See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/226356033

Comparison of GC and HPLC Methods for Quantitative Analysis of Tinuvin

622 After Saponification in Polyethylene

Article in Microchimica Acta · June 2005

DOI: 10.1007/s00604-005-0348-1

CITATIONS READS

5 4,771

6 authors, including:

Mir Ali Farajzadeh Morteza Ebrahimi

University of Tabriz Amirkabir University of Technology
135 PUBLICATIONS 5,108 CITATIONS 100 PUBLICATIONS 1,624 CITATIONS

SEE PROFILE SEE PROFILE

Ramin Maleki
Iranian Academic Center for Education, Culture and Research (ACECR), Urmia, Iran
65 PUBLICATIONS 1,134 CITATIONS

SEE PROFILE

All content following this page was uploaded by Mir Ali Farajzadeh on 18 November 2014.

The user has requested enhancement of the downloaded file.

Microchim Acta 153, 73–78 (2006)
DOI 10.1007/s00604-005-0429-1

Original Paper
HPLC and GC Methods for Determination of Lubricants
and Their Evaluation in Analysis of Real Samples of Polyethylene

Mir Ali Farajzadeh1;
, Mortaza Ebrahimi2 , Ali Ranji3 , Elham Feyz4 ,

Vali Bejani1 , and Amir Abbas Matin5
1
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
2
Polymer Engineering Department, Amir Kabir University of Technology, P. O. Box 15875-4413, Tehran, Iran
3
National Petrochemical Company (NPC), Research and Technology Company, Mollasadra, 14358, Tehran, Iran
4
Department of Chemistry, Faculty of Science, Tehran University, Tehran, Iran
5
Chemical and Food Analysis Laboratory, Jahade Daneshgahi, Urmia University, Urmia, Iran

Received May 2, 2005; accepted September 8, 2005; published online November 21, 2005
# Springer-Verlag 2005

Abstract. High performance liquid chromatography
(HPLC) and gas chromatography (GC) are introduced
for analysis of polymer lubricants (stearamide, ole-
amide and erucamide). In the HPLC method, a reverse
phase octadecylsilane (ODS) column along with
acetonitrile=methanol (60:40) as a mobile phase were
used. Detection of analytes was performed by a UV
detector at 202 nm. The analysis time was less than
8 min. In the GC method, polar capillary column and
flame ionization detector (FID) were used for sepa-
rations and detection, respectively. The analysis time
by GC was longer than HPLC and was about 30 min.
Limits of detection, linear range and repeatability of
both methods are similar, but determination of ole-
amide in real samples by HPLC method is difficult
due to complexity of the initial part of HPLC chroma-
togram in polyethylene samples. That problem is not
observed in the GC method. Detection limits in both
methods for all analytes are lower than 0.003% which
are much lower than the amount of lubricants in com-
mercial polymers (0.05–0.2%).

