10.

21 Processing and Performance Additives for Plastics

R Höfer, Editorial Ecosiris, Düsseldorf, Germany
© 2012 Elsevier B.V. All rights reserved.

10.21.1 Introduction 369

10.21.2 Radical Generation 369

10.21.3 Surface Active Additives 370

[Link] Emulsifiers for Emulsion Polymerization 370

[Link] Antistatic Agents 370

[Link] Antifogging Agents 371

10.21.4 Additives for Polymer Processing 372

[Link] Lubricants 372

[Link] Mold Release Agents 372

[Link] Heat Stabilizers 372

[Link] Acid Scavengers 373

[Link] Polymeric Processing Aids 373

[Link] Curing Agents 374

[Link] Blowing Agents 374

10.21.5 Additives for Polymer Properties and Performance 374

[Link] Plasticizers 374

[Link] Impact Modifiers 376

[Link] Antiblocking Agents 376

[Link] Slip Additives 376

10.21.6 Stabilization against Polymer Degradation 377

[Link] Antioxidants 377

[Link] Light Stabilizers 377

[Link] Flame Retardants 378

[Link].1 Inorganic additive flame retardants 378

[Link].2 Organic additive flame retardants 378

[Link].3 Reactive flame retardants 379

References 379

10.21.1 Introduction processability and performance but also satisfy environmental

and health demands.1
Polymer materials may be applied as films on surfaces such as
in coatings and adhesives; they may be used as diminutive ink
dots in printing and imaging; they may be processed and 10.21.2 Radical Generation
shaped by molding, extruding, or thermoforming to yield plas­
tic products or compounded, processed, and vulcanized to Free radical-generating additives perform functions as
yield rubber articles; and they may be fed into a single screw
extruder for the manufacture of filaments and man-made tex­ • polymerization initiators,2
tile and carpet fibers. Whatever the final use of polymer • photoinitiators for radiation curing systems,3
materials, additives participate as key components in the man­ • curing agents for unsaturated polyesters (UPs),4
ufacturing of the polymer, act as processing aids during • cross-linking agents for thermoplastics, and
shaping, and guarantee the long-term performance of the fin­ • melt flow modifiers to yield high-melt-strength polypropy­
ished goods. Additives are application related including their
lene (HMS-PP).5
terminology, which often tries to illustrate their effect. Most
additives are low molecular weight (Mw), others (such as Typical organosoluble initiators used in bulk, solution, or sus­
impact modifiers) are polymers. Normally, additives are not pension polymerization or the radical-based modification of
chemically bound to the polymer network. They may thus have thermoplastics are the following (Figure 1):
a tendency to migrate depending on time, temperature, and
concentration into materials that are in contact with the surface • diacyl peroxides, such as dibenzoyl peroxide (BPO) or laur­
of plastics. As a result, the use of additives for a polymer in food oyl peroxide (LP);
contact is regulated by authorities in order to protect consu­ • dialkyl peroxides, such as dicumyl peroxide (DCUP);
mers, and additive manufacturers are faced with the imperative • alkyl peroxyesters, such as tert-butyl peroxyneodecanoate
to develop products that not only enhance the overall (TBPND) or cumyl peroxyneodecanoate (CUPND);

Polymer Science: A Comprehensive Reference, Volume 10 doi:10.1016/B978-0-444-53349-4.00272-7 369

370 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives

O
H3C CH3
O O CH3
O H3C O
O H3C CH3
O

Dibenzoyl peroxide
tert-Butyl peroxyneodecanoate

O O

OH
O
O C O O C O
tert-Amyl hydroperoxide (formula reproduced with the
kind permission of chemBlink,
Dicyclohexyl peroxydicarbonate [Link]

OH
O
CH3
O
O 2.2�-Azobisisobutyronitrile
HO O C O OH
O
C2H5 OH
Monomer Dimer
Methyl ethyl ketone peroxide
Figure 1 Typical initiators for free radical polymerization.

