Polymer Degradation and Stability 91 (2006) 2249e2256

www.elsevier.com/locate/polydegstab

Invited review

How will additives shape the future of plastics?*

Rudolf Pfaendner
Ciba Spezialitätenchemie Lampertheim GmbH, D-68623 Lampertheim, Germany
Received 8 September 2005; accepted 11 October 2005
Available online 17 April 2006

Abstract

Additives are essential components of plastic formulations providing maintenance and/or modification of polymer properties, performance
and long-term use. The extension of polymer properties by additives has played a substantial role in the growth of plastics. At the beginning of
the plastics age additives were used mainly to maintain polymer properties and to help plastics to survive heat treatment during transforming
processes. The next generation of additives provided extension of service life as well as modification of mechanical and physical properties.
These well-established additives e antioxidants, heat stabilizers, light stabilizers and others e cover the requirements of standard plastics
and today’s mass applications. The more recent developments of high-performance additives address more stringent or new requirements,
more severe processing and use conditions and/or environmental concerns, but still with the main target of maintaining plastic properties.
The future will introduce more and more new effects and functionalities through additives in plastic applications tailoring the properties of poly-
mers and offering a vast potential of innovation in the plastics area. Recent examples of emerging technologies show that additives will not only
modify the polymer itself and add new properties, but can also, when incorporated into the plastic, beneficially impact properties, which are of
high value for the user. The paper shows the role of additives used in plastics from the past to the present with the focus on stabilization and
performance of additives incorporated during melt processing, and outlines future trends.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Antioxidants; Light stabilizers; Flame retardants; Recycling; Nanocomposites; Polymer modification

1. The history of plastics is the history of additives: no
plastic growth without additives
When we are talking about the growth and success of plas-
tic materials and that we are living in the plastic age, it is too
much simplified. Although worldwide consumption of plastics
is now 176 Mt and is growing by about 5% annually [1], most
of the plastics used today are only applicable in the intended
final application in the presence of a number of ingredients
in addition to the polymer itself.
*
Based on a presentation given at the 23rd discussion conference ‘‘Current
and Future Trends in Polymeric Materials’’, at the Institute of Macromolecular
Chemistry, Academy of Sciences of the Czech Republic, Prague, 26e30 June
2005.
E-mail address: rudolf.pfaendner@cibasc.com
Even at the dawn of plastics, when they had limited commer-
cial use and were mere curiosities, additives were a must. The
first synthetic commercial thermoplastic, Celluloid, is a success
story of additives, when camphor was added to make the intrac-
table cellulose nitrate flexible [2e4]. The effect of camphor as
an additive or plasticizer was independently detected by Alex-
ander Parkes in the UK (he named his product ‘‘Parkesine’’)
and John and Isaiah Hyatt in the US (‘‘Celluloid’’) [5]. Plasti-
cized PVC was developed in the 1930s by using dialkyl phtha-
lates and the key to processing rigid PVC was the development
of heat stabilizers such as metal soaps, lead salts and organotin
compounds. Light stabilizers were first used in cellulose nitrate
coatings on packaging to protect packaged oil and food [6].
This was soon followed by the use of benzophenones and phe-
nyl salicylate to protect plastics from weathering [7]. The
breakthrough of polypropylene, a thermally very unstable ma-
terial, and other ZieglereNatta polyolefins, was only possible

0141-3910/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2005.10.017
2250 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256