Author for correspondence. E-mail: farajzade@yahoo.com
Key words: GC; HPLC; lubricants; stearamide; oleamide; eru-
camide; polyethylene.
Lubricants are substances that when compounded in a
small quantity into a polymer, will provide a signifi-
cant increase in the movement of polymer chains or
segments without notable influence in other observ-
able properties [1]. Essentially, lubricants are added to
polymers to increase the overall rate of processing or
to improve surface release properties during extrusion,
injection molding, compression molding, etc. [2]. The
factors which will be considered during the selection
of lubricants are: compatibility with the host polymer,
no adverse effect on other physical properties, easy
introduction, no retarding effect on the gelation process,
no reduction in melt strength and extensibility, good
transparency, improved plate-out performance and
cost [3]. According to the lubricant action, they may
be divided into two basic groups based on function,
external and internal lubricants [4]. A main function of
lubricants is to prevent polymers that have a tendency
toward tackiness from sticking to metallic parts of pro-
cessing machinery. This is termed external lubrication.
Another important function is to provide lubrication to
the polymer under processing to improve the free flow
74
of the melt bulk polymer by reducing friction between
chain segments; this is termed internal lubrication.
Lubricants that were analyzed in this study are stea-
ramide, oleamide and erucamide. These compounds
are used into polymers as slip agents too. Slip agents
like lubricants are added to polyethylene films during
the extrusion process to decrease friction – both film-
to-film friction and that between the film and the pro-
duction equipment – in order to increase the output of
the line and to improve packaging line operations. The
slip effect is measured as COF (coefficient of friction).
Decreased COF is a result of the migration of slip
additive to the film surface due to the defined in-
compatibility of the slip additive with the polymer.
The migration speed of slip agent to the surface is
largely decided by the additive’s chain length (com-
patibility with the polymer) and the crystallinity of the
polymer. The larger the slip agent (more carbon
atoms) the more compatible it is with the polymer
and the slower it migrates. So oleamides migrate fas-
ter than erucamides.
The level of lubricants (slip agent) used in the poly-
mer is rather low. Normally, the concentration is
between one tenth of 1% to several percent depending
on the type of polymers and the processing conditions.
The direct analysis of lubricants in the polymer by
spectroscopic or thermal techniques is difficult be-
cause of low concentration and interference of the
parent polymer matrix. However, there is a technique
that may be applied to simplify this lubricant analysis
task. Pyrolysis-gas chromatography (PY-GC) [5] is an
important technique for polymer as well as large
molecule analysis. But this technique (PY-GC) uses
specific apparatus at high temperature. In general anal-
ysis of additives in polymers is important [6–12] due
to wide application of poly ethylene (PE) and poly
propylene (PP) films in packaging of food products
and direct dependence of studied compounds with
human health and effect of residual additives on me-
chanical properties of polymers. High performance
liquid chromatography [13–22], gas chromatography
[23–27], supercritical fluid chromatography [22, 28,
29] and spectrometric methods [30] were applied for
this purpose.
In this study, two chromatographic methods intro-
duced for lubricants analysis. First, lubricants are sep-
arated from polymer matrix by dissolving polymer in
boiling xylene and then precipitation of polymer by
adding methanol. Due to low concentration of lubri-
cants, preconcentration was performed by evaporation
M. A. Farajzadeh et al.
of filtrate into rotary and the residue was dissolved in
2 mL methanol. Finally, the lubricant content of this
solution was analyzed by GC and HPLC methods.
Experimental
Materials
Polyethylene in granule or sheet forms and standard polymer having
the known amount of analytes were obtained from Tabriz Petro-
chemical Company (Tabriz, Iran) and Petrochemical Research and
Technology Company (Tehran- Iran). Slip agents such as stea-
ramide, oleamide and erucamide were obtained from Ciba Geigy
Company (Basel, Switzerland). Other chemicals such as solvents
(xylene, methanol and acetone) purchesed from E. Merck Company
(Darmstadt, Germany). Filter paper was No. 42 from Whatman
Company.
Standards Solution
0.1 g from each slip agents is accurately weighed and dissolved in
100 mL methanol. 1 mL ¼ 1 mg.
Extraction of Analyte from Polymer
Polyethylene in granule or sheet forms (about 2 g) was accurately
weighed and dissolved in 50 mL xylene by heating on hot plate.
After completely dissolving polymer sample, 100 mL of pure meth-
anol was added to it, thereby polymer matrix was precipitated. Then
the precipitated polymer was filtered and the filtrate was completely
evaporated at 90  C into rotary. The residue was dissolved in 2 mL
pure methanol and was analyzed by HPLC and GC techniques.
GC Apparatus
Gas chromatograph STG model GC 101B equipped with a flame
ionization detector (FID) was used. Injection port system was a
spilt=splitless injector. Characteristics of capillary column and GC
conditions used in this analysis, were as follows: column length,
30 m; i.d. of column, 0.25 mm coated with CARBOWAX 20 M;
thickness of stationary phase, 0.5 mm (Macherery Nagel, Germany);
flow-rate of nitrogen as carrier gas, 30 cm s1 in 150  C; flow-rate
of nitrogen as make up gas, 35 mL min1 ; flow-rate of air and
hydrogen for FID flame, 300 and 35 mL min1 , respectively; tem-
perature of injection port and detector, 250  C and temperature
programming, 150  C for 3 min and then programmed to 220  C
with 30  C min1 and held in 220  C for 30 min.
HPLC System
The chromatographic system consisted of a PUNP K-1000
KNAUER (Germany), an UV detector Well Chrom K-2500 operated
at 202 nm, a degasser Well Chrom 4 channel K-5004, a interface
Well Chrom BOX, a software Eruo Chrom 2000 and a Rheodyne
7125 injection valve. The column used in HPLC technique was a re-
verse phase C18 Nova Pak column (150 3.9 mm i.d.) from Waters
Company (USA). Particle size of stationary phase was 5 mm. Mobile
phase was a mixture of acetonitrile : methanol (60:40, V=V) at
0.5 mL min1 flow rate and injection volume of sample 20 mL. Se-
parations carried out at 25  3  C.
HPLC and GC Methods for Determination of Lubricants in Polyethylene 75