• peroxydicarbonates, such as di-2-ethylhexyl peroxydicarbo­ [Link] Emulsifiers for Emulsion Polymerization

nate (EHPC) or dicyclohexylperoxydicarbonate (DCPC);
‘Emulsion polymerization’ (Chapter 10.27) is used to manu­
• hydroperoxides, such as tert-amyl hydroperoxide;
facture several commercially important plastics and synthetic
• ketone peroxides, such as methyl ethyl ketone peroxide rubbers such as polyvinyl chloride (PVC), acrylonitrile-buta­
(MEKP); and diene-styrene terpolymer (ABS), or styrene-butadiene rubber
• peroxyketals, such as 1,1-di-tert-butylperoxy-3,3,5­ (SBR). Many of these polymers are used as solid materials
trimethylcyclohexane. and must be isolated from the aqueous dispersion after poly­
merization by spray drying, acidification, or coagulation. The
Besides the major classes of peroxide compounds, various
surfactant must enable a fast rate of polymerization, minimize
accelerators (e.g., cobalt octoate) may be used in conjunction
coagulum or fouling in the reactor and other process equip­
with peroxides to shorten curing times.
ment, and prevent an unacceptably high viscosity during
Some azo compounds have also been used as initiators.
polymerization (which would lead to poor heat transfer).
However, one of the problems of azo compounds is their content
Examples of emulsifiers used in vinyl chloride emulsion
of cyano groups, which may cause toxic side products during
(or microsuspension) polymerization include sodium lauryl
their thermal decomposition. The first and until recently predo­
sulfate and dodecyl benzene sulfonate, whereas SBR and ABS
minantly used aliphatic azo initiator 2,2′-azobisisobutyronitrile
are polymerized at alkaline pH using a fatty acid soap (e.g., the
(AIBN) is not used anymore in industrial polymerization opera­
‘Rubber Reserve Soap’, i.e., a commercially available mixture of
tions because of the toxicity of tetramethylsuccinonitrile
fatty acids having C12 to C18 carbon atoms) or disproportio­
produced as a side product of AIBN decomposition.
nated rosin soap (wherein gum rosin or tall oil rosin is heated
Initiators with labile C–C bonds such as tetraphenylsuccinic
in the presence of a Pd/C catalyst to remove conjugated unsa­
acid dinitrile form radicals by homolytic thermal cleavage of
turation (which inhibits polymerization) by converting abietic
such bonds, depending on the kind and size of the substituent.2a
acid into dehydroabietic acid6). In addition, sodium naphtha­
Water-soluble initiators for emulsion polymerization
lene sulfonate formaldehyde condensation products are listed
are sodium, ammonium, or potassium persulfate or redox
as polymeric emulsifiers, latex stabilizers, and dispersants in
systems (Chapter 10.27).
production recipes for synthetic rubbers.7

[Link] Antistatic Agents

10.21.3 Surface Active Additives
Dissipation of static electrical charges that build up on the surface
In polymer technologies, surface active agents (also called sur­ of plastics, as they are insulating materials, is the task of ‘antistatic
factants, tensides, or emulsifiers) are employed during the agents’ (also called antistats). The static electricity needs to be
manufacture of certain polymers by emulsion polymerization dispersed to avoid problems such as sparking or dust attraction.
and in order to modify the surface properties of polymer goods. Antistats are surface active substances, which have an
 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives 371

