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HPLC technique for quantitation of Chimassorb 944, and its evaluation in

analysis of real and standard samples of polyolefins

Article  in  Microchimica Acta · July 2007

DOI: 10.1007/s00604-007-0744-9

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Microchim Acta (2007) 159: 363–369
DOI 10.1007/s00604-007-0744-9
Printed in The Netherlands

Original Paper
HPLC technique for quantitation of Chimassorb 944, and its evaluation
in analysis of real and standard samples of polyolefins

Mir Ali Farajzadeh1;
, Shirin Ghochi Eskandar1, Ali Ranji2 , and Elham Feyz2
1
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
2
National Petrochemical Company (NPC), Research and Technology Company, Mollasadra, 14358 Tehran, Iran

Received October 14, 2006; accepted January 26, 2007; published online April 2, 2007
# Springer-Verlag 2007

Abstract. A high performance liquid chromatogra-
phy (HPLC) method is presented for the determi-
nation of Chimassorb 944 in polymeric matrix. A
reversed phase column octadecyl silane (ODS) is used
as a stationary phase. As a mobile phase, a mixture of
THF:methanol:triethanol amine (90:10:1.5) (v:v:w) is
used. The HPLC system was equipped with an UV
detector and the absorbance of the analyte was re-
corded at 240 nm. In the case of polymers, 0.5 g of
them along with 100 mg Irganox 1010 (for preventing
oxidation of Chimassorb 944) were dissolved in boil-
ing xylene, and then extracted with sulfuric acid 1 M
four times. The extract was neutralized with sodium
hydroxide solution and the analyte was re-extracted
into carbon tetrachloride and then injected to the
HPLC system. This method is an accurate and rela-
tively fast technique for determination of Chimassorb
944 in polymers.
Key words: HPLC; polymer; additive; Chimassorb 944.
Additives in polymers are used to protect polymers
from degradation during processing or outdoor expo-
sure as a result of reaction with, e.g. oxygen or UV
light. There are several classes of additives, each with
their own specific properties [1]. Important classes of