Results and Discussion

In this study, gas chromatography and high perfor-
mance liquid chromatography methods were proposed
for the analysis of lubricants such as stearamide,
oleamide and erucamide. Light density polyethylene
(LDPE) polymers were used as real samples and lu-
bricants content of them were evaluated. The main
advantage of HPLC method in comparison with GC
was the shorter analysis time. Analytes separation was
carried out in less than 8 min. But analysis time of GC
method was longer, about 30 min.

Analytes Absorption
As it is expected, lubricants that were analyzed in this
study are transparent in most wavelengths of UV-
visible region and do not absorb radiation at wave-
lengths longer than 210 nm. Lubricants are transparent
due to lack of a suitable chromophore in their struc-
tures. Absorptive spectra of analytes (1500 mg L1 in
methanol) were plotted in Fig. 1. From this figure is Fig. 2. HPLC chromatograms of (a) standard solution of lubricants
(4000 ppm) and (b) blank. Stationary phase, NOVA Pak C18;
concluded that the wavelength about 202 nm is a suit-
column length, 150 mm; column i.d., 3.9 mm, mobile phase, ace-
able one for this analysis by HPLC. tonitril: methanol (60:40, v=v); flow-rate of mobile phase,
0.5 mL min1 ; detection wavelength, 202 nm and injection sample
volume, 10 mL
Analysis of Lubricants by HPLC
and GC Methods
Figures 2 and 3 consists of HPLC and GC chromato-
grams of analytes, respectively. Fig. 2 obtained from
the standard solution of lubricants in the concentration
4000 mg L1 of each analyte injected to HPLC system
with an analysis time shorter than 8 min. This Fig.
indicates that HPLC method is a high efficient method
in separation of analytes. In this experiment, analytes
are separated based on their polarity. HPLC chroma-

Fig. 3. GC chromatogram of blank and standard solution of lubri-

cants. Injection volume is 2 mL and each analytes concentration of
standard solution is 1500 mg L1 . Stationary phase, PERMABOND
Fig. 1. Absorptive spectra of analytes in methanol as solvent in CW, 20 M; column length, 30 m; column i.d., 0.2 mm; stationary
concentration of 1500 mg L1 . Erucamide; phase thickness, 0.25 mm; carrier gas, nitrogen; detector, flame ioni-
Stearamide; Oleamide zation detector (FID)
76 M. A. Farajzadeh et al.

