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Degradation of polyethylene glycol. A study

of the reaction mechanism in a model
molecule: Tetraethylene glycol
Departtnenr

of Comrtwarion,

The

(Received

Jens Glastrup
National Musewtl of Denmurk.
14 September

B&e.

1995: accepted 26 October

DK 2800. Lynghy,

Detmurk

1995)

A model for the degradation of polyethylene glycol (PEG) is presented.

Heating to 70C in a current of air leads to formation of formic acid. Under
dry conditions this reacts with the terminal hydroxyl group of the polyethylene
glycol, resulting in formic acid esters. Under wet conditions the acid stays in
solution or evaporates. 0 1996 Elsevier Science Limited

after one week. Under a relative humidity of

75% this degradation proceeds somewhat slower
and after one week 35% is left. Under humid
conditions this degradation can be completely
inhibited (no degradation is seen after one week)
by some trace elements (Fe, Cu) or enhanced by
others
(Ni) so that the degradation
rate
resembles degradation
under dry conditions.
Attempts
to incorporate
antioxidants
have
previously been made in polyethylene
glycol
stationary phases with limited success.4
The degradation
products
found by gas
chromatographic analysis are few. During the dry
reaction five reaction products were found. The
identification
of these products, and of the
reaction mechanism
leading to them, is the
purpose of this article.

1 INTRODUCTION
In gas chromatography
polyethylene
glycol
(PEG, carbowax@) is known to be susceptible to
degradation
at elevated temperature
in the
presence of oxygen and water. In other industrial
applications, however, polyethylene glycol is used
without any consideration of this susceptibility to
oxidation. In the conservation industry, practical
experience shows that stabilisation can last at
least 20 years, without any apparent degradation.
Heating over more than two years at 65C caused
a degradation
of no more than 20% of the
original amount of PEG.
Practical experience in the waterlogged wood
laboratory has shown that PEG at relatively low
temperatures,
under some circumstances,
has
shown a remarkably fast decomposition
rate.
Heating the PEG 4000 for 2-4 h has in some
cases led to the formation of a liquid which
would not solidify after cooling. We have shown
that this liquid more resembled PEG 600 than
the original PEG 4000. This is clearly unacceptable for a material which is used in the
conservation of archaeological material.
We have continued our experiments in the
laboratory with a model molecule, tetraethylene
glycol (TEG) and have demonstrated
that this
molecule indeed decomposes very fast at 70C.
Under dry conditions no more than 20% is left

2 MATERIALS

AND METHODS

2.1 Experimental setup

The chemical
used as a model
for the
degradation
of PEG is tetraethylene
glycol
(TEG, CARN 112-60-7). All degradation experiments were performed at 7OC, in an oven held at
63C. The reaction vial was 5 ml 33-expansion
borosilicate glass from Wheaton. 2.0 ml of TEG
was put in the vial which was then placed in an
217

218

J. Glastrup

insulated aluminium block in the oven. The block

was heated to 70C. The oven contained a flask
of water through which air was bubbled. The
saturated air stream from the water flask at 63C
was further heated to 70C in a coil in the
aluminium block. This lowered the RH to 75%.
The air was then bubbled through the TEG,
which has 27% water content at equilibrium with
75% RH. For the dry experiments the vial was
placed in the aluminium block and dry air passed
directly through it. Tri- and tetraethylene glycol
were supplied by Sigma.
2.2 Pneumatics
All tubing was l/8 and l/16 teflon. The air was
passed through Molecular Sieve 3A and activated
charcoal (Merck 2514 and 5704). The air pressure
was set at 170 kPa. The flow was controlled by a
2 cm long restrictor made of polyimide-coated
fused silica with an internal diameter of 60pm (J
and W Scientific, Folsom, CA) giving a flow rate
of 10 ml/min. A flow rate of lOml/min or more
gives maximum degradation rate.
2.3 Analysis
2 ~1 aliquots