Author for correspondence. E-mail: farajzade@yahoo.com
additives that protect polymers from UV radiation are
the so-called hindered-amine light stabilizers (HALS).
These additives are used for their radical scavenger
ability. Some of these HALS additives have a poly-
meric structure. Due to their high molecular weight,
these additives have the advantage of limited mobility
in polymers and therefore loss of additive during pro-
cessing or use is negligible. HALS additives are used
in various amounts, depending on the type of polymer.
For example, in polyolefins like LDPE or PP the
amount of HALS additives may be as high as 3 wt.%
while in thermoplastics the amount of HALS rarely
exceeds 0.5 wt.% [2].
As a result of their complex chemical structure, the
analysis of HALS additives is not straightforward and,
probably, did not receive as much attention as other
classes of polymer additives, e.g. antioxidants and,
plasticizers. One of the first techniques used to study
HALS additives in polymers, was the application of
pyrolysis coupled to gas chromatography (Py-GC).
Due to their polymeric structure, pyrolysis of these
additives results in smaller degradation products that
can be analyzed with gas chromatography. Some ear-
lier studies have shown the capability of Py-GC to
quantify HALS additives in polymers [3–5]. How-
ever, these authors did not have a specific detection
method, e.g. mass spectrometry, in order to identify
HALS additives unambiguously. Furthermore, prior
364
to analysis the HALS additives were extracted from
the polymer, instead of direct analysis of the polymer
sample containing the HALS additives. However, sim-
ple and quick sample preparation is actually one of the
major advantages of the use of Py-GC for the analysis
of additives in polymers. Other techniques that have
been used to analyze HALS additives are UV-spectros-
copy and NMR but these techniques are not able to
differentiate between different HALS additives. Wang
have already shown that pyrolysis GC-MS is able to
identify various classes of additives using character-
istic peaks and masses that discriminate between the
various additives [6]. Montaudo showed some prom-
ising results for HALS additives using pyrolysis
GC-MS [7]. Interestingly, no report of a successful
analysis of Chimassorb 944 with liquid chromatogra-
phy has been made so far. Some attempts have been
made, but the polymeric structure and the presence of
secondary amine-groups are thought to be the major
cause of the lack of liquid chromatography methods
for it [8]. A HPLC method with both ultraviolet (UV)
and evaporative light scattering detection (ELSD) is
developed to quantify the other HALS additives in
extracts of polymers. Although high performance
liquid chromatography (HPLC) is a very good method
for separation of complex additives, there are some
difficulties in identification of some components [9].
Recently, liquid chromatography=chemical ionization
mass spectrometry was applied to the analysis of anti-
oxidants and UV stabilizers in polymers. Because of
the long extraction times, several spectroscopic meth-
ods have been employed for the in situ determination
of polymer additives [10, 11]. The UV determination
of antioxidants in hot-pressed polyethylene films has
been described [10]. Similarly, IR and phosphores-
cence analyses [11] of antioxidants using double-
beam spectrophotometers with some pure polymer
film in the reference beam have been reported. The
main disadvantage of the spectroscopic techniques is a
lack of specificity.
In this study, an isocratic liquid chromatographic
method was presented and tested for quantifica-
tion of Chimassorb 944 in standard and real samples.
Standard solution of Chimassorb 944 was prepared in
carbon tetrachloride and injected to HPLC as a
separation system. In the case of polymer as a real
sample, 0.5 g of it along with Irganox 1010 (for pre-
vention of degradation and oxidation of Chimassorb
944 during extraction) was weighted and dissolved in
boiling xylene. This solution was transferred into a
M. A. Farajzadeh et al.
separatory funnel and after cooling it was extracted
with sulfuric acid solution four times. All of the aque-
ous phases were collected and neutralized with
sodium hydroxide. This solution was again extracted
with carbon tetrachloride two times and 20 mL of the
extract was injected to HPLC equipped with an UV
detector.
Experimental
Apparatus
The chromatographic system consisted of HPLC 1100 series
(Agilent Technologies, USA) equipped to a quaternary pump,
degasser and UV detector. The software Chemstation 2D was used
in data processing.
Chromatographic separation
A 25 cm  4.6 mm I.D., particle size of stationary phase 5 mm
reversed phase column (ZORBAX Eclipse XDB-C18) was used.
A mixture of 90% tetrahydroforan (THF), 10% methanol and
1.5% triethanol amine was used as a mobile phase. Analyses
were run in an isocratic mode and at a flow-rate of 1 mL  min1
using an injection volume of 20 mL. Separation was carried out at
25  3  C.
Materials and solutions
Polyethylene in granule or sheet forms and standard polymers
having the known amount of analyte were obtained from Tabriz
Petrochemical Co. (http:==www.nipc.net) (Tabriz, Iran) and Petro-
