Heat stabilizers
As with UV light, heat tends to oxidize polymers.The symp-
toms are embrittlement, melt flow instability, loss of tensile
properties and discolouration.The mechanism of stabiliza-
tion is therefore to prevent oxidation or to mitigate its
effects. Plastics, particularly thermoplastics, may also require
stabilization protection against degradation from heat during
processing or in use. John Murphy reviews the systems cur-
rently available, recent developments in technology and the
present market trends in heat stabilizers.
How they work Development in recent years has centered masterbatch. The most expensive stabiliz-
on technical improvement of the product, ers are organotin stabilizers. Lead
Because of its structure, PVC is particu- and easier handling and dispersion. The compounds are the cheapest.
larly sensitive to heat and is by far the main technical objectives have been a Antioxidants interrupt the degradation
largest user of heat stabilizers. Other vul- more durable effect at lower dosage levels, process in two ways, depending on
nerable polymers are chlorinated poly- with good retention of colour and trans- structure:
ethylene and PVC/ABS blends. The parency when required. Improvement of l Chain-terminating primary antioxidants
increasing use of engineering plastics in toxicological properties, for food-contact l Hydroperoxide decomposing secondary
applications involving prolonged expo- and medical applications has also been a antioxidants
sure to heat also calls for special stabilizer continuing aim of developers. For It is possible to use more than one type
systems. improved handling, pelletized and liquid of antioxidant, producing a desired result
Another important growth area for heat systems have been introduced, and there by different routes. Synergism between
stabilizers is recycled materials, where they is a general trend towards greater use of two stabilizers can often produce better
will be used increasingly in inhibiting
degradation and secondly in re-stabilizing
Summary: Heat stabiker&mtioxidrPnts
post-use plastics waste.
There are many different stabilizer sys- Function Used to prevent oxidation of plastics by heat, especially during
tems for plastics, depending on the type processing but also in application; widely used in PVC
and products of oxidation. Metallic salts compounds. Heat stabilizers act by stopping oxidation, or by
were originally used to stabilize PVC, the attacking the decomposed products of oxidation
most common being based on barium, Properties affected Stability during processing; resistance to thermal breakdown of
cadmium, lead or zinc, often mixed component under mechanical stress or toad@ retention of
together to obtain a synergistic effect. colour, transparency
Organometallic compounds are also
Materials Metallic salrs: Leaad;combinations of barium, cadmium, zinc;
used, mainly based on tin. A third group
organotin compounds
is non-metallic organic stabilizers, in
Hindered phenol& secvndary aromatic amines (primary
which phosphites play an important role,
antioxidants)
improving transparency, initial colour
F%osphites/phosphonites, thivethers, soya-based epoxies
and light-fastness. Epoxies (particularly
(secondary antivxidants)
derivatives of soya bean oil) are also
Synergistic comMnativns of these
used, acting also as plasticizers, for non-
toxic products. DiSUJVWtages No serious drawbacks: stabikers ha= been arvund sv long,
For applications in contact with food, they have become an accepted part vf the prvcess; lead and
FDA and BGA regulations recommend cadmium being replaced in respvnw to envkvnmental pressure
liquid antioxidants based on Vitamin E. New developments Mutti-functional stabilizer systems, development vf synergistk
These have been developed as patented reactions, improved retention of colour and transparency, more
systems and also open up new areas of convenient fkwms fvr hkwdling; replacement vf he&y metal
application, in polyolefins and compvundr
polyurethane foam systems.
Plastics Additives & Compounding August/September I999
q
results than a single system at the same
concentration and, in polymers such as
polyethylene and polypropylene, the
total effect of synergism can be to
improve efficiency of the antioxidant by
up to 200%. A considerable amount of
recent development has also focused on
harnessing this phenomenon.
Primary antioxidants
Primary antioxidants react rapidly and are
termed ‘radical scavengers’. The most
important are sterically hindered pheno-
lies and secondary aromatic amines.
Hindered phenolic is a high molecular
weight antioxidant, for polymer systems
that are sensitive to thermal and oxidative
degradation, due to formation of free rad-
icals and peroxides. It protects against
degradation at high processing tempera-
tures and is highly efficient, low in volatil-
ity and non-staining, with wide toxicolog-
ical clearance. The efficiency can be
enhanced by using hindered phenolic
with other antioxidants such as phos- trend towards non-dusting products, cable insulation), polypropylene (especial-
phites and thioesters, producing synergis- including pelletised solids and liquids. ly hot water applications), high impact
tic effects for effective and economical The antioxidant is effective at very low polystyrene, ABS and MBS. It can also be
formulations. It is normally available as a dosages (0.01 - 0.1%) in low and high added to PVC plasticisers (in which it can
free-flowing powder, but 50% aqueous density polyethylene (especially carbon be dissolved) to inhibit oxidative degrada-
dispersions are also available. There is a black-filled grades for pipe and copper tion and embrittlement of PVC wire and
cable insulation. The material can be used
in polyamides and hot melt adhesive for-
mulations. It is losing ground, however, in
PU foam because of volatility, as the use
of non-CFC blowing agents requires
higher processing temperatures.