were withdrawn from the reaction

flask and transferred
to a vial with 1.0 ml
acetone. The diluted samples were analysed by a
Varian 3500 Gas Chromatograph.
Carrier gas:
Hz, initial column temperature:
110C hold
0.5 min, ramp rate 40C/min to 175C hold
0.3 min. Injector: 275C, Split: 25, Column flow:
2.0ml/min. Detector: 23oC, att: 16-32. Column:
DB-5, 4 m long, 0.32 mm i.d., coating 0.25 pm,
from J and W Scientific.
Analysis of the degradation
products was
performed on a Varian Saturn II GC/MS. GC:
carrier gas: He, column 20 m DB-wax (121-7023),
20 m long, 0.18 mm i.d., coating 0.30 pm, from J
and W Scientific. MS: manifold temperature:
220C mass spectrometer
tuned through autotune, scan segment from 35 to 399 amu and
1 scan/s.
Liquid injection of acetone samples: injector:
SPI, initial temperature
65C
ramp
rate
200C/min to 2OoC, hold 12 min. Initial column
temperature:
40C hold 2 min, ramp rate
4OC/min to 80C ramp rate lC/min to lOOC,
ramp rate SC/min to 240C hold 3 min. Transfer
line: 240C.
To
perform
high-sensitivity
screening
of

condensed waste water from the experiment run

at 75% RH, Solid Phase Micro Extraction
(SPME) samples were taken. SPME is essentially
an inverted piece of column, with the column
coating on the outside, positioned
inside a
needle. The needle is positioned in the air or
water sample, and the column is ejected. After a
certain time period the column is withdrawn, the
needle is transferred
to the chromatograph
injector and the column is again ejected for
desorbtion.
Injector: SPI, initial temperature
4oC, ramp rate 200C/min to 200C hold
12 min. Initial column temperature: -30C hold
2 min, ramp rate 40C/min to 80C ramp rate
lC/min to 100C ramp rate SC/min to 240C
hold 3 min. Transfer line: 240C.
The SPME column coating was 100 pm
methylsilicone (Supelco, Bellefonte, PA, USA).
The extraction period from a water sample was
15 min.
2.4 Synthesis of components

Synthesis of tetraethylene
glycol monoformate
(TEG-MF) and tetraethylene
glycol diformate
(TEG-DF): 0.5 ml of TEG was added to a vial
and bubbled with N, (N, > 99.998, Hede Nielsen)
which was previously saturated at 20C with 85%
formic acid (technical quality). The vial stayed at
70C for 24 h before analysis of the reaction
products.
The synthesis of the mono- and
diformates of triethylene glycol was done in the
same way.

3 RESULTS
3.1 Description

AND

DISCUSSION

of the model molecule

Tetraethylene glycol (TEG) is used as a model

molecule for PEG. Besides the two end hydroxyl
groups it contains two vicinal ether groups which
may be under the influence of the hydroxyl
groups. It also contains one central ether group
which is expected to be under the influence of
other ether groups only. This molecule can
therefore be expected to be susceptible to all
types of reactions found on larger molecular
weight PEGS.

Degrnclrrtion

o,f poiyerhylene

glycol

219

3.2 The dry reaction

_!.

!:!
k

The degradation of TEG through aeration with

dry air results in the formation of five new peaks,
see Fig. l(A), of which two of these are
apparently (peak 5 and 6), based on the longer
retention time, and have a larger molecular
weight than TEG. These peaks are found to be
mono- and diformylated derivatives of TEG (see
Fig. I(B)). Th e only reasonable explanation for
this degradation is an oxidation at one of the
hydroxyl groups:

I
A

HO-CH,C&-0-CHQJ-O-W&&-0-CycH,-OH

HO-CH$H,-O-CH+&-0-CHJH@CH+H

(1)

+ HCOOH

(2)

As the oxidation
is occurring
under
dry
conditions the formic acid is trapped by the
remaining TEG to give a formic ester. Initially as
the monoformic
acid derivative
but as the
reaction proceeds the diformic acid derivative
begins to appear in the chromatogram
as well,
see below. This has been confirmed by GUMS.
The mass spectra are seen in Fig. 2(A) and (B):

HO-CH,Cq-O-CH,CH$-CH&H=0-CH$H=OH

+ HCOOH

J
HO-CH,CH,-O-CH,CH,-0.C&C&-0-CH$H#-OCIf

+ H,Ot

$+HCOOH
HCO-0-CHQ-&O-CH$I+O-C%c%-o_c%c%-0-CHJ~-O-OCH
+ H,O?

