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DOI 10.1007/s10973-009-0142-0
Received: 30 March 2009 / Accepted: 26 May 2009 / Published online: 19 June 2009
Akademiai Kiado, Budapest, Hungary 2009
Abstract A combination of pyrolysis and gas chroma- exceptional optical clarity due to polymer compatibility and
tography were used to investigate thermal degradation non-yellowing. The thermal degradation behaviors of
products formed from acrylic copolymers containing alkyl poly(acrylic acid) and acrylic copolymers with other unsat-
acrylate and methacrylate. The method provided an ana- urated monomers have been examined in a number of studies
lytical tool for characterizing the chemical composition and [36] that have identified water and carbon dioxide as the
structure of the degradation products. Thermal degradation main gaseous pyrolysis products. However, these volatile
of the synthesized copolymers was analyzed using iso- products cannot be used for accurate qualitative analysis of
thermal (250 C) pyrolysisgas chromatography. The deg- the copolymer degradation. Studies of the degradation of
radation process, and the nature and amount of pyrolysis poly(acrylic acid) have revealed anhydride formation, indi-
products, provides relevant information about the thermal cating competition between dehydration and decarboxyl-
degradation of acrylic copolymers and the mechanism of ation reactions. Quantitative analyses of the thermal
pyrolysis. During pyrolysis, the formation of corresponding degradation of poly(alkyl acrylates) have revealed products
olefins, alcohols, acrylates and methacrylate was observed. including alkenes, carbon dioxide, carbon monoxide and
hydrogen [7]. The alcohols corresponding to the alkyl group
Keywords Acrylic and methacrylic copolymers are the major liquid products, with traces of monoacrylates
Pyrolysis Thermal degradation products and the corresponding methacrylates. All these products are
Analysis and identification accounted for in terms of radical reactions with a unique
initiation step [8]. Pyrolysisgas chromatography (PyGC)
can be used to easily, rapidly and inexpensively characterize
Introduction polymer formulations as polymers or compound polymeric
materials [9, 10]. The complex components of thermal
Acrylate and methacrylate copolymers have excellent degradation at high temperatures can be divided into three
physical, chemical and mechanical properties. Such fractions: gaseous, liquid and residue. Heating of a sample in
copolymers have many uses, for example as raw materials a closed system in an inert gas produces a pyrolysate that can
for adhesives, paints, varnishes and sealants in technical and be fed directly into a gas chromatograph, enabling identifi-
medical applications [1, 2]. Copolymers based on acrylic or cation of the constituent unsaturated monomers [1113].
methacrylic acid esters and acrylic acid offer particular
advantages, including excellent aging characteristics, resis-
tance to elevated temperatures and plasticizers, and Experimental
123
642 Z. Czech, R. Peech
The polymerization process was carried out under the acrylate and acrylic acid (Fig. 1) contained three principal
following conditions: dosage time of residual monomers peaks representing methanol, methyl acrylate and methyl
with residual AIBN, 1 h; time of post-reaction, 5 h; poly- methacrylate, the latter corresponding to the acrylic acid
mer content, 50 wt%. methyl ester incorporated into the acrylic polymer chain.
The viscosities of the synthesized solvent-borne acrylic The pyrogram of the ethyl acrylate/acrylic acid copolymer
copolymers are listed in Table 1. For evaluation purposes showed ethanol, ethyl acrylate and ethyl methacrylate as
an acrylic copolymer TEC MEB-2 from ChemCycle Bit- the thermal degradation products. The peaks in Fig. 3
terfeld GmbH, Germany comprising methyl acrylate correspond to 1-butanol, butyl acrylate and butyl methac-
(10 wt%), ethyl acrylate (20 wt%), butyl acrylate rylate. The presence of these three peaks in the pyrolysis
(30 wt%), 2-ethylhexyl acrylate (37 wt%) and acrylic acid chromatogram is possibly due to thermal decomposition of
(3 wt%) was used. The optimum conditions for pyrolysis butyl acrylate groups in the side chain. The pyrolysis
of the acrylic polymers included a temperature of about
500 C for 30 s in a helium atmosphere. The pyrolysis
products of the acrylic copolymers were subject to gas 100
Peak height
rier gas (80 kPa); FID at 250 C, injection temperature 60
250 C, oven temperature program 50 (0 min) to 230 C at
10 C min-1 (32 min); injection volume 0.3 lL, and (Py 40
GC)/mass spectrometry techniques.
The pyrolysis apparatus was disassembled at the 20
reduction union, and a 5 mg sample of acrylic polymer was
placed in the bottom of the loop. The pyrolysis apparatus 0
was reassembled and connected to the gas sampler valve 0 5 10 15 20 25
instead of the constant volume tube. Plugs were placed in Retention time/min
the regular sample inlet and in the vent openings of the gas Fig. 1 Chromatogram of the pyrolysates of acrylic copolymer
sampler valve. Helium was used to flush air from the methyl acrylate-acrylic acid
apparatus, and the system was closed. The loop of the
apparatus was heated at 500 C for 30 s. Products resulting
100
from the pyrolysis were carried into the gas chromatogra-
ethyl acrylate (EA)
ethyl methacrylate (EMA)
phy column using helium.
ethanol
20
Results and discussion
0
Figures 1, 2, 3 and 4 show chromatograms of the thermal 0 5 10 15 20 25
breakdown products of acrylic copolymers containing Retention time/min
commercial alkyl acrylates and acrylic acid. The pyrolysis Fig. 2 Chromatogram of the pyrolysates of acrylic copolymer ethyl
chromatogram of the acrylic copolymer based on methyl acrylate-acrylic acid
123
Identification of acrylate copolymers using pyrolysis and gas chromatography 643
butanol-1
O
100
60
CH2 CH CH2 CH CH2 CH H3C O
n
C O C O COOH H2C C C O C4H9
40 O O methacrylic acid butyl methacrylate
ester
C4H9 CH3 CH3 O
H2C C C O CH3
20 BA MA AA
methyl methacrylate
Fig. 3 Chromatogram of the pyrolysates of acrylic copolymer butyl the corresponding monomers 2-ethyl 1-hexanol, 2-ethyl-
acrylate-acrylic acid hexyl acrylate and 2-ethylhexyl methacrylate were
observed in the liquid phase. Figure 5 shows the chro-
100 2-ethylhexyl acrylate (2-EHA) matogram of the pyrolysate of an externally synthesized
acrylic copolymer (TEC MEB-2) containing methyl acry-
80 late, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate
2-ethyl 1-hexanol and acrylic acid. Comparison of the retention times of the
Peak height
60
major peaks for various polymerizations using unsaturated
acrylate monomers indicated the presence of four main
40
monomers. The additional peaks present were accounted
2-ethylhexyl methacrylate (2-EHMA)
20
for by comparison with the chromatograms of individual
polymers. The acrylic copolymer was identified as being
0 composed of methyl acrylate, ethyl acrylate, butyl acrylate
0 5 10 15 20 25 30 35 and 2-ethylhexyl acrylate. The mechanism of formation of
Retention time/min the liquid breakdown products can be explained on the
Fig. 4 Chromatogram of the pyrolysates of acrylic copolymer basis of the characteristic properties and thermal resistance
containing 2-ethyl hexyl acrylate and acrylic acid of typical acrylic copolymers (Fig. 6).
2-ethyl 1-hexanol
80 Conclusions
butanol-1
2-EHA
40
Small samples of copolymers were pyrolyzed, and the
methanol
EA
123
644 Z. Czech, R. Peech
123
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