4 PIGMENT AND RESIN TECHNOLOGY J ANUARY 1981

Appl i cat i ons of gas

chromat ography in t he
pai nt & al l i ed i ndustri es.
Raw mat eri al s: Par t 2
Ann J. Wal t on
Cashew nutshel l l i qui d
The liquid extract obtained from the natural
cashew nutshell is rich in phenolic substances which
are derived from anacardic acid C
6
H
3
(OH) (CO
2
H)
(C
15
H
31
-n), where n may have values of 0, 2, 4 or 6
and represents various degrees of unsaturation in the
aliphatic C
15
side-chain. Industrial decarboxylation of
this material affords cardanol C
6
H
4
(OH) (C
15
H
31
-n) plus
other substituted phenols and polymeric residues.
Tyman et al. (197, 198) have studied the analysis of
all these products using GC, molecular distillation,
TLC and mass spectrometry. After hydrogenation and
the formation of the corresponding methyl esters, the
products were analysed by GC using glass columns
(5ft x 3/16in) packed with acid washed and silanized
Diatomite as support material and which was coated
with non-polar stationary phases such as SE30, SE25
or APL, or semi-polar phases such as 0V17, Dexil
300 or PEGA. Alternatively, the samples were sub-
jected to an acetylation procedure prior to GC exami-
nation on columns containing Dexil 300, SE30 or
SE52. The GC equipment consisted of a Pye-Unicam
model 104 instrument operated with nitrogen carrier
gas (flow rate 45cm
3
min
-1
) and equipped with FID.
The saturated (15:0), monoene 15: 1) , diene
(15:2) and triene (15:3) constituent phenols were de-
termined by mass spectrometry following a TLC sepa-
ration, whilst both TLC and GC separations required
that correction factors were applied in order to
account for different response characteristics of the
detector system. The more highly-polymeric samples
were handled by molecular distillation techniques,
which gave fractions that were subsequently
examined by GC.
It was concluded that the bulk of cashew nut-
shell liquid was sufficiently volatile to allow GC
analysis along the lines indicated above and, since
the derivatives employed could be quantitatively pre-
pared, the GC peaks could be handled by standard
integration procedures that permitted quantitative de-
termination of the component phenols.
Resi n aci ds
The methyl esters of abietic and dehydro-
abietic acids were separated by Medyantsev et al.
(134) using a column (1.8m x 2mm dia) containing
4.2% Varnisch 3R-728 as stationary phase that opera-
ted at 125C and with helium as carrier gas at a flow
rate of 100cm
3
min
-1
. The methyl esters of laevopi-
maric, palustric and neoabietic acids, which were
obtained by isomerising abietic acid at 180 under
carbon dioxide or 200C under argon, were analysed
by Fomin et al. (155) using GC, infrared and ultra-
violet spectroscopy.
Pine rosin acids including pimaric, isopimaric,
laevopimaric, abietic and neoabietic, alongside C12
to C22 fatty acids were resolved simultaneously in a
GC procedure described by Lapshina and Kosynkova
(117). The acids were converted into their corres-
ponding methyl esters using diazomethane and sub-
sequently separated on a column packed with 5%
polyethanediolsuccinate on Chromatron N-AW-DMCS
which was operated under a temperature program-
ming schedule between 150 and 230C.
In an alternative procedure, suggested by
Mahood and Rogers (129), the fatty acids were sepa-
rated initially from the resin acids by preliminary
methylation followed by the addition of 2,2,4-tri-
methylpentane prior to extraction with 5% potassium
hydroxide solution in water, whereby the resin acids
were carried into the aqueous phase. After applying
suitable recovery techniques each of the acid samples
were subjected to treatment with diazomethane, to
ensure total methylation, followed by GC analysis on
a column containing EGSS-X on Gas Chrom P at
175C. A review dealing with the analysis of the
lower fatty acids, with up to 18 carbon atoms, by
capillary GC has been published by Krupcik et al
(114). Amongst the topics discussed were the separa-
tion of free fatty acids as opposed to the correspond-
ing methyl esters, qualitative and quantitative aspects
including the calculation of Kovats indices, plus fea-
tures of the equipment such as ovens, detectors,
stationary phases and the use of support-coated as
opposed to wall-coated open tubular columns.
