J Therm Anal Calorim (2012) 109:517–520

DOI 10.1007/s10973-012-2530-0

Effect of glycols used as glycolysis agents on chemical structure

and thermal stability of the produced glycolysates
J. Datta

Bretsznajder Special Chapter

Ó The Author(s) 2012. This article is published with open access at Springerlink.com

Abstract In this study, the influence of glycols on chemical Introduction

structure and thermal stability of glycolysates as polyurethane
intermediates were investigated. The intermediates were Research on polyurethane (PU) glycolysis has been con-
obtained by the glycolysis process of waste polyurethane ducted worldwide with a stable intensity for many years
foams in the reaction with different glycols ranging from [1–9]. Studies are aimed at elaborating technologies which
ethylene glycol to hexane-1,6-diol. The used glycols were not would allow the production of semi-products useful for
separated from the product after the glycolysis process has industry and therefore possessing certain functionality,
been terminated. The effects of different weight ratio of molecular mass, medium reactivity, and low viscosity at
glycols to polyurethane (PU) foam on chemical structure and room temperature. Reactions are studied under atmospheric
thermal stability were investigated by FTIR, GPC, and pressure at temperatures lower than the boiling point of
TG/DTG. FTIR analysis of the glycolysates revealed their low-molecular-mass glycol or diol which serve as glycol-
similar chemical architecture as manifested by the similarity ysis agents. Usually, the catalysts are used, and in some
of absorption peaks within the entire wavenumber range of cases, amines are added which results in aminoglycolysis.
spectra. This may indicate that the glycol has no influence on The products of glycolysis are the so-called glycolysates,
the chemical composition of glycolysates. GPC analysis which consist of a homogenous mix of various compounds,
showed that the glycolysates were characterized by polydis- also including those with amphiphilic properties. The
persity smaller than 2 which is lower as compared to some conditions of PU depolymerization via transesterification
commercial polyols used for PU synthesis. GPC chromato- and the applied glycolysis agents influence the direction of
grams showed that the applied glycols and the conditions of the reaction and therefore the amount of the obtained
PU glycolysis allowed recreation of the original polyol as glycolysate [10, 11]. Based on our studies, we can conclude
documented on the chromatograms by a single, well-formed that the use of low-molecular-mass glycols, ranging from
peak at the beginning of retention time. Based on TG ther- ethylene glycol (EG) to hexane-1,6-diol (HDO), during PU
mograms, it was established that glycol used in transesteri- glycolysis allows obtaining glycolysates with such chemi-
fication of PUs affected the temperature at which the loss of cal structure and thermal stability which make them suit-
glycolysate mass by 5 and 10 % occurs. It was also observed able for the direct application in PU synthesis and the
that glycol affected the temperature at which the decompo- production of elastoplastic materials characterized by sig-
sition rate of glycolysates was the highest. nificant elastoplastic deformation.

Keywords Glycols  Glycolysis process  Thermal

stability  TG  FTIR  Waste polyurethane foam Experimental

Materials
J. Datta (&)
Department of Polymer Technology, Chemical Faculty,
Gdańsk University of Technology, 80-233 Gdańsk, Poland Elastic PU foam was a production waste from Eurofoam
e-mail: datta@urethan.chem.pg.gda.pl Gdańsk LLC (Poland). EG (POCH Gliwice, Poland),