through the development of efficient antioxidants benefiting 235

from the symbiosis between the polymer and the additive
industries.
The primary target of the early additives was mainly to help
the plastic to survive the processing used to transform it into
the desired shape. Typical examples of these additives are an-
tioxidants, heat stabilizers, processing aids, plasticizers and lu-
bricants. Soon came the commercial need not only to maintain
properties of plastics but also to extend their service life, for
example, in outdoor applications. This forced the development
of light and UV stabilizers. Further protection requirements
(biocides, flame retardants) and the wish to modify mechanical
and physical properties led to the use of additional materials
(e.g. fillers, glass fibres, impact modifiers, antistats, nucleating
agents). These well-established additives cover today’s re-
quirements of standard plastics and their mass applications.
Overall, additives embrace a wide area of different ingredi-
ents used in plastics. The consumption today is in the range of
8000 kt corresponding to a value of 18 billion US$ (Fig. 1;
[8]). PVC is still the main polymer of additive consumption
as most of the plasticizers and heat stabilizers representing to-
gether one-third of the additives production are used there.
Plasticizers still dominate the market but growth is slow and
per kilogram value is low. Flame retardants are the fastest
growing market with about 6% annually [9]. 40% of antioxi-
dants and 45% of light stabilizers are used in polypropylene
applications [10].
Not surprisingly, the growth of additives parallels the
growth of plastics [11e15] as shown for the representative
classes of antioxidants and light stabilizers (Fig. 2).
2. Additives today: optimized for targeted requirements
The more recent developments of high-performance addi-
tives address more stringent or new requirements, more severe
processing and use conditions and/or environmental concerns,
but still with the focus on maintaining the plastic properties.
In parallel to the growth of polyolefins the industry has seen
a dramatic improvement of additive performance especially in
the processing stabilizer/antioxidants and light stabilizer area,
either through new chemical structures or through synergistic
effects. A well-known example of improved processing stabil-
ity is the combination of phosphites (e.g. IRGAFOSÒ 168) and
33.5 250
80 176
6 12
0
0.3 58
0
1.6
0
1940 1950 1960 1970 1980 1990 2000 2010 2020
Plastics production worldwide (mio t/a)
Light stabilizers consumption worldwide (kt/a)
Antioxidants consumption worldwide (kta)
Fig. 2. Consumption of plastics, light stabilizers and antioxidants since 1950.
phenolic antioxidants (e.g. IRGANOXÒ 1010) outperforming
the performance of the individual components [16]. This com-
bination can be even further improved by using as a third com-
ponent a benzofuranone derivative (e.g. IRGANOXÒ HP 136;
[17]), which is a very powerful radical scavenger and proves
its efficiency at the increased processing temperatures, com-
monly used today (Table 1).
The development of UV and light stabilizers was mainly
marked by new chemistries. The family of UV stabilizers
based on benzotriazoles and benzophenones has been ex-
tended, e.g. by hindered amine light stabilizers (HALS) and
hydroxyphenyltriazines. The HALS chemistry, introduced in
the early 1970s, was soon extended by designing new chemi-
cal structures with improved performance such as polymeric
derivatives as well as benefiting from synergistic blends.
Through these measures a tremendous improvement in light
stabilization of plastics, equal to several orders of magnitude,
has been achieved in the course of the last 30 years.
The trend for innovative additives in protecting the polymer
properties and extending service life time is unbroken. New
developments in the traditional area of processing, long-term
heat and light stabilizers take place where additives with im-
proved performance or at low use concentrations are needed
to provide an effect. Niche plastic markets which can demand
higher market prices have created the opportunity for additive
suppliers to exploit new and modified additive chemistries. A
few recently published examples should be at least mentioned
to give some indications of the specific areas:

Plasticizers Flame Table 1

Retardants
Stabilization of polypropylene homopolymer: effects of the extrusion tempera-
4763
1997 ture and stabilizer system on the melt flow rate (MFR) during multiple extrusion
1887 1454 Stabilizer system MFR, multiple extrusion in 1st and 5th path at
525 1715 220
C 250
C 280
C 310
C
1330 807
1 5 1 5 1 5 1 5
Others 0.033% IRGANOX 1010 3.5 4 5 7.5 7 17 9 60
Light Impact 0.067% IRGAFOS 168
Stabilizers Antioxidants Heat Modifiers
Lubricants / Stabilizers 0.033% IRGANOX 1010 3.5 4.5 3 6.5 5.5 11 7 18
Acid Scavangers 0.067% IRGAFOS 168
0.01% IRGANOX HP 136
Fig. 1. Turnover of additives (M$) in 2004, according to Ref. [8].
 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256
- TINUVINÒ XT 833: light stabilizer for outstanding dura-
bility of flexible PVC [18];
- TINUVINÒ NOR 371: light stabilizer for agrofilms in con-
tact with pesticides [19];
- TINUVINÒ XT 850: long-term weatherability of
moulded-in-color TPO exterior parts [20];
- IRGANOXÒ 1726: a multifunctional stabilizer providing
excellent process stability and long-term protection of ad-
hesives, e.g. based on SIS/SBS [21];
- IRGASTABÒ Cable KV 10: liquid stabilizer system for
peroxide cross-linked PE power cables [22].
Even in fields such as lubricants and PVC heat stabilizers
new market introductions can be mentioned. For example met-
allocene catalysts could deliver a new range of waxes [23]. En-
vironmental pressure on lead stabilizers forced the
development of a new generation of pyrimidine PVC stabi-
lizers [24].
A few other developments will be illustrated in the following
examples in more detail. The targeted markets cover the increas-
ing need of less migrating or non-migrating stabilizers, the need
for alternative solutions for traditional applications (e.g. halo-
gen free flame retardants) and the protection of new plastic ma-
terials and compositions (recyclates, nanocomposites).
2.1. Graftable antioxidants with non-staining
performance
Amines, e.g. 6PPD are used in the elastomer area as effi-
cient stabilizers providing antioxidant, antiozonant and antifa-
tigue behaviours. Without these additives the typical
properties of e.g. car tyres would not have been possible.
These aminic stabilizers inherently show a number of disad-
vantages that reduce their potential use such as discoloration,
staining (i.e. transfer of discoloration), extractability, migra-
tion and thermo-oxidative formation of primary aromatic
amines which result in limited food contact approval.
Binding antioxidants to the polymer backbone via grafting
reactions is a suitable approach to cope with the mentioned
disadvantages. The new IRGAZONEÒ 997 was developed as
a graftable antioxidant, antiozonant and antifatigue agent
[25]. It shows non-staining, low discoloration behaviour and
is significantly less extractable than 6PPD, with FDA and
BfR food contact approval. IRGAZONEÒ 997 retains its effi-
cacy even after extended contact with liquid media as shown
in a model experiment for a NR/BR vulcanizate (Table 2).
The mechanical properties, measured as tensile strength after
extraction and subsequent oven-aging, are maintained at
high level compared to 6PPD, proving the low extractability.
With these properties the additive can be used for milk liners,
hoses, wiper blades and engine mounts, suitable for NR, SBR,
NBR and CR elastomers.
The key feature of the described graftable antioxidant is on
the one hand to keep the amine functionality for performance
and on the other hand to provide with the thioether group
a graftable link, which is able to react with the double
bonds of the elastomer. As it was found that during the
2251
Table 2
NR/BR vulcanizate after 3 days extraction in acetone and subsequent oven-ag-
ing at 80
C
Stabilizer Tensile strength (MPa) after weeks at 80
C
0 1 week 2 weeks 3 weeks 4 weeks
None 20 8 6 5 5
6PPD 21 8 6 5 5
Irgazone 997 22 19 15 10 6
manufacturing process oxidation results in the corresponding
sulfoxide, which is the reactive intermediate in the process,
an even improved class of graftable antioxidants could be de-
veloped [26].
2.2. NOR-HALS: from light stabilizers to flame
retardants
It is a well-known problem that the excellent HALS addi-
tives lose a certain part of their performance in greenhouses
when pesticides are used. Sulfur and halogen containing com-
pounds from agrochemical decomposition form acidic resi-
dues. These acids deactivate the basic piperidine groups of
the HALS, thus inhibiting the formation of active radical scav-
engers. Furthermore, sulfur and halogen containing chemicals
can react with nitroxyl radicals, thereby depleting the concen-
tration of the active radical scavengers. This weakness led to
the development of low interacting NOR-HALS, which pro-
vide UV, thermal and chemical resistances, light transmission
and durability for sulfur burning greenhouses and mulch films
exposed to heavy dosages of pesticides [19].
In a similar way to pesticides flame retardants such as hal-
ogens or phosphorous compounds generate thermally or pho-
tochemically acidic species which result in inferior UV
stability. Therefore, the efficiency of NORs in combination
with brominated flame retardants could be demonstrated. Sur-
prisingly it was found that the nitroxyl ethers not only improve
the UV stability but also contribute to flame retardancy. Even
without any additional flame retardant it was demonstrated
that NORs alone can achieve flame retardancy, e.g. in polypro-
pylene fibres and films according to the standards. For exam-
ple FLAMESTABÒ NOR 116 provides flame retardancy at
a concentration of only 0.5% passing the NFPA 701 fibre
test [27] on polypropylene knitted socks [28].
Moreover the addition of NORs as FR synergist can im-
prove the efficiency of conventional brominated flame retar-
dants as demonstrated in Table 3, where the combination of
NOR and decabromodiphenyloxide surpasses the FR alone.
Therefore, it is possible to design with NORs flame retar-
dant polyolefin moulding compositions with lower levels of
halogenated flame retardants and, in addition, to eliminate an-
timony trioxide which is often used as FR synergist. Low FR
concentrations and no antimony trioxide result in polymers
with improved processability, better mechanical properties
and reduced smoke density. For example UL 94 V-2 rating
is achieved in PP injection moulded plaques at concentrations
as low as 3.5% of formulations containing FLAMESTABÒ
NOR 116 [29].
2252 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256