chemical Research and Technology Company (Tehran, Iran).
Chimassorb 944 and Irganox 1010 (as an antioxidant) were obtained
from Ciba Specialty Chemicals Company (http:==www.cibasc.com)
(Basel, Switzerland). Other chemicals such as solvents (xylene and
carbon tetrachloride), sulfuric acid and sodium hydroxide were ana-
lytical grade and purchased from E. Merck Company (http:==
chemdat.merck.de) (Darmstadt, Germany).
Standard solutions of Chimassorb 944 were prepared in carbon
tetrachloride for preparation of calibration curve in the range of 50–
10,000 mg  L1 . The solution of analyte in xylene or methanol was
used for optimization of extraction procedure. Due to easily oxida-
tion of Chimassorb 944 and especially its adsorption on the glass-
ware, analyte solution was prepared daily.
The preparation of synthetic samples
0.5 g polymer samples without any additives (blank polymer)
were weighted and 100 mg of Irganox 1010 was added to them.
To these mixtures, 0.5, 1 and 2 mL solution of Chimassorb 944
(400 mg  L1 ) in methanol was added. In the case of study of
Irganox 1010 amount, Chimassorb 944 was added at a constant
concentration (2 mL solution of 800 mg  L1 ) in the presence of
5–100 mg Irganox 1010. After evaporation of methanol, the mix-
tures were melted in an oven at 170–200  C. The melted polymers
were dissolved in 20 mL boiling xylene and transferred into separa-
tory funnels. After cooling, extraction procedure was performed
with sulfuric acid 1 M.
HPLC determination of Chimassorb 944 in polyolefins
Extraction of analyte from polymer
0.5 g of polyethylene in granule or sheet forms along with 100 mg
Irganox 1010 were accurately weighted and dissolved in 20 mL
xylene by heating on hot plate. After completely dissolving polymer
sample, solution was transferred into a separatory funnel. After
cooling, 10 mL sulfuric acid 1 M was added to it and shacked for
a short time. The aqueous phase was collected and 10 mL of fresh
sulfuric acid (1 M) was again added to upper phase. After extraction,
this aqueous phase was added on the previously collected aqueous
phase. Extraction was overall repeated four times. All of aqueous
phases were collected and neutralized with sodium hydroxide 4 M.
The obtained solution was re-extracted two times and each time with
2 mL carbon tetrachloride. Finally, 20 mL of the extract was injected
to HPLC and eluate was monitored at 240 nm.
Results and discussion
In this study, a high performance liquid chromatogra-
phy (HPLC) technique was proposed for analysis of
Chimassorb 944. Low density polyethylene (LDPE)
and polypropylene (PP) were used as real samples.
Separation was performed in less than 8 min using
isocratic elution. Some effective parameters such as
extracting solvent kind, concentration of sulfuric acid,
amount of Irganox 1010 and times of extraction were
optimized.
Analyte absorption
To select the wavelength in which detection of analyte
in HPLC experiment can be performed, solution of
Chimassorb 944 (1000 mg  L1 ) was prepared in the
mixture having the same composition of mobile phase
THF:methanol:triethanol amine (90:10:1.5). Twenty
microlitre of this solution was injected to HPLC and
eluate was detected at different wavelengths (230–
250 nm). From the obtained results 240 nm was se-
lected as the optimum wavelength.
Optimization of the extraction procedure
Selection of extracting solvent
Chimassorb 944 is a hindered amine light stabilizer
and its chemical structure (Scheme 1) contains amino
Scheme 1. Chemical structure of Chimassorb 944 (Poly-{6- [1,1,3,3-
tetramethylbutyl]-amino]-1,3,5-triazine-2,4-diyl}{2-(2,2,6,6-tetra-
methylpiperidyl)-amine}
365
groups, which can be protonized at lower pHs. Then
this additive is extractable with inorganic acids. On
the other hand, most additives used in polymers do
not have protonizable groups. This extraction method
seems to be selective for Chimassorb 944. To select
the suitable acid for extraction, different acids such
as nitric, perchloric, phosphoric, acetic, sulfuric and
hydrochloric acids were tested. From the obtained
results sulfuric acid was selected as extracting solvent.
Nitric and perchloric acids are oxidizing acids and
they (especially nitric acid) oxidized analyte. On the
other hand, acetic acid is a relatively weak acid and
can not protonate analyte for extraction. The other
acids tested had almost similar results with a rela-
tively preference in the case of sulfuric acid.
Effect of sulfuric acid concentration
on the analyte extraction
Ten millilitre solution of Chimassorb 944 in xylene
(20 mg  L1 ) was transferred into a separatory funnel
and extracted with 10 mL of sulfuric acid solutions
with different concentrations (0.05–5 M). As seen
from data in Fig. 1, no significant variation in peak
area was observed at different concentrations of sul-
furic acid. But in the absence of H2SO4, extraction of
the analyte is not feasible. However, sulfuric acid 1 M
was selected as an extractant. It is mentioned that
in some polymers Chimassorb 944 is used at a very
high concentration (till 4000 ppm). Therefore, in these
cases the concentration of sulfuric acid must be high
to protonate all analyte molecules.
Fig. 1. Effect of sulfuric acid concentration on the extraction
efficiency
366 M. A. Farajzadeh et al.