Unplasticized PVC (PVC-U) Secondary antioxidants
Pipe +++ + +
Secondary antioxidants react with
Injection moulding ++ +
+++ + + ++ hydroperoxides to produce non-radical
Profile extrusion
++ + ++ products and are therefore often termed
Sheet
+-I-+ ‘hydroperoxide decomposers’. They differ
Film
++ + from primary phenols and amines in that
Bottles
they are decomposed by reaction with
PlaJticized PVC (PVC-P)
+++ + hydroperoxide, rather than containing it.
Cable
++ + + They are particularly useful in synergistic
Coatings
++ + combinations with primary antioxidants.
Imitation leather
++ + Systems that do not contain a phenolic
Profiles
++ + + can provide good colour stability and gas
Film
fade resistance, which are important
properties in PI’ fibres and other applica-
Source: HenkellSidobre SinnovolPlostiques Modernes et Elostomkes
tions. A breakthrough was claimed by
Ciba with FS Systems, the first of which
la
Plastics Additives & Compounding August/September I999
Additives
A breakthrough in lactone chemistry for
polymer stabilization (making the manu-
facturing process significantly more effi-
cient) was recently claimed by Ciba
Specialty Chemicals. The technology is
based on a combination of a high per-
formance phosphite or phosphonite pro-
cessing stabilizer and a hindered phenolic
antioxidant, offering an improved
cost-performance profile compared with
traditional two-component systems
based on a phosphitelphosphonite and a
phenolic antioxidant.
Ciba recently commissioned its first plant
to manufacture the phosphorus-based sta-
blizer P-EPQ, and will market it under
the Irgafos brand name in several forms,
including the superior pastille form FD,
which offers advantageous handling
properties. It also forms a component in
the lactone Irganox XP 400 stabilizers.
A solid phosphite antioxidant has been
developed by GE Specialty Chemicals in
its Ultranox range. Designed to meet the
demand for a high activity stabilizer with
superior hydrocarbon stability and
improved handling characteristics, it is
based on butyl ethyl propane diol chem-
istry, rather than the usual pentaerythri-
tol. It has been granted FDA approval for
food contact in certain applications and is
expected to find applications in poly-
olefins, styrenics, PVC, engineering ther-
moplastics, elastomers and adhesives.
Blends of phosphites with primary antiox-
idants are also a centre of active develop-
ment. Blends (such as the Irganox LC
range) of primary antioxidants and a high
temperature hydrolytically-stable
was based on a new hydroxyl-amine -a most frequently used processing stabilizer organophosphite secondary antioxidant
high molecular weight compound offer- in high-performance additive systems. have been developed for high temperature
ing outstanding compatibility with Among recent developments are systems processing of polyolefins, polyamides and
polypropylene, which functions through with better colour fidelity and handling polycarbonates in colour-critical applica-
several different stabilization mechanisms properties. Typical is Dover’s Doverphos tions. Irganox LM blends of primary
to give both processing and long-term HiPure 4, which is a high-purity tris- antioxidants and a new phosphite process-
thermal ageing stability. It also appears to nonylphenyl phosphite (TNPP) process- ing stabilizer offer melting at 90°C and
improve the activity of the hindered ing and heat stabilizer and is claimed to can be applied to polymer reactor prod-
amine stabilizer that is also a component reduce overall costs. With 0.1% residual ucts, especially polyolefins, linear poly-
of the system, as both a thermal and light nonyl phenol, it is FDA-approved for esters, polycarbonates, polyamides, HIPS,
stabilizer. food-contact applications and is also used ABS, SAN and elastomers.