Mi scel l aneous compounds
The lower primary aliphatic amines were
separated, as their corresponding fluorine-containing
Schiff bases, on a temperature-programmed GC
column containing Tenax SE-30 as stationary phase
and with an electron-capture detector, according to
Hoshika (88, 89). Residual secondary and tertiary
amines were analysed as the free bases. Amongst the
samples examined were methylamine, ethylamine, n-
and iso-butylamine, n- and iso-amylamine, dimethyl-
amine, diethylamine, di(n-propyl)amine, trimethyl-
amine and triethylamine. Zatkovetskii and Safonova
J ANUARY 1981 PIGMENT AND RESIN TECHNOLOGY 5
(210) reported the GC separation of toluene diisocy-
anate and hexamethylene diisocyanate using sintered
PTFE powder (Polychrom 1) as column packing
material. The same substances were determined in
their respective prepolymers or adducts by J anmot
(96) who used a sample solution in ethylacetate
which was injected on to a GC column containing
silicone gum rubber and operated at 150C. In the
latter procedure 1-chloronaphthalene served as inter-
nal standard.
Dimethylacetamide is present as an impurity
in concentrations below 2% in regenerated synthetic
glycerol. The former substance was determined using
a GC column (1m x 3mm i.d.) packed with 20% of a
3:1 mixture of poly(oxpyhenylene) and poly(ethylene-
glycol) supported on Chromatron N-AW-DMCS by
Sergeeva et al. (169). The column was eluted with
nitrogen as carrier gas (30cm
3
min
-1
) and operated at
135C. After the analysis the column was cleaned up
by heating it to approx. 300C.
A comprehensive list of GC retention data on
50% methyl and phenyl silicone columns, operated
under temperature programming, was published by
Mattson and Peterson (132) for the trimethylsilyl de-
rivatives of aromatic compounds such as phenols,
naphthols, alcohols, carboxylic acids, chloro-com-
pounds, aldehydes and ketones, the latter two being
analysed both as oximes and O-methyl oximes. An
interpretation of the correlation between structure and
retention behaviour was given. Alkyphenols produced
from the olefin fractions of petroleum were analysed
according to a GC method developed by Shchegol et
al. (170). The technique was applied in particular to
the analysis of p-tert-octyIphenol produced from
2,4,4- trimethylpent-l-ene. A total of 14 impurities,
which included acetone, methylacrylate, methyliso-
butyrate, ethyl methacrylate and methyl 2-hydroxy-2-
methylproprionate, were resolved in samples of
methyl methacrylate by Sokolowska et al. (181) using
a GC column packed with Ucon-LB-550X on Chromo-
sorb W that was operated at 85C.
Acetaldehyde, as a source of interference in
the quantitative GC analysis of lower levels of vinyl
chloride, was eliminated using a mixture of glass
wool and sodium bisulphate prior to the GC column
proper according to the method of Krishen and Tucker
(113). White (206) proposed the use of a column of
OV-1 on acid-washed Diatomite, that was temperature
programmed from 180 to 380C, in the identification
of waxes that were taken from museum objects. The
presence of free parent acids in cyclic anhydrides was
determined by Haas and DuBois (68). Each anhydride
sample was initially reacted with morpholine so that
the residue of free carboxylic acid could then be con-
verted into the corresponding silyl derivative using
bis(trimethylsilyl)acetamide reagent. The sample so
obtained was analysed by GC on a column of 5%
SE52 on Gas Chrom Q under temperature programme
control from 125 to 250C. TLC, on plates comprising
a mixture of silica gel and boric acid, was used to
separate , , and tocopherols from the unsaponi-
fiable matter of vegetable oils, prior to their determi-
nation by a GC technique employing a silicone SE-30
column according to Riera (160). Squalane served as
an internal standard and tocopherols were measured
in samples of soya bean, safflower and other oils. A
very similar technique for the GC analysis of toco-
pherols was also recorded by Dompert and Beringer
(46).
ADDITIVES
Pl asti ci sers
A GC procedure for the qualitative and quanti-
tative analysis of dicarboxylic aliphatic acid esters,
which are frequently used as plasticiser components
in surface coatings, has been reported by Bloom (26).
