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Eckhart Kornejew, Kiril Dimitrov, Michael Herzog

Abstract Zusammenfassung

China sent shock waves through the global recycling mar- China hat den globalen Recycling-Markt letztes Jahr mit
ket last year when it announced it would no longer be der Ankündigung geschockt, nicht länger niederwertige

accepting poor qualities of recyclable waste from foreign Qualitäten von rezyklierbaren Abfällen von ausländischen
exporters – the so-called green fence action started in Exporteuren zu akzeptieren – die so genannte „Aktion Grü-
the beginning of year 2013. The answer should be a wave ner Zaun“ startete zu Beginn des Jahres 2013. Die Antwort
of innovation and investment in recycling technology to im Westen sollte ein Innovations- und Investitionsschub
catalyze successful recycling markets in the west. This in Recycling-Technologie zur Entwicklung eines erfolgrei-
could include more sophisticated handling and treatment chen Recycling-Marktes sein. Dies sollte hochentwickelte
techniques and more high-technology processing plants. Behandlungstechnologien und installierte Anlagentechnik
In the case of PET from returnable bottles we developed umfassen. Für PET-Getränkeflaschen aus den Pfandsyste-
a process of chemical recycling to produce feedstocks for men haben wir einen Prozess des rohstofflichen Recyclings
several technical applications. Aromatic polyester polyols entwickelt, mit dem Ausgangsstoffe für verschiedene techni-

(APP) are a major class of raw materials to produce poly- sche Anwendungen gewonnen werden können. Die gewon-
urethanes. nenen Aromatischen Polyesterpolyole (APP) dienen hierbei
als Ausgangsstoffe zur Herstellung von Polyurethanen.

I. INTRODUCTION by the re-esterification of poly (ethyl- The process is started with feeding
ene terephthalate) (PET) with glycols the reactor with the necessary amount
There are four main classes of such of different origin (Vaidya 1991, Baglia of diethylene glycol, catalyst and, if
polyester polyols (Randall, 2002): li- 1989, Inada 1999). Due to the different so necessary, with any additive used
near or lightly branched aliphatic po- raw materials APP of different quality during the reaction. With stirring, the
lyester polyols with terminal hydroxyl will be obtained. mixture is heated to about 180°C and
groups, low molecular weight aro- any volatiles (mainly residual water)
matic polyester polyols for rigid foam In this paper we report our experience removed via the column condenser

applications, polycaprolactones and with various types of post-consumer and combination. When the volatile distil-
polycarbonate polyols. The linear or industrial wastes of PET to produce APP, lation ceases and the temperature is
lightly branched polyester polyols describe the quality obtained, and reached the PET is added via the ele-
may be aliphatic or aromatic. Aro- throw some light on the application of vating system. The PET is dissolved
matic polyester polyols are produced the materials obtained and their eco- while rising the temperature to 250°C.
from phthalic acid, isophthalic acid, nomic value. During the whole process the reactor
or terephthalic acid. While the manu- is purged with nitrogen so that a con-

facture from phthalic or isophthalic II. GENERAL PROCESS stant stream of nitrogen is ensured.
acids is generally based on the mono- Any further volatiles are removed by
mers terephthalic acid oligomers may The reactor used is a stainless steel jacketed the column condenser combination
as well be produced from monomeric reactor with a volume of 0.1 to 10 m³ and collected on a balance. The trans-

esters such as the dimethyl ester of depending on the desired amount esterification reaction is performed at
terephthalic acid (DMT) or polyesters of APP to be produced. The reactor is 250°C over a period of 3.5 to 6 hours
such as polyethylene terephthalate equipped with a specially designed depending on the type of material
(PET), polybutylene terephthalate combination of demister, distillation used. During the reaction time any
(PBT) or polypropylene terephthalate column(s), and heat exchanger on top. volatiles are removed by the condenser
(PPT). The contents of the reactor are agitated and outlet and collected. After comple-
by a stirrer at rather high speed. Further tion of the reaction the temperature is
APP based on terephthalic acid are installations include a nitrogen inlet, a gradually lowered down to 180°C and
presently produced by two different feed elevator, and a bottom valve with the reaction product removed by the
ways: the transesterification of tere- a filtering unit. The temperature is con- bottom valve via a filter unit into the

phthalic acid dimethyl ester (DMT) or trolled via an oil heater with control unit. storage containers.