Phosphite/phosphonites are generally in medical applications, colour-critical Liquid blended systems (such as GE’s
regarded as the most effective stabilizers polyolefins and styrenic block copoly- Weston blends of trisnonylphenyl phos-
during processing, protecting both the mers. It is effective also in acrylics, elas- phite and octadecyl3.5 di-tert-butyl-4-
polymer and the primary antioxidant. tomers, nylon, polycarbonate, poly-ure- hydrozyhydrocinnamate) reduce the num-
Hydrolytically stable phosphites are the thanes, polystyrene, PVC, ABS and PET ber of feeders required and eliminate
Plastics Additives & Compounding August/September I999
EQ
on-site mixing, reduce loss from dusting Heut st5Mzefs: tmfe numes
and give more accurate feeding ratios. Actirox modified zinc phosphate Colores Hispania
Anox PAM blends from Great Lakes is a Advapak multifunctional stabilizers Morton Int
blend of Anox 20, a hindered phenol Alkanox phosphite antioxidants Great Lakes
antioxidant, and Alkanox P-24, an
Anox antioxidants, phenol Great Lakes
organo-phosphite antioxidant. The blend
provides good protection against thermo- Baropol additive systems Barlocher
oxidative degradation during long term Bruggolen H heat stabilizers Briiggemann
ageing, while providing process stability Chimassorb light/UV stabilizers Ciba Specialty Chemicals
to polymer systems such as polypropy- Corn&tab stabilizers Comiel
lene, polycarbonate, HDEP, ABS and Corduma UV stabilizers Nemitz
other engineering thermoplastics. Doverphos HiPure TNPP Dover Chemical
Great Lakes has also introduced a prod-
FS Systems stabilizersi Ciba Specialty Chemicals
uct specifically for the wire and cable
industry, where the presence of metals in Garbefix phosphite antioxidants Great Lakes
plastics can lead to the introduction and Hostanox stabilizers, metal deactivators Hoechst
accelerated production of degradation Interlite PVC stabilizers Akcros Chemicals
products. Lowinox MD24 combines Interstab PVC stabilizers Akcros Chemicals
both an antioxidant and a metal deacti- Irgafos processing stabilizers Ciba Specialty Chemicals
vator for the protection of polyolefins Irganox antioxidants/heat stabilizers Ciba Specialty Chemicals
and elastomers used in wire and cable
Lankromark liquid PVC stabilizers Akcros Chemicals
insulation. Protection is provided from
the auto-oxidation process that can occur Lowinox antioxidants Great Lakes
through the presence of trace metals Markstab organic phosphites Witco
from catalyst residues, for example. Markstab PVC liquid stabilizer Witco
Thioethers increase long-term stability in Naftomix stabiliser/lubricant systems Chemson
conjunction with phenolic antioxidants. Naftosafe stabiliser/lubricant systems Chemson
Their use is limited to applications where Naftovin heat/light stabilizers Chemson
possible effect on odour or taste and nega-
Plastabil PVC stabilizers Diadema Industrias
tive interaction with HALS (hindered
amine light stabilizers) is not important. PlastiStab mixed metal heat stabilizers OM Group
Rea-tin-or organotin derivative stabilizers Reagens
Reablend stabilizers, lubricants for PVC Reagens
Replacement of heavy
Reaflakes stabilizers, lubricants for PVC Reagens
metals Rhodialux benzophone stabilizers Great Lakes
Rhodianox phenolic antioxidants Great Lakes
Environmental concern has promoted the
Ricinolts stabilizers Jayant Oil Mills
development of systems to replace lead
(especially from cables and cellular prod- Sanduvor UV stabilizer Clariant
ucts). Cadmium-based stabilizers are also Sarmastab heat/light stabilizers Sarma
being phased out. To achieve the same Stabilox CaZn stabilizer/lubricant mix Henkel
effect, however, the replacements have to be Stabinex lead stabilizer for PVC Mitsui
a complicated mixtures of salts. Organotin Stabiol CaZn stabilizers Henkel
and calcium/zinc systems are favoured at Suconox Seal Sands
polyamide antioxidant
present, but much will depend on the shape
Thermolite tin compounds Elf Atochem
of any legislation in the future. In general,
alternatives based on calcium and zinc are Tinstab PVC stabilizers (tin) Akcros Chemicals
less effective, but are cheaper than those Tinuvin light/heat stabilizers Ciba Specialty Chemicals
based on aluminium or magnesium. Water Topanol antioxidants SealSands
absorption can be a problem with systems Ultranox solid phosphite GE Specialty Chemicals
not using heavy metals. Univul light stabilizers, UV absorbers BASF
Ciba has developed both tin and calcium W Chek light stabilizers Erbsloh
zinc stabilizers for cellular PVC. Liquid
Uvasil I-IALS light/W stabilizers Great Lakes
systems, for easy processing, are generally
featured in new developments. Akcros has Weston stabilizer blends GE Specialty Chemicals
Plastics Additives & Compounding August/September I999
ii
Additives
a barium/zinc liquid stabilizer for flexible
PVC, Lankromark LZ 1727, which gives
good clarity and is self-lubricating.