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518 J. Datta

propane 1,3 diol (PG) (Sigma Aldrich, Germany), butane Results and discussion
1,4 diol (BDO) (BASF, Germany), pentane 1,5 diol (GP)
(BASF, Germany), HDO (POCH, Gliwice Poland) as FTIR spectra of the glycolysates produced for the same mass
decomposing agent, and potassium acetate (KAc) (POCH, ratio of PU: glycol of 10:1 and with the use of various gly-
Poland) as catalyst were used. Glycolysis reaction was car- cols are presented in Fig. 1. An outstanding peak for the
ried out at PU foam/glycols mass ratio of 10:1. The amount of wavenumber value of 1,085 cm-1 is interpreted as origi-
catalyst was 0.5 % of PU foam mass. Reaction was carried nating from tC–O–C polyol group. The peaks characteristic
out in a 2-l steel reactor with mechanical stirrer and reflux for –OH groups of hydroxyl compounds (tOH 3,440 cm-1)
condenser at the temperature between 190 and 250 °C. and NH groups of urethane bonds (tNH 3,343 cm-1) are also
Reaction time was 33/80 min depending on glycolysis agent. noticeable. Intensive absorption bands at wavenumber
Two phases were obtained. The weight ratio of upper/lower 3,000–2,800 cm-1 correspond to symmetric and asymmet-
glycolysate phase ranged from 90:10 to 70:30. The upper ric bending oscillations of –CH2– and –CH3 groups. Bands
glycolysate phase was decanted after 24 h and analyzed. present at 1,550–1,350 cm-1 are interpreted as deforma-
tional oscillations of –CH3 groups and other oscillations
Measurements from the bonds between carbon atoms. The [C=O interac-
tions from urethane groups correspond to tC=O band with
Spectroscopic analysis of the glycolysates was carried out two or three peaks at the wavenumber value of ca.
by means of a FTIR Nicolet 8700 spectrophotometer 1,730 cm-1. The tC–O,ureth bands of urethane bonds at
(Thermo Electron Corporation) and ATR technique. The 1,222 cm-1 and tC–O,alc band at 1,008 cm-1 from hydroxyl
Specac Heated Golden Gate single reflection diamond compounds present in glycolysates are also visible.
ATR accessory was used which operates up to 200 °C. Similar results can be found in the reports of other
Spectra were registered at room temperature for wave- authors, who have researched the glycolysis process of PUs
numbers ranging from 500 to 4,500 cm-1 at 4 cm-1 res- [4, 5, 12].
olution with 64 scans. It is noticeable that the obtained spectra indicate the
The measurements were performed at the Gdansk presence of similar chemical substances in glycolysates
University of Technology, Department of Physical Chemistry. irrespective of the glycolysis agent used. GPC chromato-
The mass values and the molecular mass distributions of grams of glycolysates obtained during glycolysis of PU
the glycolysates were determined by chromatography with a foam with EG and propylene glycol are presented in Figs. 2
Knauer 64 GPC System. A set up consisting of five PL-gel and 3, respectively. For a similar retention time (ca.
columns (250 9 8 mm, 10 lm particle size) and refracto- 22–24 min) well-defined peaks of high intensity are present
metric or UV–Vis detector was used. Column calibration in the chromatograms. This indicates that the applied
was performed using polystyrene standards (Watters). glycolysis conditions allowed foam degradation until the
The measurements were performed at the Cracow Uni- total decomposition of PU chains and the separation of
versity of Technology, Faculty of Chemical Engineering specific components, including the main ingredient origi-
and Technology, Independent Department of Chemistry nally used for producing the foam, i.e., polyether polyol.
and Technology of Plastics. The shape of the peak 1 with a very visible maximum
The hydroxyl number (LOH) was determined according (Mp1 = 957 in Fig. 2 and Mp1 = 1,068 in Fig. 3) confirms
to PN-EN ISO 2554. Based on hydroxyl value, the number
average molecular mass (Mn) was calculated from Eq. (1): prop 10
but 10
56:1  1000  f
Mn ¼ ð1Þ pent 10
LOH heks 10
Transmittance/%

where f is the assumed functionality of glycolysate. υ OH υ NH

υ C=O
TG analysis was carried out by using a NETZSCH TG υ CH3, as υ CH2, sym δ CH3, as υ C-O, ureth
υ C-O, alc
υ CH2, as υ CH3, sym δ CH3, sym
209 apparatus. Samples were heated between 20 and
600 °C at the rate of 10 °C min-1. The analysis was per-
formed under argon atmosphere. Temperature values for
which the loss of glycolysate mass by 5 and 10 % (T5% and
υ C-O-C
T10%) had occurred were assessed from TG thermograms.
4000 3500 3000 2500 2000 1500 1000 500
The temperatures at which the highest rate of mass loss
Wavenumber/cm–1
(Tmax) had been observed were determined from the DTG
curve. The measurements were performed at the University Fig. 1 FTIR spectra of glycolysates obtained for the mass ratio of
of Gdansk, Physicochemical Laboratories. polyurethane:glycol of 10:1 and various glycols

