmed by IR spec tral analysis where signals at 1056, 1122, 1266, 1382 cm, etc., have been assigned to ether functionality. The broad signals at 3000-3500 cm” are due to the presence of the -OH group. Tribotest journal 94, June 2003. (9) 330 ISSN 1354-4053 $10.00 + $10.00Detailed characterisation of sulphur and nitrogen coniponents ina multifunctional, ashless 331 lubricant additive by spectroscopic and chromatographic techniques In order to determine the exact nature of this polar component, 2D HETCOR of fraction F-5 and 2D COSY of fraction F-5R (Figures 5 and 6) was carried out. The 2D NMR contour plot facilitated the assignment and connect- ivity of signals due to hydrogen and carbon in the 'H and !°C NMR spectra. The main purpose behind this study was to correlate the signals between 3.2 and 4.4 ppm in the 'H NMR spectrum and between 68.0 and 74.0 ppm in the 3C NMR spectrum. The peaks a,b, and ¢ (-CHp) and ¢ (~CH) in the 3C NMR spec- tram show correlation with the equivalent peaks in the 'H NMR spectrum. Similarly the 2D COSY contour plot shows connectivity between the signals, in- dicating that proton signals on the carbons at 3.4 and 3.6 ppm in the 'H NMR spectrum are on adjacent carbon atoms. These signals form a part of the polar functionality attached to the 2-ethyl hexyl moiety. Thus, the 2D NMR connectiv- ity correlation experiment clearly indicates the following connectivity in an S-3 type component: -OCH,-CH(O)-CH,O-. CONCLUSIONS Combined analyses by NMR, IR, and chromatographic techniques have en- abled the identification and characterisation of different types of dialkyl polysulphide, alkyl! thiadiazole, alkyl phosphate/alkyl amine salt of phosphoric acid, and ether-type components. The optimised chromatographic separation schemes based on TLC/ preparative TLC and open column chromatography for the isolation of components of interest followed by their characterisation by molecular spectroscopic techniques such as NMR and IR provided unambigu- ous identification and characterisation of different types of S and N components. IR and 'H/“C multipulse NMR techniques have helped in the correct assignment of signals leading to structure elucidation with regard to the exact nature of alkyl chain length, degree of sulphur condensation, and func- tionality in the components. 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