Chapter 4

ADDITIVES FOR RECYCLING AND DEGRADATION OF POLYMERS

4.1. Additives for recycling

The demand of recycled plastics is widely accepted and increasing at the present,
therefore, recycling system may open significant markets for additives. Depending on the
concentration of the active stabilizers in the waste material and the long-term
requirements for thermal/photo stability, it may be necessary to re-stabilize the
reprocessed compound. Two types of additives may be used to achieve this goal: (i) to
enhance the properties of plastics recovered from waste and also (ii) additives which may
facilitate the recycling process, particularly for providing fast and effective identification
of types of the plastics.
4.1.1. Re-stabilizing additives: It is reasonable to consider the recycled industrial srap as
a virgin polymer from the stabilization point of view and therefore, should be re-
stabilized, prior to re-processing, in the same way as the original material.This also holds
good for stabilization of post-consumer recycled plastics but other factors e.g. degree of
degradation, amount of residual stabilizers and extent of contamination, should also be
considered. Combination of a hindered phenol with a hydrolysis-resistant phosphite has
been shown to have an effect on polypropylene with only small amount (0.05%) addition
of phosphite exhibiting good inhibition of degradation during extrusion upto five passes.
The phosphite not only protects the polymer but also protects and conserves other
stabilizers that are important for long-term stabilization e.g. hindrered phenols. Good
results have also been achieved with with HDPE bottle wastes in re-stabilizing with 0.2
0.3% of phenolic antioxidant blends.
Several companies have been looking at the potential of additives in recycling
plastics as materials by physical reprocessing. Ciba Giegy formed a specialized group in
1990 for additives in recycling based on its Marienberg subsidiary. It already has
developed stabilizer blends for commingled plastics (Recyclostab) and has a special
project working on ‘tracer’ additives, which would help in automatic separation of
different types of plastics. Recyclostab improves the ultimate elongation of reclaimed PP
bumpers by a factor of three. The resistance to thermal degradation is also doubled
compared with straight reclaim. Another aspect is destabilization degradation of plastics
post-use, aiming at a degradation product that is in the domain of the basic raw materials
(namely oil or monomer) for which it does not see an immediate solution.
Most manufacturers have added to their stabilizers a suitable range formulations
for recycled material. Akcros has developed calsium/zinc stabilizers containing a number
of co-stabilizers in its Interlite range for PVC flooring and profile recycling. Ciba Giegy’s
Irganox 245 antioxidant cuts to 25% yellowing index of recycled PS yoghurt pots during
ageing. Irgastab CZ 2000 calsium/zinc stabilizer at 2% addition reduces the yellow index
of PVC window profiles. A 4:1 blend of Irgafos 168 and Irganox 1010 at 0.3% addition
aids PET to retain more of its intrinsic viscosity through repeated processing (up to five
times). Rohm and Haas offers EXI 3600 an encapsulated rubber additive that can restore
the melt strength of low molecular weight polycarbonate to about the same level as
virgin. It can also improve notched Izod impact from less than 50 J m-1 (for normal

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recyclate) to about 300 J m-1 at 20% addition level. Electrical properties are virtually
identical to the virgin material. Dosing waste PET with EXI 5375 (20%) restores
properties to virgin level. Quantum offers a Spectratech line of colorant and additive
concentrates for recycling: the antioxidants boost heat stability and improve the oxidation
resistance of the recyclate.
Bennet BV reported that addition of its BRC 200 compatibilizer to a mixed waste
stream of equal parts of LDPE, LLDPE and PP homopolymer and copoloymer boosted
impact strength to higher than the single components in injection moulded parts.
Compatibilizers containing branched ethylene, EVA and elastomers are added to scrap of
LDPE, HDPE and PP make drainage pipes. Dexco (Exxon / Dow) has developed styrenic
block copolymers as compatibilizers to improve impact strength. Vector SBS (without
halide salts) gives better heat stability than conventional block copoloymers due to
absence of residual halides which can lead to property degradation. It can boost ultimate
elongation and impact strength of PP waste. DuPont Fusabond compatibilizers (mainly
based on maleic anhydride-grafted polyolefins) have been used in Finland with
miltilayered film waste, allowing the recycler to reprocess it as video film cassettes or
bottles.
Reclaimed thermoplastics often contain significant amounts of water. Addition of
calcium oxide makes it possible to scavenge up to 32% moisture and to mould at only
marginally extra cost. In inherently hygroscopic materials such as polyamides, calcium
oxide may often avoid the use of prolonged oven drying. Moreover, fillers can import
moisture into polyolefin compounds that can contain as much as 25% leading to porosity
in mouldings. A peroxide concentrate for polypropylene has been developed as an
alternative to liquid peroxide for melt flow modification of recyclate and off-grade PP
material.. A high level of active peroxide is said to make the material very economical: a
1% loading can increase the melt flow rate of standard PP to over 150 g (10 min)-1.
Chemson company reports that its additive systems for foamed PVC pipe production
reached a stage at which they will permit recyclate material to be incorporated without
any trade-off in terms of quality. The company suggests that for a foamed core pipe plant
with an output about 350 kg h-1 , the savings in materials costs could run to a six-digit
amount during a year.
4.1.2 Additives for identification of plastics: Much interest has been expressed in the
possibility of developing safe and reliable additive systems which could act as ‘markers’
in waste plastics products and triggering the separation mechanism. There are major
problems to be overcomed in developing a system that can operate on a fully commercial
scale. An organic marker system which can be added to polymer molecules has been
developed by Eastmen Chemicals and if successful, it is envisaged that such a marker
could provide a relatively commercial means of identification and therefore separation of
different types of plastics which could be operated on a continuous industrial scale. This
system is said to work both with transparent and opaque plastic. Chlorine and bromine
components, heavy metals and various types of filler can be identified in plastic by a
number of technologies in post comsumer waste.
Additives can add problems for recycling of plastics but they could also be one of
the means of identification which might simplify the process. The vital factor is that any
method of automatic selection and/or separation must able to operate on a large scale
over large volumes of plastic wastes probable conveyorised. Elements of high atomic