Table 3 (RECYCLOSTABÒ 451 AR) (Table 4) and have been proved

NFPA 701 (1996) test results in polypropylene fibres to be beneficial in PP recyclate applications [30].
Additive Weight loss (%) Drip burn time (s) Rating In the typical standard 120
C thermal test, the mixed
None >40 50þ Fail HDPE/PP sample, containing only 5% PP, survived only for
4% Decabromodiphenyloxide 0.8 7 Pass 18 days (Table 5). In the case of 100% HDPE, this survives
2% Decabromodiphenyloxide 5 10 Fail 73 days without restabilization and 144 days with restabiliza-
1% Decabromodiphenyloxide 0 4 Pass
0.25% FLAMESTAB NOR 116
tion by 0.2% RECYCLOSTABÒ 451 AR, achieving by this
easily the same level as virgin HDPE (131 days). It means
that in any case the mixed material cannot be used for typical
The activity of the nitroxyl ether as flame retardant is based HDPE applications without proper restabilization. Adding as
on the thermal degradation of nitroxyl ethers which leads to little as 0.2% of the stabilizer blend to the mixed polyolefin
the formation of either alkoxy and aminyl radicals or alkyl increases this period to the 100 days level once again. With in-
and nitroxyl radicals. Aminyl and alkoxy radicals are very re- creasing proportions of PP in the PO mixture, the long-term
active and provide on the one hand degradation of polypropyl- thermal stability of the recyclate decreases accordingly. Addi-
ene (and cross-linking of polyethylene). On the other hand tionally the negative impact of impurities like PVC is signifi-
they are involved in the free radical chemical reactions during cant even at low concentrations and has to be countered by
the combustion process. adding a higher stabilizer concentration.
In synergistic combinations NORs can interact with bromi- The need for specific stabilizers of recyclates is true as well
nated flame retardants and facilitate the release of bromine, for outdoor applications as shown, e.g. in the restabilization of
consequently increasing the overall FR performance. Addi- bottle crates, where a synergistic blend of polymeric HALS,
tionally ignition of a polymer leads to the formation of volatile process and long-term thermal stabilizers (RECYCLOS-
combustion products, releasing heat during burning. This heat SORBÒ 550) is used. By adjusting the stabilizer level the per-
energy from the flame is then fed back to the polymer to sus- formance of virgin material can be matched and closed-loop
tain the burning process. It is believed that the thermolysis of recycling from bottle crate to bottle crate is feasible [32].
NOR significantly reduces the amount of thermal feedback
from the flame.
The example of NOR flame retardants shows that continu- 2.4. Stabilizers for nanocomposites
ous improvements of traditional chemistry like HALS can
even find entrance with new effects in different applications. Nanotechnology is one of the big buzzwords of the 21st
century. One of the already realized examples in plastics is
2.3. Recyclates need tailor-made additives the use of nanosized clay to provide nanocomposites with su-
perior mechanical performance at low filler level in compari-
The mechanical recycling of plastics, i.e. the reuse of used son to standard filled materials. In order to be compatible
material through remelting is a substantial part of an integrated with the polymer the clay is modified by ion exchange with
approach to waste management. Mechanical recycling is also long-chain ammonium compounds allowing first intercalation
a challenge for the selection of efficient additives as well of the clay with the polymer and finally exfoliation. Despite
[30,31]. Fundamental differences of virgin material and recy- the benefits of the process it is a challenge for the long-term
clate include structural inhomogeneities due to irreversible performance as the filler with its huge surface and the presence
changes induced by the first life through thermo-oxidative or of ammonium groups, which are susceptible to Hofmann’s
photo-oxidative effects. Furthermore recyclates contain impu- elimination, considerably reduces the thermal stability.
rities in trace concentrations that could not be removed by pu-
rification steps. As a result, most recyclates are more sensitive Table 4
Long-term heat stability of polyolefin recyclate
to oxidation and photo-oxidation than virgin polymers.