togram of the analytes show that the peaks of ole-

amide and stearamide are baseline separated although
the carbon number of them is equal. Due to double
bond in the oleamide structure, the polarity of olea-
mide is further than the stearamide and due to this
factor, oleamide leaves the column sooner than the
stearamide.
GC chromatograms of blank and standard solution
of analytes in the concentration of 1500 mg L1 are
shown in Fig. 3. Blank chromatogram has only one
peak (solvent peak). The chromatogram of standard
solution has three peaks related to the analytes. As can
be seen from the GC chromatogram of standard solu-
tion and its comparison with HPLC chromatogram Fig. 4. HPLC chromatogram of commercial polyethylene (sample
indicated that the order of stearamide and oleamide 11) consists of oleamide 226 ppm obtained by GC-FID. Extraction
peaks is reversed. Due to using a polar capillary col- method is performed on the commercial polyethylene sample and
10 mL of the extract was injected to the HPLC system
umn in GC (Carbowax), oleamide retention time is
longer than of stearamide owing to presence of double
bond in the oleamide structure. It is mentioned that
the non-polar column (Optima-17) and semi-polar
column (Optima-1) were also tested for separation of
lubricants by GC method. Since on those columns,
retention times of the analytes were longer due to
strong interaction of lubricants with stationary phase
of them consequently those are not suitable for the
separation of interest lubricants by GC method. It
appears to HPLC method is better than GC method
due to shorter analysis time, but unfortunately when
we are dealing with real samples (polyethylene poly-
mers), the initial part of HPLC chromatogram is com-
plex and having many peaks that overlap with the
oleamide peak especially in low concentrations. This
overlapping is shown in HPLC chromatogram of real
sample containing oleamide (Fig. 4). As is seen from
the HPLC chromatogram, oleamide peak is appeared
as a shoulder and determination of area and height of
peak is faced with serious difficulties particularly in
low concentrations. While GC method has a relatively
longer analysis time, but it does not encounter such Fig. 5. GC chromatogram of polyethylene samples having the stud-
ied lubricants. Extraction method is performed on the commercial
difficulties. In Fig. 5 three GC chromatograms related polymer samples and 2 mL of the extract was injected to the GC
to three polymer samples are shown which indicate system

Table 1. Analytical characteristics of gas chromatographic method

Compound Calibration curve Detection limit Linearity RSD Linear range
equation (r) (%) (mg L1 )
In solution In polymer
(mg L1 ) (%)
Stearamide A ¼ 1512C  23917 10 0.0010 0.998 2.11 30–1500
Oleamide A ¼ 3704C  68280 15 0.0015 0.999 0.68 40–1500
Erucamide A ¼ 2870C þ 24511 8 0.0008 0.999 6.55 20–1500
HPLC and GC Methods for Determination of Lubricants in Polyethylene 77

Table 2. Analytical characteristics of high performance liquid chromatographic method

Compound Calibration curve Detection limit Linearity RSD Linear range
equation (r) (%) (mg L1 )
In solution In polymer
(mg L1 ) (%)
Oleamide A ¼ 0.0481C þ 12.708 20 0.0020 0.997 1.91 50–4000
Stearamide A ¼ 0.0396C þ 20.636 15 0.0015 0.999 5.49 40–4000
Erucamide A ¼ 0.0345C þ 15.345 30 0.0030 0.999 0.86 80–4000

that each sample having one of the studied lubricants.
In these chromatograms, analytes peaks are well sepa-
rated and no interferences peaks observed.
Analytical Characterizations of GC
and HPLC Methods
Calibration curve equations, limit of detections, corre-
lation coefficients, relative standard deviations (RSD%)
and linear ranges are shown in Tables 1 and 2 for GC
and HPLC methods, respectively. Characteristics of
both methods are approximately similar and one meth-
od has not preference relative to another method. While
limits of detection of GC method are better than HPLC
method, but the linear ranges of HPLC method are
better than GC method. In both methods, a good linear
correlation is obtained between peak area and concen-
tration of analyte (r>0.997).
Reliability of GC and HPLC methods was evaluated
by performing five repeated experiments on the stan-
dard solution having concentration of 1500 mg L1 and
1000 mg L1 (relative to each analytes) in GC and
HPLC methods, respectively. Bias from the actual
values was measured for the obtained results. Since
the bias of obtained results from the actual concentra-
tions are less than 7.5% for all analytes, therefore, both
methods can be classified as accurate methods. The rel-
ative standard deviation (RSD%) is less than 4.5% and
4.3% for GC and HPLC methods, respectively. These
show that the repeatability of both methods is good.