Badocher has patented a stabilizer based
on calcium/aluminium hydroxyphosphite,
‘Ooot ‘OOot ‘OOOt ‘ooot
claimed to be an environmentally-friendly
Heat stabilizers 280 66 150 64
raw material superior to all other known
UV stabilizers 16 7 5.5 3.5
systems in external applications.
Heat and UV stabilizers 296 73 155.5 67.5
Performance comparable with lead,
together with greater thermal stability, Sources: based on estimates by Business Communications Co, Ropra and Townsend
. . . -- .
better weathermg than CaLn and
improved processability is claimed by Elf company has become the only US pro- and to add strength and stability to PVC
Atochem for a new organotin, ducer to have all three tin stabilizers for products. They can be used in the pro-
Thermolite PA 2400. With the addition the PVC industry. Methyltin stabilizers duction of rigid PVC exterior building
of a new methyltin product line to its are used to improve the performance of products such as window profiles, fenc-
US butyl and octyl tin facilities, the colour development during processing, ing and siding, and also in bottles, cal-
endered sheet, pipe and injection
moulded fittings.
Commercial trends
With a world consumption of around
280 000 tonnes, heat stabilizers are con-
siderably larger than UV stabilizers. PVC
is overwhelmingly the largest user - which
may put some check on growth - but, as
thermoplastics are processed faster and
hotter, there are many niche opportunities
opening up for other materials such as
polyolefins and engineering plastics.
Within the total there will be significant
changes in materials, in response to envi-
ronmental concerns. There is a decline in
use of lead compounds (the most popu-
lar type) and the threatened phase-out
of cadmium will have a major impact,
but will signal opportunities for other
stabilizers.
The most significant of the heat stabiliz-
ers are lead compounds, which account-
ed for nearly 68% of volume in 1989,
but by 1994 had declined to 64%.
Barium/cadmium compounds are the
next most important, followed by organ-
otin compounds (which actually come
second in value terms). Barium/zinc and
calcium/zinc compounds have a high
growth rate due to substitition in some
cases of barium/zinc for barium/cadmi-
um because of fears for the effects of cad-
mium on the environment and health,
after it had been found that soluble cad-
mium products could have an adverse
effect on the environment when used at
above certain critical levels.
Plastics Additives & Compounding August/September I999
i e
Unfortunately, in the absence of any spe- and organotins lo- 15%, while the In the $200m US market, the main heat
cific data on cadmium in insoluble form, remainder is liquid or paste combina- stabilizers include lead compounds, organ-
the restrictions were also applied to these tions of calcium and barium salts otin compounds and mixed metai/salt
materials as a precautionary measure. This with zinc (according to estimates by blends based on chemicals such as barium,
has led to confusion, with the result that Akcros). Stabilizers for UPVC window cadmium and zinc, and significant changes
many legislative bodies have taken their profiles are: lead-based 68041, barium, are expected. Over $75m of the business is
own decisions. cadmium and lead, and barium cadmi- in lead and cadmium-containing stabiliz-
In the USA, OSHA issued a Notice of um are 23%, calcium- and zinc-based ers, but these are under increasing scrutiny
Proposed Rulemaking, significantly are 3%. on health and safety grounds. n
reducing the permissible exposure limits
for cadmium. while a new risk assessment
study on lead toxicity is expected. In the
meantime, individual states have passed
The chemistry of polymer
their own laws restricting the use of cad-
mium and lead. degradation
In Europe, after introducing increasing Organics can react with molecular oxygen in a process called autoxidation, initiated by heat,
restrictions on the use of cadmium over light (high energy radiation), mechanical stress, catalyst residues or reaction with impurities,
the last 20 years, legislators are suddenly to form alkyd radicals. The free radicals can, in turn, react to cause the polymer to degrade.
embarrassed by their own latest study Oxidation - in-chain scission, producing a change in molecular weight, discolouration
which concludes that cadmium pigments and loss of properties - is the main chemical process causing plastics to degrade.
(at least) do not present any significant Hydroperoxides break down into free radicals, which cause the damage. Under heat,
threat to human health or to the environ- some polymers may undergo chain scission with cross-linking and formation of
ment. It is unlikely that there will be any hydroperoxides and free radicals.
dramatic reversal of the legislation. Oxidation can be slowed by chain-breaking antioxidants, to reduce rate of propagation, or
Lead stabilizers hold about 60% of preventative antioxidants, which prevent initial formation of free radicals. Antioxidants
the European PVC stabilizer market deactivate the sites by decomposing the hydroperoxide or by terminating the free radical.
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