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Effect of glycols used as glycolysis agents on chemical structure 519

otherwise would have been present in the chromatogram as

200 1 peak 4 for the above mentioned retention time.
Chromatographic analysis showed that glycolysis, con-
ducted according to the method previously described by the
150
author [11], allowed obtaining glycolysates with the mean
Intensity/mV

2
polydispersity lower than 2. This is advantageous because
100 glycolysates are supposed to serve as semi-products in the
3
production of urethane polymers. High polymolecularity
could significantly reduce or exclude the production of PUs
50
characterized by ordered structure that influences sought
after properties of the product. Number average molecular
0 masses (Mn) of glycolysates calculated by GPC method from
18 20 22 24
LOH values obtained from titration of terminal hydroxyl
Retention time/min
groups (Table 1) are similar. This finding proves that the
Fig. 2 GPC chromatogram of the glycolysate coded Et10. Peak 1 assumed functionality of glycolysate in Eq. (1) is correct.
recovered polyether polyol (Mp1 = 957); peaks 2, 3 reaction by- TG–DTG analysis indicates that the thermal stability of
products (Mp2 = 331, Mp3 = 199) glycolysates increases with the increasing molecular
weight of the glycol used in glycolysis. This phenomenon
1 occurs for the temperature at which degradation is marked
150 by the loss of glycolysate mass by 5 % (T5%), as well as for
the temperature at which such mass loss is 10 %. Our
research results, which have been partially published
Intensity/mV

100 [10, 11], indicate that a 5 % loss of glycolysate mass was

2 mainly caused by evaporation of the remnants of unreacted
3 glycol (temperature range 225–242 °C). Within this tem-
50
perature range, there is no serious damage to oligomerol
chains that contain PU-specific groups. Above 242 °C
urethane bonds probably break, and that initiates degra-
dation of glycolysates. This hypothesis has been confirmed
by other studies, inter alia [13]. Within the temperature
16 18 20 22 24 26
range between 260 and 314 °C a glycolysate loses ca. 10 %
Retention time/min
of its mass, while the main degradation process, which is
Fig. 3 GPC chromatogram of the glycolysate coded Prop10. Peak 1 very rapid, occurs above 360 °C. Destruction is initiated
recovered polyether polyol (Mp1 = 1,068); peaks 2, 3 reaction by- inside rigid segments via decomposition of urethane groups
product (Mp2 = 325, Mp3 = 182)
which is followed by the decomposition of ether groups
the aforementioned conclusion. The peaks marked 2 and 3 in elastic segments [1, 4, 14]. I described the products
are interpreted as mixtures of post-reaction adducts most originating during this process, i.e., amine compounds and
likely containing, inter alia, mono- and dicarbamates. At the carbon monoxide (IV) in the earlier report [4].
same time, the author’s assumption that unreacted glycol in TG–DTG thermogram obtained from the sample coded
the glycolysate obtained for the 10:1 mass ratio is practically Heks10 is presented in Fig. 4.
gone has been confirmed. This manifested itself by the lack The loss of glycolysate mass occurs at the highest rate at
of a well-defined single peak of low intensity which ca. 368 and 399 °C for EG and hexanediol, respectively. We

Table 1 Average molecular mass and polydispersity of glycolysates

Glycolysate code Number average Mass average Polydispersity Hydroxyl number/ Average mass calculated
molecular mass GPC molecular mass GPC GPC mg KOH g-1 from hydroxyl number

Et10 615 1,192 1.94 152 737

Prop10 655 1,435 1.67 148 756
But10 735 1,540 1.76 144 776
Pent10 810 1,780 1.85 136 822
Heks10 914 1,990 1.42 121 927

123
520 J. Datta

100 urethanes and urethane groups, as confirmed by the results

obtained by other authors [1, 10, 13]. It also shows that the
80 foam degradation reached the level of complete decomposi-
tion of PU chains and the separation of specific components,
60
including the main component, i.e., polyetherol. The results

dm/dt, %/min
of TG–DTG analysis indicates that thermal resistance of
Mass/%

glycolysates increases with the increasing molecular weight

40 of glycol used in glycolysis. Moreover, glycolysates display
thermal resistance up to ca. 240–260 °C. The temperature at
20 which a 5 % mass loss occurs most likely does not result from
398.9
degradation but from evaporation of unreacted glycol. The
0 shape of DTG curves proves it.
100 200 300 400 500
Temperature/°C Open Access This article is distributed under the terms of the
Creative Commons Attribution License which permits any use, dis-
Fig. 4 TG and DTG curves of the glycolysate coded heks10 (10:1) tribution, and reproduction in any medium, provided the original
author(s) and the source are credited.