Wissenschaftliche Beiträge 2014 71
Some peculiarities of this process lecular weight product with very little The bottle PET is delivered usually as
have to be considered. This is firstly to contamination meeting food regula- preforms. Preforms usually do not
establish a functionality of the APP tions (e. g. acetaldehyde). Other pro- contain any contamination and maybe
produced somewhat exceeding two ducts are not contained, the ethylene used as such in the transesterification
by incorporating a calculated amount glycol used sometimes is combined process. It has to be considered that
of a triol, in general glycerol, into the with other diols. PET from such pro- the rather large pieces need a pro-
reaction mixture (Stoychev, 2006). duction is obtained in the form of longed time in the dissolution stage
By using only minor amounts of such a blocks, fibres, dust, granules. so that a milling stage before the
triol the viscosity of the final APP is not introduction into the reactor is recom-
affected but the stability of the polyol PET for fibres in general is doted with mended.
is increased. Another feature of this small amounts of silica and/or titanium
process is to use only minor amounts dioxide both in micronized form. This When using fibre PET from production
of organo-metallic compounds as leads to particles of less than 10 μm lines as blocks or coils the inorganic
catalyst. In general, a mixture of tin which are difficult to filter off, either solids have to be agglomerated during
and titanium compounds in the range due to higher investment costs for the the process to be transformed into a
of 15 to 30 ppm is used but in special filter modules or by extended recovery filterable mode. To this end, certain
cases rare earth compounds may be time. The result of employing this filter aids are added in the end phase
added to accelerate the first stage of material is usually a dispersion polyol of the process at 250°C to absorb the
the reaction. For adjustment of the vis- containing the micronized solids. micronized particles on their surface
cosity the mixture is balanced by the to give particle sizes between 200 and
addition of some percent of aliphatic PET from bottles, i. e. flakes from one- 800 μm which are removed in a two
dicarboxylic acids such as adipic acid way or multi-way bottle recycling, module filter unit.
or sebacic acid (Behrendt, 1999). If occur in several colours and usually
these additives are used, there will have some additives. These additives When using PET flakes from bottle re-
be a short esterification step in the are not only dyestuffs or pigments to cycling one has to take into considera-
gap between the heating-up process give blue, brown, green or yellow co- tion the various ways of bottle produc-
and the addition of PET which usually lours but more linings of the bottles tion for various liquids. As mentioned
lasts 30 to 60 minutes depending on with silanes (such as hexamethylene above, the layers lead to some prob-
the amount used. Furthermore, some disiloxane), with intermediate layers lems when producing APP. If polyami-
renewable resources such as oils or from polyamides, or with outer layers des are used as an intermediate layer
modified oils maybe introduced into of polyacetylenes. Since the silanes are to decrease gas diffusion the APP may
the process before PET is added to forming a layer of few nm of silicates turn brown or dark due to reaction
adjust properties of the APP, e. g. to this is an inorganic substance which is products of the polyamide. The poly-
improve the solubility of pentane or as hardly to filter off as the additives amide is transesterified in a similar way
chlorinated hydrocarbons. for fibres. Any organic additive or layer as is PET leading to reactive oligomers.
will affect the reaction and the resul- These are not affecting the properties
After receiving the calculated amount tant APP. Main appearances for these of foams, but the colour of the APP
of distillates, mainly monoethylene are turbid or deeply coloured APP. only. More problems arise from layers
glycol and some water, the cooling in the μm or nanometer range. They
module of the reactor is started to cool When using bottle grade PET from the lead to particles of less than 1 μm of
the contents to about 200 to 180°C production process of PET one has to different properties so that only one
and filter them via a specially designed make sure that the process is running filter aid will not be sufficient. In case
filter unit of two or three different the easiest way. To this end, blocks are of using such raw materials different
filter modules. The number and type milled to particles of 2 to 8 mm size by filter aids have to be tested to find the
of filter modules depend on the PET a mill delivered with the plant in case optimum one for the raw material to
material used. of using such material. In this case, the be used in the respective plant and to
milled product is directly transferred make sure the filter unit works.
III. PET MATERIALS TO BE USED to the silo and from there via the con-
veyer into the reactor. If granules are IV. PROPERTIES OF THE APP PRODUCED
PET residues occur in several types and the basic material care has to be taken
have to be analyzed according to the because of some percentages of dust in APP are produced for three main ap-
possible consequences for the over- it. Thus the material has to be flushed plications in polyurethane chemistry:
all reaction. At present, PET is mainly with nitrogen to avoid dust explo-
used to produce bottles or fibres with sions or electrostatic effects which are ■ polyisocyanurate foams (PIR) where
little amounts in engineering thermo- known to occur with polymeric dusts. a low hydroxyl number is desired
plastics and bulk containers. We are After reacting the material according and the functionality does not play
here concentrating on the two main to the process described above there an important role (hydroxyl num-
production variants. is need of only one filter module to get bers are in the range of 200 to 260
rid of some coarse impurities. mg KOH/g);
PET for bottles is generally a high mo-