Table 3. Stearamide, oleamide and erucamide percent in the standard and commercial polymers obtained by GC and HPLC methods and
their bias (%) from the actual percent or each other
Polymer Concentration (ppm) obtained by Bias (%)
HPLC GC HPLC GC
Standard polymer 1 452 482 9.60a 3.60a
(Stearamide 500 ppm)
Standard polymer 2 1664 1498 þ10.93 0.13
(Oleamide 1500 ppm)
Standard polymer 3 1016 1079 þ1.60 þ7.90
(Erucamide 1000 ppm)
Commercial polymer
1 1155 (Stearamide) 1244 (Stearamide) þ7.71b
704 (Oleamide) 858 (Oleamide) þ21.9
2 X (Oleamide) 732 (Oleamide) –
3 516 (Erucamide) 530 (Erucamide) þ2.71
4 465 (Erucamide) 504 (Erucamide) þ8.39
5 X (Oleamide) 509 (Oleamide) –
277 (Erucamide) 343 (Erucamide) 23.8
6 1587 (Erucamide) 1448 (Erucamide) þ8:76
7 1625 (Erucamide) 1485 (Erucamide) þ8.61
8 114 (Oleamide) 111 (Oleamide) þ2.63
9 X (Oleamide) 91 (Oleamide) –
10 X (Oleamide) 175 (Oleamide) –
11 549 (Stearamide) 504 (Stearamide) þ8.20
X (Oleamide) 226 (Oleamide) –
12 507 (Erucamide) 562 (Erucamide) 10.8
a
Bias from the actual value.
b
Bias obtain for GC results from HPLC results.
 78 HPLC and GC Methods for Determination of Lubricants in Polyethylene
Evaluation of Proposed Methods for Analysis
of Standard Polymer and Commercial
Polymer Samples
In this work, three standard polymers and 12 com-
mercial polymers were analyzed for the determina-
tion of stearamide, oleamide and erucamide content.
Concentration of stearamide, oleamide and eruc-
amide in standard polymers were 500, 1500 and
1000 ppm, respectively. Standard and commercial
polymers were analyzed with GC and HPLC meth-
ods and the obtained results are shown in Table 3.
The results obtained for standard polymer hav-
ing 500 ppm of stearamide are 452 and 482 ppm
by GC and HPLC methods, respectively. Results
of standard polymer having oleamide 1500 ppm
are 1664 and 1498 ppm by HPLC and GC methods,
respectively. Erucamide concentration in standard
polymer (1000 ppm) was obtained 1016 and 1079 ppm
by GC and HPLC methods, respectively. The devia-
tion values of obtained results from the actual values
(in standard polymers) and from each other (in
commercial polymers) are shown in Table 3. Devia-
tions of obtained results from the actual values are
less than 11% in all standard polymer samples indi-
cate that both methods are accurate. Also, a good
agreement between two groups of results (GC and
HPLC) obtained from the measurments performed
on the commercial polymers are observed. As men-
tioned earlier, the oleamide peak in HPLC chro-
matogram is overlapped with peaks of unknown
compounds in some polymer samples and integra-
tion of the interest peak is difficult, especially in
low concentrations.
Conclusions
In this study, two chromatographic techniques (GC
and HPLC) are described for the analysis of lubri-
cants. Stearamide, oleamide and erucamide were
separated by GC and HPLC columns without per-
forming derivativation reaction and detected with
universal detectors, FID and UV detector, respec-
tively. For the extraction of these lubricants from
polymer samples, the dissolution-precipitation pro-
cedure was performed. The obtained results from