Recyclate of HDPE bottles with caps made from PP is an Substrate Stabilizer Time (days) until
embrittlement at 120
C
example of mixed polyolefins which are not used as such as
virgin material. In comparison to 100% HDPE of similar Virgin HDPE Standard 131
100% HDPE No restabilization 73
type, the impact of the PP in the recyclate on processing and
recyclate Restabilized þ 0.2% 144
even more significantly, on long-term thermal stability, is RECYCLOSTAB 451 AR
rather strong. HDPE that contains only small quantities of sta- Recyclate 95% No restabilization 18
bilizers, can, in terms of oven-aging, be considered relatively HDPE/5% PP Restabilized þ 0.2% 116
stable; PP, on the other hand, can only be used for long-term RECYCLOSTAB 451 AR
Recyclate 90% Restabilized þ 0.2% 94
applications when it is well fortified with stabilizers. Improve-
HDPE/10% PP RECYCLOSTAB 451 AR
ment of the stability through addition of blends of phenolic an- Recyclate 80% Restabilized þ 0.2% 74
tioxidants and phosphites is very limited. It seems that the HDPE/20% PP RECYCLOSTAB 451 AR
specific behaviour of the blend is regulated mainly by the Recyclate 80% Restabilized þ 0.2% 50
relatively low concentration of PP. These facts are confirmed HDPE/20% RECYCLOSTAB 451 AR
PP þ 0.2% PVC
by using stabilizer combinations that include antiacids
 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256
Table 5
Stabilization of polypropylene nanocomposites (composition: 80% PP, 15%
PP-g-maleic anhydride, 5% Nanofil 15 (supplier Südchemie))
Substrate Stabilizer MVR after Time (days) until
1 and 5 embrittlement
extrusion cycles at 135
C
PP Standard >40
PP/PP-g-MAH 80/20 0.2% IRGANOX 11.5/16.5 >40
B 225
PP nanocomposite 0.2% IRGANOX 6.8/8.3 14
B 225
0.2% IRGANOX 7.3/10.0 n.d.
HP 2225
0.2% CGX n.d. 23
NC 66
0.5% CGX n.d. 33
NC 66
0.7% CGX 5.9/5.0 >40
NC 66
n.d. ¼ Not determined, MVR ¼ Melt volume rate.
The state-of-the-art polypropylene nanocomposites are
blends of PP, maleic anhydride-grafted PP and the organically
modified clay. These blends show a strong increase in MVR, in-
dicating degradation of the PP matrix after thermal stress. As ex-
pected, the degradation can be reduced by adding conventional
stabilizers, but even at high concentrations or with high-perfor-
mance stabilizers containing benzofuranone derivatives (IR-
GANOXÒ HP 2225) there is still a significant MVR increase.
However, the degradation can be almost completely prevented
even after five extrusion cycles by using a recently developed ex-
perimental stabilizer system (CGX NC 66), which addresses the
specific stabilization needs of polyolefin nanocomposites, act-
ing as filler deactivator and amine scavenger ([33]; Table 5).
A further weakness of conventional polyolefin nanocompo-
sites is the reduced long-term thermal stability due to the or-
ganic modification of the clay and the fact that the
compatibilizer (PP-g-MAH) negatively influences the thermal
performance. A conventionally (0.2% IRGANOXÒ B 225) sta-
bilized PP nanocomposite becomes brittle already after 14
days in the accelerated heat-aging test at 135
C. Using the
proper quantity of CGX NC 66 leads to a significant improve-
ment of the long-term thermal stability almost up to a value
known for unfilled, stabilized PP.
The nanofiller, like all fillers, adsorbs stabilizing additives
which are then no longer available to fulfil their protective ac-
tivity. Due to its huge surface this phenomenon will be even
more crucial. Moreover, the nanoclays used are mainly natural
materials and therefore include ionic impurities, e.g. metal
ions, which are known to accelerate the degradation of poly-
mers. And last but not least the photodegradation of the
maleated polypropylene leads to volatiles, which further accel-
erates the degradation.
The new tailor-made stabilizer system CGX NC 66 is well
dispersed in the polyolefin nanocomposite and is able to scav-
enge the resulting volatiles. Therefore, the degradation during
processing as well as the odour are reduced. Overall, the ad-
vantages of nanocomposites, such as significant increase in
elasticity modulus, by almost maintaining the impact strength
2253
combined with high elongation at break, are no longer over-
compensated by the disadvantages such as decreased long-
term thermal stability or enhanced degradation during
processing.
As described, the ammonium modifier and the compatibil-