72 THWildau
Wissenschaftliche Beiträge 2014
rigid polyurethane foams such as Main types of APP
sandwich panels where a hydroxyl

number somewhat higher as with Parameter\APP M20 M21 M22
PIR and a higher functionality are
Hydroxyl number (mg KOH/g) 240 320 380
desired (hydroxyl numbers are in
the range of 300 to 380 mg KOH/g); Acid number (mg KOH/g) <1 <1 <1

■ polyurethane duromer foams whe- Water content (%) <0,2 <0,2 <0,2
re a hydroxyl number somewhat
Viscosity (25°C) (mPas) 8,000 4,500 4,500
higher as with PIR and a higher
functionality are desired (hydroxyl Functionality 2.03 2.05 2.07
numbers are in the range of 300 to

Tab. 1) Main types of APP.
360 mg KOH/g);

Further applications are in the area
of coatings, adhesives, sealants, and Linear APP
casts. For these products special poly-
ester polyols have to be developed to Parameter\APP A31 A42 A46
exactly meet the requirements of the
Hydroxyl number (mg KOH/g) 220 320 380
Acid number (mg KOH/g) <1 <1 <1
By the process described several types
of APP are produced (Schaffrath 2006). Water content (%) <0,2 <0,2 <0,2
There are three main types according

Viscosity (25°C) (mPas) 5,500 4,000 3,500
to the classification above which are
characterized in Table 1. Functionality 2.00 2.00 2.00

Tab. 2) Linear APP.

Besides these lightly branched APP
linear ones with a defined hydroxyl
functionality of exactly 2 are available
by proper adjustment of the reaction Flame Retarded APP
mixture. Examples of purely difunc-
tional APP are given in Table 2. Parameter\APP F03 F04 F06

Hydroxyl number (mg KOH/g) 260 330 390

Any of the APP has an inherent flame
retardance due to the content of ar- Acid number (mg KOH/g) <1 <1 <1
omatic nuclei. A modification of the
APP produced may be obtained for Water content (%) <0,2 <0,2 <0,2

higher flame retarded polyurethanes
Viscosity (25°C) (mPas) 3,500 2,000 1,500
by directly blending the APP with
flame retardants such as liquid phos- Functionality 2.03 2.04 2.05
phorous compounds. When doing
Tab. 3) Flame Retarded APP.
so, a second unit (blending station)
should be considered to increase pro-
ductivity of the overall process. In

Table 3 some examples of APP blended APP with high content of secondary hydroxyl groups
with flame retardants are given.
Parameter\APP H62 H65 H66
Typically, the glycol used is diethylene

Hydroxyl number (mg KOH/g) 220 320 360

glycol which results in APP with
nearly only primary hydroxyl groups Acid number (mg KOH/g) 0.35 0.30 0.30
resulting in highly reactive polyols
with an OH-functionality of fn = 2. By Water content (%) <0,1 <0,1 <0,1
introducing a triol such as glycerol or
Viscosity (25°C) (mPas) 7,900 4,400 2,900
(trimethylol)propane into the poly-
ethers the functionality may be in- Functionality 2.00 2.00 2.00
creased to values of about fn = 2.25
Tab. 4) APP with high content of secondary hydroxyl groups.
but resulting in an increase in the
viscosity of the products. Thus, the

incorporation of triols has to be exer-


Wissenschaftliche Beiträge 2014 73
cised carefully so as not to increase Hydroxyl-No. Field of application
the viscosity beyond a tolerable limit. APP Peculiarities
range (mg KOH/g) recommended