C
Fig. 1. Gas chromatograms of: (A) TEG which under dry
conditions has been bubbled with air at 70C for 10 days.
(B) TEG bubbled with N, + formic acid gas for 24 h. (C)
Triethylene glycol bubbled with Nz + formic acid gas for
24 h. (1) Triethylene glycol, (2) triethylene glycol monoformate, (3) triethylene glycol diformate, (4) tetraethylene
glycol (TEG), (5) tetraethylene
glycol monoformate,
(6)
tetraethylene glycol diformate.

In this theory the reaction product from the

primary oxidation
(2) is the hemiacetal
of
triethylene glycol and formaldehyde.
Being an
unstable
product,
this should lead to the
formation of free triethylene glycol. This should
later, in the reaction period, lead to formation of
the mono- and diformylated derivatives following
the same reaction scheme as above. This is
indeed the case. As seen in Fig. l(A) the peaks
numbered 1, 2 and 3 correspond to triethylene
glycol and its mono- and diformylated derivatives, see Fig. l(C). These results have also been
confirmed by GC/MS.

220

J. Glastrup

1%
49

Fig. 2. Mass spectra

69

88

of tetraethylene

190

128

149

glycol formates.

169

lee

2e9

(A) Tetraethylene
diformate

3.3 The wet reaction

During a reaction at 75% RH there is (as
mentioned
above) 27% water present in the
solution. The formic acid derivatives would not
be expected to be found because of the constant
presence of water and the acidic environment
formed in the reaction solution. The terminal
hydroxyl group therefore
stays unprotected.
Instead, successively smaller polyethylene glycols
and free formic acid will be formed and either
stay in solution or evaporate at the reaction
temperature,
70C. Condensed water from the
hot reaction vessel should therefore contain free
formic acid. Figure 3 shows a chromatogram of
an SPME analysis of the condensed water and

W7 219229
229

243

24e

glycol monoformate.

(B) Tetraethylene

glycol

Fig. 4 shows a chromatogram

of TEG decomposed under humid conditions
for 10 days.
Approximately
20% of the original material is
left. Figure 3 shows clearly that the main
component
found in the condensed water is
formic acid, and Fig. 4 shows that not many other
components
are present
together
with the
remaining TEG (4), the only visible peaks being
diethylene glycol (2) and triethylene glycol (3).

4 CONCLUSION
The formation
of formic acid during the
degradation
of PEG
has been
described
previously.~~ However the main oxidation of

221

Fig. 3. Total ion chromatogram

the mass spectrum

of an SPME analysis of condensed

of the peak at scan 1080 in the chromatogram.
acid.

Fig. 4. Total ion chromatogram

acetone).

water after wet degradation of TEG for IO days. Inserted is

This mass spectrum and the retention time matches formic

of TEG after IO days of degradation at a humidity of 75% RH. (I) Diacetone

(2) diethylene glycol. (3) triethylene glycol. (4) tetraethylene
glycol (TEG).

PEG is normally expected to occur at the ether

bond through a peroxidation reaction,4.sm described thoroughly by Riecke and co-workers..
This would lead to the formation of many
components with great complexity. However, our
results with the model molecule TEG show that
the degradation almost exclusively leads to the
formation
of formic acid and formic acid
derivatives.
This can be fully explained by a model which
assumes that the oxidation must take place at the
terminal hydroxyl group leading to the formation
of formic acid and-under
dry conditionsformic acid esters. It further
predicts the
formation of an unstable hemiacetal of formal-

(from

solvent

dehyde and triethylene glycol. The triethylene

glycol and-again
under dry conditions-the
mono- and diformates are also found in the
reaction solution. Under wet conditions none of
the formates are found, leaving the hydroxyl
groups unprotected. The tetraethylene glycol is
therefore fully oxidised.

ACKNOWLEDGEMENT
The author is very indebted to Varian, and
especially to Bjorn Rohde, Analytical Instruments, for the loan of a Varian Saturn II Mass
Spectrometer.
Also sincere thanks to Tim

222
Padtield and Paul Jensen for their
willingness to discuss this research.

never-ending

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