izer PP-g-maleic anhydride impart several weaknesses into the
composite. A more recent approach of preparing composite
materials omits maleic anhydride compatibilizers and uses un-
modified filler. This new version shows at 5% filler level
clearly superior mechanical properties, e.g. impact properties
and a higher Vicat temperature than the state-of-the-art nano-
composites. This material is in itself thermally more stable
during processing and with regard to long-term thermal stabil-
ity. Additives based on copolymers provide dispersion of the
unmodified filler and are the key elements for direct prepara-
tion of the composites [33].
3. Additives today and in the future: shaping polymer
properties and beyond
Additives and polymers together form a strong team to de-
liver plastic materials for today’s and tomorrow’s applications.
Due to the fact that the introduction of new polymer structures
on a large scale is not very likely today and the trend to larger
production scale of standardized plastics with fewer grades
due to benefiting from the economics of scale, the importance
of engineering, polymer mixtures and additives to achieve new
and extended properties is more and more increasing.
Consequently, additives will introduce more and more
functionalities into the plastic application. They will modify
the properties of polymers and support the success of com-
modity plastics in demanding applications which have been
the traditional field of engineering plastics [34]. Examples
include modification of polymers by reactive additives,
branching of polyolefins [35] and chain extension of polycon-
densates, adjusting the molecular weight, rheology and pro-
cessing behaviour.
The influence of additives is not only limited to modifying
the bulk properties but can also be targeted to the surface or
the interphase between the surface and the environment as
well. The most common examples are antistatic additives, pro-
viding protection from issues through static electricity such as
dust pick-up or electrical discharges. In the latter case the an-
tistatic agent does not protect the plastic material but the addi-
tive is essential to protect packaged goods, such as electronic
parts, from damage. Moreover permanent antistatic agents
(e.g. IRGASTATÒ P) can provide protection over several years
and even when the surface is cleaned regularly, combining sur-
face effect and long-term properties.
Additives provide multifunctional benefits to the plastic ma-
terial during use and processes, but can even be smarter: incor-
porated into plastics they protect the content of packaged goods,
e.g. food and extend their fresh appearance or prevent valuable
ingredients such as vitamins from degradation by, e.g. UV light
(SHELFPLUSÒ UV) or by oxygen (SHELFPLUSÒ O2) [36].
A few more detailed selected emerging examples will support
the hypothesis that additives will shape the future of plastics.
2254 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256
3.1. Additives for melt strength enhancement of
polyesters
The mechanical recycling of plastics created the challenge
not only of maintaining the properties of polymers but also of
regaining the properties before the degradation during service
life. This target was achieved by the repair concept for recy-
clates [37].
The concept of adjusting polymer properties by reactive
additives can be used as well in virgin material to target
tailor-made properties. Polycondensation polymers such as
polyesters and polyamides are naturally more accessible to
tailored processes than polymerisation products. For example
reactive additives can adjust the properties of polyesters dur-
ing processing in a chain extending and/or controlled branch-
ing reaction.
The melt polycondensation of PET generally achieves a mo-
lecular weight that is only suitable for general fibre production.
However, a number of growing applications such as bottles,
strapping, industrial fibres need higher molecular weight,
which is obtained by solid state polycondensation. During pro-
cessing and use degradation of the polyester leads to the loss of
molecular weight either by hydrolysis or through thermo-oxi-
dation. The loss in molecular weight (measured as intrinsic vis-
cosity, IV) impacts the end-use performance negatively. A
direct extrusion process to increase the molecular weight of vir-