Table 1. Optimization of times of extraction Table 2. Optimization of volume of CCl4 in the extraction of
Chimassorb 944 from alkaline solution. The extraction performed
Conc. of Recovery (%) of on the 40 mL solution of Chimassorb 944 (1000 mg  L1 ) in sulfuric
Chimassorb acid 1 M
944 (ppm) 1st 1st þ 2nd 1st þ 2nd 1st þ 2nd
in polymer extraction extractions þ 3rd þ 3rd þ 4th Volume of Recovery (%) of Concentration
extractions extractions CCl 4 (mL) factor
1st 1st þ 2nd
400 5.60 31.7 96.2 104.1 extraction extractions
800 26.3 51.7 64.1 97.2
1600 54.7 80.6 91.4 103.7 1 75.3 87.2 20
2 85.4 99.3 10
5 92.8 102.4 8

Optimization of extraction times by sulfuric acid

To obtain the optimum times of extraction, 0.5 g of
standard polymer samples were dissolved in xylene on
heating and transferred into separatory funnels. After
cooling, the analyte was extracted with sulfuric acid
1 M. From Table 1, it can be seen with four times of
extraction the recoveries reached to nearly 100%, in
three concentration levels tested. It is mentioned that
the selected concentrations belong to 400, 800 and
1600 ppm in polymer.
Optimization of CCl4 volume
To obtain the optimum volume of carbon tetrachlor-
ide for preconcentration of sample before its injec-
tion to HPLC, 40 mL solution of Chimassorb 944
(1000 mg  L1 ) in H2SO4 (1 M) was neutralized by
adding 12 mL 4 M sodium hydroxide solution, and
then Chimassorb 944 was extracted with the different
volumes of carbon tetrachloride for two times. After
each extraction, the bottom phase was collected and
20 mL of it injected to HPLC system. From the ob-
tained results in Table 2, volume of 2 mL was selected
for extraction due to reasonable extraction recovery
and concentration factor.
Optimization of Irganox 1010 amount
Irganox 1010 was added to the samples and standard
solutions to prevent of degradation and oxidation of
Chimassorb 944 during extraction. To obtain the opti-
mum level of Irganox 1010, 0.5 g of standard polymer
samples having 5–100 mg Irganox 1010 were used.
The extraction procedure was performed on them
and evaluation of Irganox 1010 effect was carried out
by injection of extract to HPLC. In the absence of
Irganox 1010 more than 25% of Chimassorb 944
was decomposed in extraction procedure in compared
with direct injection of analyte to HPLC system. Irga-
nox 1010 reduced Chimassorb 944 decomposition to
less than 20% at an amount of 5 mg, but it almost

Fig. 2. HPLC chromatograms for Chimassorb

944 solutions in different concentrations
HPLC determination of Chimassorb 944 in polyolefins
Fig. 3. Chromatograms of a blank polymer (a), a commercial
polymer (b) and a standard polymer (Chimassorb 944 concentra-
tion 1500 mg  L1 ) (c)
completely prevents decomposition of Chimassorb
944 at 100 mg level.
HPLC chromatograms
Figure 2 shows HPLC chromatograms of Chimassorb
944 solutions (100–4000 mg  L1 ) in carbon tetra-
chloride. HPLC chromatograms of a blank polymer, a
standard polymer contains 1500 mg  L1 of Chimassorb
944 and a commercial polymer was given in Fig. 3.
No peak was detected in the case of commercial
polymer after extraction in the retention time range of
analyte, which indicate that other additives incorpo-
rated to the commercial polymers do not interfere in
the analysis of Chimassorb 944 with the presented
method (see also next section).
Table 3. Quantitative characteristics of the proposed method
Calibration curve equation r2 LOD (mg  L1 )
a b
A ¼ 0.5135C þ 143.21 0.9913 15
a
A and C are peak area and concentration (mg  L1 ), respectively.
b
S=N ¼ 3.
c
Obtained from six repeated experiments (C ¼ 3000 mg  L1 ).
d
Performed in three different days (C ¼ 3000 mg  L1 ).
367
Analytical characteristics of the proposed method
Calibration curve equation, limit of detection (LOD),
linear dynamic range (LDR), square of correlation co-
efficient (r2) and relative standard deviation (RSD%)
of the HPLC technique are shown in Table 3. The
proposed method has an extent linear dynamic range
(50–10,000 mg  L1 ), which completely covers the
concentration range of analyte in polymers (500–
2000 ppm). Also, relative standard deviation (RSD%)
for between runs (repeatability) and between days
(reproducibility) are 1.30 and 2.08%, respectively,
which indicated that the proposed method is repeatable.
Recovery study
For the evaluation of recovery in the extraction step,
0.5 g of polyethylene samples without additives along
with 100 mg of Irganox 1010 were spiked with 0.5, 1
and 2 mL solution of Chimassorb 944 (1000 mg  L1 )
in methanol. After evaporating of solvent, the mix-
tures were melted in an oven at 170–200  C. Then
the polymers were dissolved in 20 mL boiling xylene
and transferred into separatory funnels. After cooling,
the extraction procedure was performed on the sam-
ples. The obtained results show that the recoveries are
between 91 and 103%. From the data we can conclude
that quantitative recovery of analyte from polymeric
samples are attainable.
Interferences study
Some additives incorporated into polymers can be
interfered under the experimental conditions in iden-
tification and quantification of Chimassorb 944. Addi-
tives studied in this work were Tinuvin 622, Tinuvin
783, Chimassorb 2020, Irganox 1076, Irganox 1010
and Irgafos 168. To study interference effect of these
additives on the Chimassorb 944 determination, 10 mg
of them was dissolved in 10 mL mixture of 90% THF,
10% methanol and 1.5 g of triethanol amine and 20 mL
of the obtained solutions was injected to HPLC sys-
LDR (mg  L1 ) Repeatability Reproducibility
c
50–10,000 1.30 2.08d
368 M. A. Farajzadeh et al.