A 0.5-microlitre quantity sample dissolved in carbon
disulphide, and equivalent to between 2 and 5 micro-
grammes of ester, was injected at 260C on to a
spirally-wound glass column (8m x 1.8mm i.d.)
packed with 1% QF-1 (a trifluoropropylmethylsilicone
liquid phase available commercially from Applied
Science Labs.) on 100 to 120 mesh Chromosorb Q.
The instrument used was a Hewlett Packard
Series 7400, having a FID which operated at 260C,
and which provided an oven temperature programme
from 160 to 250C at a heating rate of 3 deg. min
- 1
.
The carrier gas was nitrogen admitted at a pressure
of 29 psi which enabled a flow rate of 16cm
3
min
- 1
to
be maintained. Amongst the esters examined were 14
alkyl adipates, 8 alkyl azelates and 9 alkyl sebacates
and their retention times were compared to that of
methyl arachidate which was employed as the inter-
nal standard. Even when these materials were used
as mixtures to test the GC technique, at least 25 of
them could be resolved and identified unequivocally.
The pre-determined elution properties of any of the
above-mentioned compounds allowed them to be
readily identified as components in two commercial
plasticisers namely Duroplaz DIOA and Adimoll BB.
Imia (91) described the determination of the alcohol
components of ester-type plasticisers by GC in a pro-
cedure that required a preliminary ester interchange
reaction to be carried out on the sample using metha-
nol. Dioctylphthalate (DOP), 2-ethylhexanol (2EH)
and other substances which arose during the reaction
of 2EH with phthalic anhydride were separated by
Mosinska (144) using a GC column packed with 5%
DC 200 deposited on Chromosorb G-AW-DCMS. The
column was temperature programmed from 110 to
250C at 20 deg. min
- 1
and the 2EH was determined
at 110C with a carrier gas (hydrogen) flow rate of
60cm
3
min
- 1
whilst DOP was determined at 240C
with a carrier gas flow rate of 120cm
3
min
- 1
. Hydro-
chloric acid is a possible degradation product of PVC
that may react with the epoxy ester added as stabili-
ser and plasticiser to form chlorohydrins. Although
these would decompose during GC to form oxo com-
6 PIGMENT AND RESIN TECHNOLOGY J ANUARY 1981
pounds, it was reported by Startin et al. (187) that
the chlorohydrins could be converted into the corres-
ponding trimethylsilyl ether derivatives which were
sufficiently stable to allow their examination by GC-
mass spectrometry. Results were quoted for a series
of fatty acid methyl ester chlorohydrins.
Kochel and J aroszynska (105) employed a GC
column packed with Chromosorb W and coated with
OW25, SE30 or Apiezon L as stationary phase in the
identification of 13 common ester plasticisers, inclu-
ding tricresyl phosphate, and 17 frequently-used anti-
oxidants present in nitrile and neoprene rubbers. It
was found that the plasticisers could be examined by
evaporating them directly from the samples at 480C,
prior to GC analysis at 250C, and that no interfer-
ence was evident from the degradation products of
the rubbers. The antioxidants needed to be extracted
from the rubbers over a 3-hr. period using acetone at
the ambient temperature followed by GC examination
of the extracts.
Surf act ant s
Surface-active agents, derived from the re-
action of a long-chain aliphatic alcohol with ethylene
oxide, have been extensively studied by GC. Stancher
and Favretto (186) reported the fractionation of
samples having the general formula RO(CH
2
CH
2
O)
13
H,
where R represents an n-alkyl radical, and found that
only the components having n = 1 to 4 were capable
of resolution on a glass column packed with 3% SE30
on Gas Chrom Q. The volatility of the oligomers was
improved by conversion to the corresponding tri-
methylsilyl derivatives, but the resolution was no
better than before even when temperatures above
330C were employed. In order to quantify the alkyl
radical distribution of ethoxylated alcohols, Sones et
al. (183) first converted the samples into the corres-
ponding alkyl iodides prior to GC analysis.