gin and recyclate PET is a favourable approach, provided that
critical issues of this process (discoloration, gel particle forma-
tion, food contact clearance, easy to use) can be solved. IRGA-
MODÒ RA 20 contains a blend of chain extenders and reaction
moderators and is a ready-to-use concentrate in a selected poly-
ester carrier. This new additive protects PET against degrada-
tion (at concentrations of 0.25e0.5%), increases molecular
weight (0.5e1.0%) and enhances melt strength and melt elas-
ticity (1e3%), potentially enabling extrusion blow moulding
and other processes requiring high melt strength (Table 6).
This high melt strength is achieved by long-chain branching
at higher use levels, whereas gel formation is avoided [38].
3.2. Tailoring the interphase: surface modifiers
As shown for polyester melt strength increase, the bulk
properties of plastics are not only maintained, but also sub-
stantially improved/changed by specific additives incorporated
into the polymer. As already mentioned, the effect of additives
is not only limited to the bulk but also can be targeted to the
surface of the plastic article thus opening new opportunities
for plastic applications.
Polyolefin fibres and non-wovens are increasingly used. Due
to their chemical compositions they are naturally hydrophobic.
However, there are growing applications, such as wipes and hy-
giene products, where fast water absorbance is requested. Con-
sequently the non-polar polyolefin has to be given a hydrophilic
character. Additives can provide this feature. IRGASURFÒ HL
560 is a durable hydrophilic internal additive for polyolefin fi-
bres and non-wovens [39]. Compared to the PP itself water is
absorbed in seconds, proven by very short strikethrough times,
Table 6
Reactive extrusion of PET in the presence of chain extender
Concentration of IV (dl/g) Degree of
IRGAMOD RA20 (%) branching
PET fibre grade No additive 0.63 0.1
PET fibre No additive 0.57 0.1
grade 0.25 0.65 0.5
extruded 0.50 0.67 0.4
1.00 0.72 1.8
1.50 0.74 2.2
2.50 0.85 4.5
and the hydrophilicity is retained after multiple insults. The wa-
ter absorption capacity of a non-woven fabric containing 2.5%
IRGASURFÒ HL 560 is more than eight times its weight.
Moreover the consumer gets improved softness and more pleas-
ant feeling of non-woven fabrics.
3.3. Light management: promoting growth of plants
Smart additives incorporated into a greenhouse film are
able to modify the spectrum of outside solar radiation and shift
UV light to visible red light. These changes in the radiation
transmission can result in significant modification of plant ar-
chitecture and shape as the photosynthetic process strongly de-
pends on the total amount of light that plants receive in
photosynthetic active radiation (400e700 nm). As SMART-
LIGHTÒ RL 1000 converts part of the absorbed UV light
into red light, the amount of light useful for the photosynthetic
process is increasing. The positive effect on plant growth was
confirmed by field trials in major cut flower markets world-
wide. Yields, growing cycle and quality (like stem length
and thickness) of the plants were generally improved for cut
flowers, e.g. roses. The production of red roses (yield/m2) un-
der a SMARTLIGHTÒ RL 1000 greenhouse film showed a cu-
mulated higher yield of 50% over two growing seasons,
proving the high commercial value of the effect [40].
4. Conclusion: additives are shaping the
future of plastics
Innovation in additives for plastics is unbroken. Due to the
trend in plastics to larger volumes and less grades the impor-
tance of additives in plastics will not only sustain but also in-
crease providing new applications and new effects.
Even in the traditional area of polymer properties retention
and extension new additives were recently commercialized
where improved performance for demanding applications in
selected use areas are required. Another driver for new addi-
tives is the increasing awareness of the environment resulting
in environmentally friendly additive solutions. This area
covers the introduction of oligomeric/polymeric stabilizers,
graftable stabilizers, halogen free flame retardants as well as
additives for the mechanical recycling of plastics.
Beyond polymer properties extension additives will provide
more and more functionalities to the polymer and to the
 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256 2255