2
weights can be identified rapidly by means of X-ray florescence. This technique could be
used to separate compounds containing chlorinated or brominated flame retardants but to
date it has been used in practice only for separating PVC bottles from other plastics.
Transparent bottles can be separated from opaque green colored bottles by detecting the
difference the tarnsferency with the aid of transmission sensors which determine the
transmission of waves of specific length so making it possible to separate PET from
HDPE. Rapid spectroscopic method include a) analyzing the whole polymer molecule
without altering composition, near infra-red (NIR), mid infra-red (MIR), Raman
spectroscopy (FTR) and X-ray method, and b) using pyrolytic decomposition. The only
systems used on an industrial scale so far are based on X-ray and IR, mainly for bottles,
since the high cost of PET providing an incentive. NIR systems are also used in many
parts of the world and its combination with a colour identified systems has been
developed by Binder, Austria, offering simultaneous sorting of up to ten fractions at 1200
kg h-1 to 99.9 % accuracy.
Laser light is also used in thermo-optical methods of identification, creating local
heating on the specimen by directing a beam from a CO2 laser fro a fraction of a second.
Depending on the coefficient of absorption, thermal conductivity or heat capacity
characteristic of the material, there are different temperature distributions. The technique
is been studied at the laser center in Hanover, Germany and has been used successfully to
date in the identification of polymers including polyamides, fluoropolymers,
polycarbonates and acrylics. It is a particularly interesting technology because the error
of measurement is not affected by factors such as colouring, additives such as plastisizers
or the contamination of the surface

4.2. Additives for degradation

The degradation which is caused by the addition of some chemicals called as
chemical degradation or additive sensitized degradation. They are acids, bases and/or
other chemicals which they can proceed hydrolysis, ionization and/or decomposition of
polymers.
Certain inorganic and organic compounds are excited by light, heat or high-
energy radiations and transfer their excitation energy to polymer molecules or to oxygen
molecule forming singlet oxygen (O2). Thus, these compounds induce and promote
polymer degradation by transferring energy to polymer or are decomposed itself into free
radicals which may initiate degradation and oxidation of polymer. These compounds are
called sensitizers and this phenomenon as ‘sensitized degradation’. The sensitized
reactions in polymer chemistry have been widely reviewed [1-3] and divided:

4.2.1. Inorganic metal oxides: The activities of inorganic pigments are related to their
semi conductor zones. Upon UV irradiations, these pigments (zinc oxide or titanium
dioxide) generate exciton (electron +ve hole pairs), each species being delocalized in the
conductance or valence bond, respectively. It was found that zinc oxide and titanium
dioxide catalyze the formation and decomposition of peroxides under UV irradiation by
the following reaction mechanism.[4]

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 [ Ti4+ OH]
hν e- + P+

TiO2
H2O + O2 OH + HO2
hν

In which water and oxygen are constantly being consumed to destroy the polymer.