GC and HPLC methods performed on the standard
and real samples were in agreement with the actual
values or together.
View publication stats
References
[1] Lutz J T (1989) Thermoplastic polymer additives. Marcel
Dekker, New York, p 282
[2] Stepek J, Daoust H (1983) Additives for plastics. Springer
Berlin Heidelberg New York Tokyo, p 23
[3] Murphy J (1996) The additives for plastics handbook. Elsevier
Advanced Technology, Oxford, p 240
[4] Riedel T (1993) Plastics additives, 4th ed. In: Gachter R,
Muller H (eds) Hanser=Gardner, Cincinnati, OH, p 424
[5] Wampler T P (1995) Analytical Pyrolysis Handbook. In:
Wampler T P (ed) Marcel Dekker, New York, p 1
[6] Forrest M F (2002) Analysis of plastics, Rapra review report
No. 149. Rapra Technology Ltd, Shawbury
[7] Crompton T R (1998) Manual of plastics analysis. Plenum
Press, New York
[8] Crompton T R (1993) Practical polymer analysis. Plenum
Press, New York
[9] Crompton T R (1989) Analysis of polymers. An introduction.
Pergamon Press, Oxford
[10] Mitchell J (ed) (1987) Applied polymer analysis and char-
acterization: recent developments in techniques, instrumenta-
tion, problem solving. Hanser Publishers, Munich
[11] Krause A, Lange A, Ezrin M (1983) Plastics analysis guide –
chemical and instrumental methods. Hanser Verlag, Munich
[12] Johnson W, Keck-Antoine K, Lee R E, Callierotti C (2001)
Plast Addit Compd 3: 14
[13] D-6042 Standard test method for determination of phenolic
antioxidants and erucamide slip additives in polypropylene
homopolymer formulation using liquid chromatography.
American standards for testing materials
[14] D-5815 Standard test method for determination of pheno-
lic antioxidants and erucamide slip additives in linear low
density polyethylene formulation using liquid chromatograph.
American standards for testing materials
[15] D-1996 Standard test method for determination of pheno-
lic antioxidants and erucamide slip additives in low den-
sity polyethylene formulation using liquid chromatography.
American standards for testing materials
[16] Carpenter T, Poore D D, Gee A J, Deshpande P, Merkler D J,
Johnson M E (2004) J Chromatogr B 809: 15
[17] Jasperse J L (1988) J Am Oil Chem Soc 65: 1804
[18] Nakagawa T, Vermeer J H, Dean J R (1971) J Chromatogr Sci
9: 293
[19] Jenke D, Poss M, Stoty J, Odufu A, Zietflow D, Tsilipetros T
(2004) J Chromatogr Sci 42: 388
[20] Jenke D (2003) J Liq Chromatogr Relat Technol 26: 2417
[21] Schaefer A, Kuechler T, Simat T J, Steinhart H (2003)
J Chromatogr A 1017: 107
[22] Sandra P, David F (1990) J High Resolut Chromatogr 13: 414
[23] Hanus L O, Fales H M, Spande T F, Basile A S (1999) J Anal
Biochem 270: 159
[24] Frisina G, Busi P, Serini F (1979) J Chromatogr 173: 190
[25] Gee A J, Groen L M, Johnson M E (1999) J Chromatogr 849: 541
[26] Gee A J, Groen L M, Johnson M E (2000) J Mass Spectrom 35:
305
[27] Metcalfe L D (1975) J Chromatogr Sci 13: 516
[28] Doehl J, Farbrot A, Greibrokk T, Iversen B (1987) J Chro-
matogr A 392: 175
[29] Smith S H (1998) Extraction of additives from polystyrene and
subsequent analysis. MS Thesis, Polytechnic Institute and
State University
[30] Sankhe S Y, Hirt D E (2003) Appl Spectrosc 57: 37