product itself, taking over functionalities from the polymer CibaÒ IrganoxÒ B 225: blend of Irganox 1010 and Irgafos
(e.g. modification of polymers by reactive additives), being 168
competitive to new polymer structures as well as introducing CibaÒ IrganoxÒ HP 2225: blend of Irganox 1010, Irgafos
new effects (e.g. plant growth promoter). 168, Irganox HP 136
In a nutshell, plastic additives are and will be essential
components in polymer formulations and will provide innova- Ciba® IRGAZONE® 997
tive solutions for the resin producer, the plastic converter and
more and more value for the user of the plastic article.
OH
N
S-t-dodecyl
Appendix. Chemical formulas of mentioned additives N
H

Ciba® IRGANOX® 1010 Ciba® FLAMESTAB® NOR 116

OH R R
HN N N NH

H R

N N
O C4H9 C4H9
N N N
O O R=

HO O O OH
N N
O O O O
O

6PPD
H
N
OH
Ciba® IRGAFOS® 168 HN

O
O P CibaÒ TINUVINÒ XT 833, CibaÒ TINUVINÒ XT 850,
O Ciba TINUVINÒ NOR 371, CibaÒ IRGASTABÒ Cable
Ò

KV10, CibaÒ RECYCLOSTABÒ 451 AR, CibaÒ RECY-

CLOSSORBÒ 550, CibaÒ IRGASTATÒ P, CibaÒ SHELF-
PLUSÒ O2, CibaÒ SHELFPLUSÒ UV, CibaÒ IRGAMODÒ
RA 20, CibaÒ SMARTLIGHTÒ RL 1000, CGX NC 66 are
Ciba® IRGANOX® HP 136 proprietary compositions.
O
O C H References
CH3
[1] www.messe-duesseldorf.de/md/en/about_us/aboarvhives_newsarchiv_
trade_show, April 18, 2004.
CH3
[2] Hyatt JW, Hyatt IS. US 156,353; October 27, 1874.
[3] Hyatt IS, Hyatt JW. US 156,352; October 27, 1874.
[4] Hyatt JW, Hyatt IS. US 105,938; July 12, 1870.
Ciba® IRGANOX® 1726 [5] Combey M. In: Ritchie PD., editor. Plasticisers, stabilisers and fillers.
OH London; 1972. p. 5.
C12H25 [6] Hunter AS. US 2,129,131; September 6, 1938.
S
[7] Klemchuk PP. In: Pospisil J, Klemchuck PP., editors. Oxidation inhibi-
tion in organic materials, vol. 1. Boca Raton; 1990. p. 11.
C12H25 [8] Widmer A. Chemische Rundschau November 23, 2004. p. 5.
S [9] www.bccresearch.com/editors/RP-169.html.
2256 R. Pfaendner / Polymer Degradation and Stability 91 (2006) 2249e2256
[10] Zweifel H, editor. Plastics additives handbook, 5th ed. Munich; 2001.
p. 3, 142.
[11] Ullman’s encyclopedia of industrial chemistry, vol. A20; 2000. p. 556.
[12] Encyclopedia of polymer science and technology, vol. 2; 1965. p. 190.
[13] Encyclopedia of polymer science and technology, vol. 14; 1965. p. 137.
[14] Gächter R, Müller H, editors. Plastic additives handbook, 2nd ed.
Munich; 1984. p. 2, 98.
[15] Gächter R, Müller H, editors. Plastic additives handbook, 3rd ed.
Munich; 1990. p. 2, 130.
[16] Zweifel H, editor. Plastic additives handbook, 5th ed. Munich; 2001. p. 41e5.
[17] Pauquet JR. J.M.S.-Pure Appl Chem 1999;A36:1717.
[18] Capocci G., Hubbard M. ANTEC 2005, Boston, MA, USA. Presentation;
May 1e5, 2005.
[19] Gosh J. Canadian greenhouse conference, Missisauga, Canada. Presenta-
tion; October 6e7, 2004.
[20] Wegmann A, Huber G. 10th International conference of TPOs in automo-
tive, Barcelona, Spain. Presentation; June 2e3, 2004.
[21] Fay J, Fagouri C. TAPPI Hot Melt Tutorial, Indianapolis, USA. Presen-
tation; August 30, 2004.
[22] Kolb M, Stricker F. VDI Fachtagung Kabelextrusion, Bad Neuenahr,
Germany. Presentation; October 8e9, 2003.
[23] Bechstedt M. Plastverarbeiter 2004;55(12):42.
[24] Hopfmann T, Wehner W, Ryningen A, Stoffelsma JU, Clucas P,
Pfaendner R. Plast Rubber Compos Process Appl 1998;27:442.
[25] Meier H, Knobloch G, Rist G, Szelagiewicz M. Additives 2003, San
Francisco, CA, USA. Presentation; April 6e9, 2003.
[26] Knobloch G, Meier H. Additives 2005, New Orleans, LA, USA. Presen-
tation; April 3e6, 2005.
[27] Standard methods of fire tests for flame-resistant textiles and films.
National Fire Protection Association; 1996.
[28] Srinivasan R, Rotzinger B. RETEC, Houston, TX, USA. Presentation;
February 2000.
[29] Kaprinidis N, Zingg J. Additives 2003, San Francisco, CA, USA.
Presentation; April 6e9, 2003.
[30] Zweifel H, editor. Plastic additives handbook, 5th ed. Munich; 2001.
p. 973 ff.
[31] Pospisil J, Sitek FA, Pfaendner R. Polym Degrad Stab 1995;48:351.
[32] Kartalis CN, Papaspyrides CD, Pfaendner R, Hoffmann K, Herbst H.
Macromol Mater Eng 2003;288:124.
[33] Wermter H, Pfaendner R, Moad G, Li G. 8th European symposium on
blends and eurofillers. Bruges, Belgium. Presentation; May 9e12, 2005.
[34] Balsam M, Simon CJ, Kunststoffe 2001;91:46.
[35] Pfaendner R. 3rd Conference on modification, degradation and stabilisa-
tion (modest), Lyon, France. Presentation; August 29eSeptember 2, 2004.
[36] Morvillier M-R. Speciality plastics films 2004, Düsseldorf, Germany.
Presentation; October 18e19, 2004.
[37] Pfaendner R, Herbst H, Hoffmann K. Macromol Symp 1998;135:97.
[38] Simon D. Polyester 2004, 9th annual world congress, Zurich, Switzer-
land. Presentation; December 7e9, 2004.
[39] Behrens D, Shields P. RETEC polyolefins conference 2004, Houston.
Presentation; February 22e25, 2005.
[40] Tullo AH. Chem Eng News 2003;81:35.