Farkas (53) studied the products obtained by
catalytic oxyethylation of lauryl alcohol on a GC
column packed with 60-80 mesh Chromosorb and
coated with 7% Dexsil. In order to eliminate tailing
effects, the hydroxyl groups present in the sample
were subjected to ketene acetylation. The same
author also examined the product distribution of do-
decylalcohol oligomers at 190-290C by GC on 30-
60 mesh Chromosorb W-AW-DMCS which was
coated with 10% SE301 as liquid phase. Acetylation
or methylation of the samples prior to chromato-
graphy led to the elimination of peak tailing, but it
was found that the methylated compounds gave rise
to superior separation performance. Goto et al. (65)
used a GC column (75cm x 3mm i.d.) that was
packed with 2% OV-I on Chromosorb W (80-100
mesh) and which operated at 232C using nitrogen as
carrier gas (40cm
3
min
-1
) to study the state of solu-
tion of the non-ionic surfactant hexaoxyethylene n-
lauryl ether. The technique was used in conjunction
with the initial GPC (gel permeation chromato-
graphic) separation of the surfactant solution on
Sephadex G-200. The results suggested that a con-
tinuous self-association of the surfactant existed at
low concentrations, whereas a more constant micellar
size was assumed at higher concentrations. Sones et
al. (183) have also reported the alkyl homologue dis-
tribution in alkyl suphates and alkylether sulphates,
whereby the samples were initially subjected to acid
hydrolysis prior to their conversion into the corres-
ponding alkyl iodides and analysis by GC.
Shilov and Molova (171) on the other hand
proposed to calculate the polarity index of sodium
alkylmonosulphate samples from their GC retention
volumes and to plot this parameter against hydro-
carbon chain length in order to determine the length
of the hydrophobic part of the surfactant.
Miscellaneous
Ermilova and Maiorova (49) described a GC
technique for the determination of formaldehyde in
formalin solutions. Polyethyleneglycol adipate. (10%
w/ w) on Polychrom 1 formed the column packing
material and detection of the samples was by thermal
conductivity. Impurities such as oligomeric glycols,
which may be present in formalin solutions, were
quantified by Dankelman and Daeman (41) who sepa-
rated the corresponding silylation products by GC.
The results of these experiments were corroborated
using a 220MHz NMR spectrometer.
Benzophenone and benzotriazole, which may
be used in plastics to absorb UV light, were deter-
mined by FID on a GC equipped with dual stainless
steel columns containing 10% SE-30 on Chromosorb
W, and which were temperature programmed from
180 to 270C, in a method developed by Horacek
(87). The absorber was initially extracted from the
sample of plastic using chloroform or ethyl ether, and
subsequently applied to the GC column as a solution
in chloroform, ethanol or heptane. Using calibration
graphs or internal standards, it was claimed that 0.1
microgram quantities of absorber could be deter-
mined and that the error did not exceed 20%.
According to a paper published by Uden
(199), both high performance liquid chromatography
and GC analytical techniques have been applied to
the analysis of metals. GC required neutral molecules
combined with low molar mass and typical ligands
studied contained -alkyl, -aryl, dienyl, carbonyl or
nitrosyl functionality. For example, -diketonates of
beryllium, chromium, aluminium, iron
( I I I )
and
cobalt
(III)
have been used in realistic analytical deter-
minations, whilst -thioketonates were found to be
valuable in the determination of nickel, cobalt, zinc,
palladium, platinum, cadmium and lead. The most
suitable detector for this approach was a direct cur-
rent argon plasma emission spectrometer. The sample
was transferred from the chromatograph via a heated
line with annularly introduced argon sheath gas to op-
Continued on Page 10
10 PIGMENT AND RESIN TECHNOLOGY J ANUARY 1981
APPLICATIONS OF GAS CHROMATOGRAPHY
Continued from Page 6
timise the form of the plasma discharge, to ensure a
minimum of peak broadening, and the sensitivity to
sub-nanogram levels of the metals. Gas number,
which is a parameter for characterising the foaming
properties of blowing agents, was determined from
the nitrogen content of the thermal degradation pro-
ducts in a pyrolysis-GC approach reported by
Makagon et al (130) Each determination took from
20 to 30 minutes and the results showed a standard
deviation of 0.012 to 0.038.