Otherwise, APP with a majority of Isocyanate indexes

secondary hydroxyl groups is obtai- M20, A31 220 – 240 PIR-Foams between 300 and
ned by properly choosing the glycol 600
component. One approach success-
PIR-Foams, flame For use in flame
fully applied is the use of 2-ethyl- F03 250 – 270
retarded duromers retarded foams
hexane-1,3-diol together with tere-
phthalic acid or esters (Fulev, 2007). Sealants, Adhe- Low reactivity
By this type of process APP of rather H62 200 – 240
sives polyol
low hydroxyl and acid numbers are
produced using a similar process and Duromers, panel
M21, A42 300 – 340 –
equipment as described. Table 4 foams
depicts some results.
To adjust the
Duromers, panel
The polyols of Table 4 were produced F04 300 – 340 degree of flame
by a transesterification process em-
ploying terephthalic acid dimethyl Rigid foams, panel
ester (DMT) as starting material. They M22, A46 360 – 400 –
were designed to meet the require-
ments of sealants with pot lives ex- Flame retarded To adjust the
tending 20 minutes. F06 380 - 400 rigid foams, panel degree of flame
foams retardance
Low reactivity
H65, H66 320 - 380 Sealants, coatings
The application of the APP produced
in variants of this general transesterifi- Tab. 5) Application of aromatic polyester polyols.
cation process is in nearly any field of
rigid polyurethanes. So, the properties
of the polyols can be carefully adjusted use of such APP not only ecologic and incinerated or brought to a landfill as
to the application of the client. In Table 5 technical aspects have to be consid- long as this works.
some general rules for application are ered. Emphasis is on the economy of
exemplified. the process and its products. A rough calculation of the production
costs leads, of course, to a dependence
By employing different combinations The costs of the process are to a great on the amount of APP produced. Con-
and ratios of the raw materials named extent determined by raw material sidering a 4,000 t/a plant, the produc-
one is able to meet exactly the condi- costs. The prices of the additives used tion costs are in the range of 850 €/t
tions the respective client needs. Fur- in the various processes, ethylene (with the PET calculated with 300 €/t ).
thermore, based on such a broad range glycol, adipic acid, glycerol, catalysts At higher production levels these costs
of properties of the APP it is possible to a.s.o. increased during the last years may be as low as 700 €/t and when re-
formulate nearly any rigid polyuretha- by 25 to 50 %. E.g. ethylene glycol ceiving PET at no costs even at 630 €/t.
ne system of high performance. Thus, rose to about 1100 €/t, adipic acid to The market price of high quality APP
when employing the M20 combined nearly 1700 €/t. (i. e. nearly colourless, clear) is bet-
with a proper formulation at an isocy- ween 1550 and 1850 €/t. So, for any
anate index of about 500 extraordinary The PET wastes considered here are PET producer the performance of such
thermally stable PIR foams can be pro- in the range between 0 and 850 €/t a process will be of benefit both with
duced. It was proved with such a for- depending on the type. The Chinese respect to the waste deployment and
mulation to receive a foam in the den- Green Fence Action further enhances to profit from a side stream.
sity region of 40 g/cm³ being stable in the pressure to the prices of European
the range of –190 to +190°C showing a plastics recycling materials. Any PET VII. CONCLUSION
deviation in the three spatial directions manufacturer produces some 1.5 to 3 %
of less than 1.5%. of the total production as waste, of In this paper we reported on work of
which only minor amounts are a valu- the development of a new group of
VI. ECONOMY OF APPLICATION OF APP able good to be purchased by custo- APP based on the transesterification of
mers. Most of these wastes have to be poly(ethylene terephthalate) with gly-
When considering the production and treated as “true” waste and either be cols and triols by a new process and,

74 THWildau
Wissenschaftliche Beiträge 2014
based thereon a concept for a new AUTHORS
plant, which resulted in new types

Dipl.-Chem. Eckhart Kornejew
for application in nearly any field of Fachbereich Ingenieur- und Naturwissenschaften
Technische Hochschule Wildau [FH]
rigid polyurethanes production. The
basic PET best used is material from
MSc Kiril Dimitrov
industrial production to make near-
Fachbereich Ingenieur- und Naturwissenschaften
ly no problems in transesterification Technische Hochschule Wildau [FH]
and having the highest profit marges.
In case of fibre or bottle PET additio- Prof. Dr. rer. nat. Michael Herzog
Fachbereich Ingenieur- und Naturwissenschaften
nal problems arise from contaminants
Technische Hochschule Wildau [FH]
which have to be overcome by newly
developed treatment steps at the end

of the process combined with a new
technology to perform these process

steps. The APP produced this way lead
to high performance polyurethanes
with outstanding properties. Further-
more, the APP are produced with very
good economy especially when using
in-house wastes of the PET production
and produce the APP as a side stream.


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Wissenschaftliche Beiträge 2014 75

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