4.2.2. Metal salts/ metal ions : The inorganic salts play an important role in transferring
of electrons in photoreactions. The traces of metal impurities in polymers are believed to
sensitize the polymer degradation. These metallic impurities are incorporated into
polymer matrix during manufacturing (polymerization catalytic impurities) and
processing (impurities, dusts and by chemical corrosion of the processing equipment).
The following are the various possibilities of sensitizing the degradation of polymers by
metal ions: [5]
M (n+1) + + PH M n+ + P + H+
In the presence of oxygen, macroradicals produces peroxides which subsequently induce
the degradation. In the presence of the functional groups (e.g. aldehyde) metal ions will
directly react with polymer-chain and proceed the degradation processes. The strength of
the metal ion as an oxidizing or reducing agent determines its relative ability to catalyze
the oxidation degradation of the polymer. The effect of the metal ion is thus to speed up
the rate of degradation of polymer.
The biodegradation of polymers/plastics containing iron dithiocarbamate upon
photodegradation leads to embrittlement and strongly supports the microbial degradation
within 6 months incubation in a medium in which the plastic is the only source of carbon
[6, 7]. Examination of the surface after microorganisms removal was found to have
decreased by ~15 %. This observation has considerable significance for composting of
organic waste containing degradable plastics since the rate of bioassimilation of the
degradable polymers occurs at rate similar to much biodegradable organic matter in a
managed aerobic compost and more rapidly than some of the more intractable
components of biological litter such as ligniseous materials.

4.2.3. Carbonyl compounds: The most important sensitizing carbonyl compound is

benzophenone. The photochemically reactive state of benzophenone is its first triplet
excited state. The singlet oxygen can be formed between the excited triplet state of
benzophenone and molecular oxygen. Benzophenone can abstract hydrogen from
polymer and thus sensitizes oxidative degradation of polymers. Guillet [8] synthesized a
carbonyl group containing polymer, which degrade upon exposure to sunlight but remain
intact if kept indoors. A wide range of derivatives of diketones, aldehyde, quinines and
azo- compounds also effectively sensitize the photo and thermal degradation of polymers
by the primary process as mentioned in the above paragraphs. The photochemistry of
polycyclic hydrocarbons has been extensively studied and they found to sensitize the

4
degradation. The main reactions responsible for sensitization in aromatic hydrocarbons
were fluorescence, phosphorescence, dimmer formation and energy transfer.

4.2.3.Dye - /photosensitive additives: Several different types of dyes are used for the
dyeing of polymers and textile fibers. All dye molecules are excited to singlet states by
the absorption of light, heat or high energy and then transformed to triplet states by the
absorption of light, heat or high energy and then transformed to triplet states. Over the
years, two general mechanisms have evolved to account for the dye-sensitized oxidation
of polymers. The first originated from the earlier work of Edgerton, who proposed a
mechanism in which excited state of the dye, normally triplet, is quenched by ground
state molecular O2 to produce active singlet oxygen. This singlet oxygen then reacts with
polymer or H2O to form hydro peroxide and/ or hydrogen peroxide both of which may
induce further oxidative breakdown of the polymer.[9]

D
hν 1 3
D
O2 1
D O2 + D
(Dyes)

PH
Oxidation products

Dyes initiate the degradation process by hydrogen atom abstraction which creates
a free radical center (P•) in the polymer, which is then attacked by O2 in the usual way:
hν
D 1
D + PH P
(Dyes)

The presence of alkali was found to accelerate the process and under these
conditions, the dye is believed to abstract an electron from the hydroxyl anion to give
active hydroxyl radical (O°H) and the dye radical anion (D°-). By using dyes, it is
possible to extend the spectral range for the photo degradation of polymers into the
visible region. Edgerton has found that anthraquinone dyes sensitize the photo oxidation
of nylons and cellulose. Amino acids are specially susceptible to dye sensitized photo-
oxidation.

References
1. J.F.Rabek, (1964) Polymer, 9; 128 and 221
2. J.F.Rabek, (1974) Comprehensive Chemical Kinetics, C.H. Banford, and C.F.Tipper
(Ed.) Elsevier, Oxford, 14; 265.
3. Ya.A.Ershov, S.I. Kuznina and M.B. Neiman (1969) Uspek Khim.,38; 289.
4. M.C.Morkham, M.C. Hannon, R.M. Paternostro and C.B.Rose (1998) J.Amer.
Chem.Soc., 80; 5394
5. C.E.H. Bawn, S.A. Chaudhari (1968) Polymer, 9; 81
6. J.G.L.Griffin, Adv.Chem.Ser., 134, Fillers and Reinforcements for Plastics,

5
 Am.Chem.Soc.,1974, p. 159
7. F.H.Otey, A.M.Mark, C.L.Mehltretter and C.R.Russel, Ind. Eng. Chem. Prod. Res.
Dev., 1974, p.13
8. J.E.Guillet. (1972) Naturwissenschaften, 59; 503
9. G.S.Egerton, (1947) J. Soc. Dyers. Col. 63; 161