matogram of solution containing Chimassorb 944

and Chimassorb 2020 (each 1000 mg  L1 ). This fig-
ure shows that the proposed HPLC method can be
applied to determination of Chimassorb 944 and Chi-
massorb 2020 in a single solution in less than 20 min.

Accuracy evaluation of HPLC method

Fig. 4. HPLC chromatogram of Tinuvin 783 (1000 mg  L1 )
Fig. 5. HPLC chromatogram of solution contains Chimassorb 944
and Chimassorb 2020 (each 1000 mg  L1 )
tem followed by detection at optimum conditions.
Only serious interference was observed from Tinuvin
783 that contains 50% Chimassorb 944 and 50%
Tinuvin 622 (Fig. 4). In the cases of other additives no
peak is observed in the retention time of Chimassorb
944 and they had not interfering effect on the deter-
mination of analyte. Also Fig. 5 shows the chro-
To evaluate efficiency and accuracy of the proposed
HPLC method, this method was performed on the 8
commercial polymers produced by two Petrochemical
companies (Tabriz, Iran and Sabic, Saudi Arabia) and
on the 9 standard polymers prepared in the Petro-
chemical Research and Technology Company (Tehran,
Iran). In any of commercial polymers tested here,
Chimassorb 944 or Tinuvin 783 (a 1:1 mixture of
Tinuvin 622 and Chimassorb 944) was not detected.
However, the results obtained for standard polymers
(Table 4) having known amounts of Chimassorb 944
show that the proposed method is a suitable analysis
technique in this field. The obtained results for stan-
dard polymers by the presented HPLC method were
also compared with those obtained from spectro-
photometric method [12] in this table. The obtained
results show that two methods are comparable from
the view of accuracy and most of results have bias less
than 10% from the actual values. The commercial
polymers were tested with spectrophotometric method
and analyte was not detected in any sample, too.
Conclusion
An HPLC method was developed for the analysis of
Chimassorb 944. For extraction of this additive from
polymeric materials, 0.5 g of polymer samples along
with 100 mg of Irganox 1010 were dissolved in boiling

Table 4. Comparison of HPLC and spectrophotometric [12] methods performed on the standard polymers
Polymer no. (Chimassorb Chimassorb 944 concentration (ppm) obtained by
944 concentration, ppm)
Spectrophotometry Bias (%) HPLC Bias (%)
1 (1000) 871  98.9a 12.90 816  27.5 18.4
2 (1500) 1556  52.6 3.73 1575  92.6 5.00
3 (1500) 1530  60.7 2.00 1543  0.7 2.86
4 (1500) 1497  58.0 0.20 1511  9.8 0.73
5 (1500) 1431  27.1 4.60 1454  5.6 3.07
6 (1500) 1442  13.6 3.87 1387  10.6 7.53
7 (2000) 1918  86.9 4.10 1882  101 5.90
8 (2000) 1851  95.2 7.45 1835  17.6 8.25
9 (2000) 1995  181.6 0.25 1958  91.9 2.10
a
Mean concentration  standard deviation (n ¼ 3).
 HPLC determination of Chimassorb 944 in polyolefins
xylene. Analyte was extracted with 1 M sulfuric acid
solution four times. Aqueous phases were collected
and neutralized with sodium hydroxide. The obtained
solution was re-extracted with carbon tetrachloride two
times. Then 20 mL of extract was injected to HPLC
system. This method is simple and reliable and was
successfully applied to determine Chimassorb 944
content of commercial and standard polymers. The
proposed method has an extent linear dynamic range
and no interference effect was observed from other
additives.
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