Table 2 Results of thermal stability analysis of the glycolysates.

Mass ratio of PU foam to glycol equals 10:1 References
Glycolysate code T5%/°C T10%/°C Tmax/°C 1. Molero C, de Lukas A, Rodriguez IF. Recovery of polyols from
flexible polyurethane foam by ‘‘split-phase’’ glycolysis with new
Et10 225 260 368
catalysts. Polym Degrad Stab. 2006;91(2):894–901.
Prop10 235 274 380 2. Nikje AMM, Nikrah M, Mohamadi H. Microwave-assisted
But10 240 285 385 polyurethane bond cleavage via hydroglycolysis process at
Pent10 243 297 392 atmospheric pressure. J Cell Plast. 2008;44(5):367–80.
3. Benes H, Rosner J, Hooller P, Synkowa H, Kotek J, Horak Z.
Heks10 244 314 399 Glycolysis of flexible polyurethane foam in recycling of car seats.
Polym Adv Technol. 2007;18(2):149–56.
assume that the former temperature value results, partially or 4. Lee JY, Kim D. Desaminated glycolysis of water-blown rigid
polyurethane foams. J Appl Polym Sci. 2000;77(12):2646–52.
wholly, from the presence of the glycolysate remnants in the 5. Wang J, Chen D. Studies on the glycolysis behavior of poly-
evaporated product. The values of temperature at which the urethane fiber waste with diethylene glycol. J Polym Environ.
degradation of all glycolysates starts (TG) and at which the 2006;14(2):191–5.
rate of mass loss is the fastest (DTG) are listed in Table 2. 6. Murai M, Sanou M, Fujimoto T, Baba F. Glycolysis of rigid
polyurethane foam under various reaction conditions. J Cell Plast.
2003;39(1):15–27.
7. Youssef B, Mortaigne B, Soulard M, Saiter JM. New IPN for
Conclusions high-tech applications: synthesis and functional properties.
Matériaux Tech. 2011;99(2):297–304.
8. Pielichowski J, Prociak A, Michałowski S, Bogdał D. Application
The used analytical methods confirmed that during the gly- of selected polymeric wastes in the formulation of rigid poly-
colysis of waste PU foam glycols, ranging from EG to 1,6- urethane foams. Polimery. 2010;55(10):757–64.
hexanediol, have less significant influence on chemical 9. Wu C-H, Chang C-Y, Cheng C-M, Huang H-C. Glycolysis of
architecture and probably also on chemical composition of rigid polyurethane from waste refrigerators. Polym Degrad Stab.
2002;75(4):413–21.
glycolysates as demonstrated by similar absorption bands, as 10. Datta J. Synthesis and investigation of glycolysates and obtained
well as much the same intensities of the peaks appearing in polyurethane elastomers. J Elast Plast. 2010;42(2):117–27.
FTIR spectra. The peak intensity at 1,085 cm-1 indicates the 11. Datta J, Rohn M. Thermal properties of polyurethanes synthe-
presence of oligomerols that contain ether groups and there- sized using waste polyurethane foam glycolysates. J Therm Anal
Calorim. 2007;88(2):437–40.
fore the probable presence of polyols used in the synthesis of 12. Modesti M, Simioni F, Munari R, Baldoni N. Recycling of
PU subjected to glycolysis. This observation has been con- flexible polyurethane foams with a low aromatic amine content.
firmed by the analysis of GPC chromatograms. For the similar React Funct Polym. 1995;26(2):157–65.
retention time value (ca. 22–24 min) well-defined peaks of 13. Kościelska A. Thermal degradation of polyurethanes. Polimery.
1977;42(4):355–60.
high intensity appear in the chromatograms. This is an indi- 14. Baolian N, Liting Y, Chengshuang W, et al. Synthesis and ther-
cation that the used glycols and chosen reaction conditions mal properties of soybean oil-based waterborne polyurethane
allow for conducting intermolecular transesterification of coatings. Therm Anal Calorim. 2010;100(4):239–46.

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