amphiphilic character. While the hydrophobic surfactant side 3. cationic

interacts with the surface of the material, the hydrophilic side • quaternary ammonium compounds (QACs; e.g., dimethyl
attracts the air moisture and binds the water molecules this way dihydrogenated tallow ammonium chloride, mainly used
creating a conductive layer of water on the polymeric surface that as external antistats for plastics applied from a water or
dissipates the electrical charge. alcohol solution, also used as fabric softeners; in house­
There are two types of antistatic agents – internal and hold fabric softener applications, QACs have, however,
external. Internal antistatic agents are introduced during
largely been replaced by ester quats9)
manufacturing or compounded into the polymer during
4. amphoteric
processing. They need to be compatible with the polymer
• alkyl betaines (e.g., cocamidopropyl betaine).
material, stable during processing, and innocuous in contact
with food. The amphiphilic character causes their migration
(also called blooming) to the polymer surface. ‘Permanent’
internal antistatic agents do not bloom and are alloyed with [Link] Antifogging Agents
the resin to provide a longer-term antistatic effect. Main
The condensation of tiny, discrete water droplets on the surface
application areas for internal antistats are polyolefins, ABS
of hydrophobic plastic surfaces, typically on polyethylene (PE)
plastics, PVC, and polystyrene (PS). External or topical
and polypropylene (PP) films, is called ‘fogging’. The effect is
antistats are applied to the surface of a polymer through
particularly noticeable when food in plastic packaging is stored
techniques such as spraying, wiping, or dipping. These anti­
at a temperature below the dew point of water vapor. The
static surface coatings often serve a cosmetic function by
phenomenon is dependent upon the temperature and relative
keeping dust from settling on plastic surfaces. External
humidity of the enclosed water vapor–air mixture. Besides food
antistats are easily lost from the polymer through handling
packaging, fogging occurs in agricultural films made from PVC,
(e.g., rinsing) and tend to be used more frequently in appli­
low-density polyethylene (LDPE), or ethylene vinyl acetate
cations where a short-term antistatic effect is needed, such as
(EVA); in plastic film green houses; and in the interior of
plastic packaging of electronic parts. plexiglass (acrylic glass, polymethylmethacrylate, PMMA) or
Common antistatic agents may be polycarbonate (PC) double-skin sheets used for green houses,
1. nonionic winter gardens, or verandas. Fogging reduces the light transmit­
• fatty acid esters, such as glycerol monostearate (GMS) and tance and is aesthetically undesirable.
The antifogging agent dissolves in the water droplets and low­
more particularly ‘high-mono GMS’ containing more
ers the surface tension. As a result, droplets spread on the surface
than 95% monoester; GMS is in accordance with most
and form a continuous film (Figure 2). This film reflects light the
food contact regulations. It can, therefore, be used in all same way as a dry surface would do with the result of clear
plastics employed for food packaging visibility. Like antistats, antifogging agents can be applied intern­
• fatty amine polyglycol ethers (e.g., cocoamine + 2 EO) ally and externally. Also antifogging coatings have been proposed.
• fatty acid diethanolamides (e.g., coconut fatty acid Like antistatic agents, antifogging additives in food packaging need
diethanolamide) to be in accordance with food contact regulations. Commercial
• fatty alcohol polyglycol ethers (can be used as internal antifogging agents are mainly nonionic tensides, more particularly
antistats and viscosity modifiers in PVC plastisols or as sorbitan esters and sorbitan ester ethoxylates, glycerol and poly-
glycerol fatty acid esters, and fatty alcohol ethoxylates eventually
external antistats in mold release formulations for green
end-capped with linear low-Mw alkyl groups.10
tires)8
‘Fogging’ in plastics technology needs to be distinguished
2. anionic from fogging effects occurring in living rooms11 (also called
• alkyl sulfonates (incorporated in more polar polymers ‘magic dust’) and from vehicle windshield fogging as a result of
such as styrene copolymers and PVC) outgassing of volatile components in the interior of the pas­
• phosphoric acid alkyl esters senger compartment.12

Surface tension

< 90° > 90°

Gravitational Surface attractive forces

force
Liquid on a non-wettable surface, When attractive forces to surface
surface tension-dominating exceed surface tension, the liquid
attractive forces on surface wets the surface

Figure 2 Schematic representation of surface tension and wetting. Adapted from the Chem1 Virtual Textbook by Stephen Lower, Simon Fraser
University, Vancouver, [Link] with kind permission.
372 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives

10.21.4 Additives for Polymer Processing • Fluoropolymers, such as polytetrafluoro ethylene (PTFE).

Lubricants in plastics for food contact need to be in accordance

Plastics processing aids include several classes of low-Mw and
with food contact regulations.1d
polymeric materials, which facilitate the processing of plastics
in the melt. Their presence also affects the properties of the
finished product.
[Link] Mold Release Agents
The easy, quick, and effective release of a molded plastic from
[Link] Lubricants
the mold is of crucial importance for all kinds of plastic mold­
The application of lubricants to protect interacting surfaces in ing technologies in order to capture all mold details, to avoid
relative motion against friction and wear is common in such surface defects, to reduce cycle times, and to preserve the fin­
diverse fields as mechanical engineering, textile and fiber indus­ ished products of thermal stress.
tries, and plastics processing. In plastics processing, lubricants Various mold release technologies are available that can be
serve primarily to improve flow by reducing melt viscosity, to categorized as follows:15
reduce internal frictions due to the interaction of polymer
• Permanent coatings: most often some form of PTFE coating,
chains, and to minimize external frictions and adhesion at the
interface between the molten polymer and machinery parts. which is applied to the mold. These coatings avoid the need for
The industrial processing of PVC, more particularly of rigid operator application, but may become damaged by misuse.
PVC, by extrusion, calendering, extrusion blow molding, or • Semipermanent coatings: the coating, if applied correctly,
injection molding in any case necessitates the use of an appro­ will last for a number of releases before requiring to be
priate lubricant; accordingly, compounding of PVC represents reapplied or touched up. The active chemistry involved in
the largest outlet for lubricants in plastics processing. Other these coatings is typically a polysiloxane or waxes.
resins into which lubricants are formulated include polyole­ Semipermanent mold release agents can be solvent or water
fins, styrenics, phenolics, and applications such as wood plastic based. After having thoroughly cleaned the mold surface, the
composites,13 nylon films and fibers, and engineering poly­ release agent is applied as a smooth wet film.16
mers. Usually, the lubricants are added as part of the
• Sacrificial coatings: the coating has to be applied each time
formulation during plastics processing. They also can be incor­
because most of the mold release agent comes off on the
porated in the form of a masterbatch.
A lubricant may be compatible to the greatest possible molded part when it releases from the tool.
extent with the polymer and decrease the internal molecular • Internal mold release agents are not applied as a coating to
friction in the molten polymer (internal lubrication) or may the mold but incorporated in the polymer melt. They are a
easily migrate to the interface between processed plastic melt precondition for injection molding technology and are also
and metallic machinery parts reducing shear and equipment used in film and foam applications. In principle, external
wear and by this reducing energy consumption and increasing lubricants act as internal mold release agents, that is, chemi­
production rates (external lubrication).14 cally fatty acids, wax acids and their soaps, amides, and fully
Important lubricant groups are synthetic waxes and deriva­ esterified polyol esters are used. For modern high-speed
tives of natural fats and oils: molding technologies such as structural reaction injection
• Fatty alcohols, such as cetyl/stearyl alcohol molding (SRIM) of urethane or urethane-urea polymers,
• Fatty alcohol dicarboxylic acid esters, such as distearyl adi­ which cure to be demolded within about 50–90 s after injec­
pate or distearyl phthalate tion into a mold, the combination of one of the above
• Fatty acids and fatty acid soaps, such as stearic acid or Ca­ lubricants with a polyether-modified polysiloxane surfactant
behenate (Chapter 10.25) has been disclosed.17
• Fatty acid esters, such as butyl stearate or stearyl stearate
• Fatty acid polyol esters, such as glycerol mono/distearate or
pentaerythritol tetrastearate
• Glyceryl tris-12-hydroxystrearate (hydrogenated castor oil
[Link] Heat Stabilizers
(HCO), also called castor wax) Heat stabilizers are added to plastics to protect them against
• Fatty acid complex esters, such as pentaerythritol adipate thermal stress during processing but also during the useful life
stearate of the finished article. It is well known that PVC is the most
• Fatty acid amides, such as ethylene bis stearamide (also heat sensitive of the major commercial thermoplastics.
called amide wax) Stabilization consists primarily of a stabilizing action on
labile chlorine atoms in the PVC resin in order to prevent
• Montan wax and montan wax acid
dehydrohalogenation and secondarily in the neutralization
• Oxidized PE and paraffin waxes
of HCl by incorporation of soaps or capturing of HCl by
• Polar PP waxes, that is, PP grafted with maleic anhydride epoxy groups (Figure 3).18 This hypothesis is accepted by
• Nonpolar PE waxes, such as low-density polyethylene nearly all researchers,19 although other theories tend to attri­
(LDPE) or high-density polyethylene (HDPE) waxes bute the stabilizing action to the reduction of polar
• PP waxes interaction between chlorine atoms on heating, more particu­
• Natural and synthetic paraffin waxes larly close to the glass transition temperature.20 Efficient
 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives 373

Lead soaps

Synergism of
Ca/Zn stabilization

Organo-Sn
stabilizers

Epoxidized vegetable
oil
Capturing of HCl

Substitution of labile Cl atoms

Figure 3 Stabilization mechanisms for PVC. Höfer, R.; Hinrichs, K. In Polymers: Opportunities and Risks II: Sustainability, Product Design and
Processing; Handbook Environmental Chemistry; Eyerer, P., Weller, M., Hübner, C., Eds.; Springer Verlag: Berlin, Heidelberg, 2010; Vol. 12; Höfer, R. In
Perspektiven nachwachsender Rohstoffe in der Chemie; Eierdanz, H., Ed.; VCH: Weinheim, 1996; p 91.1d,14c

stabilization of PVC against thermal stress is achieved by Acid scavengers may also act as co-stabilizers, as can be seen
addition of the following: in Figure 3 for the case of epoxidized vegetable oils in PVC
stabilization.
• Mixed metal salts (formerly Ba/Cd, now largely replaced
because of toxicity concerns by Ba/Zn and Ca/Zn salts of
fatty acids or phenolates, mainly used in flexible and semi­
rigid PVC) [Link] Polymeric Processing Aids
• Organotin stabilizers (e.g., dibutyltin maleate or di­ Polymeric processing aids are particularly important to
n-alkyltin mercaptides, preferentially used for rigid PVC) solve productivity issues, to overcome problems due to
• Lead stabilizers (tribasic, dibasic, or neutral lead stearate, stick and slip conditions during extrusion, to improve the
dibasic lead phthalate; inorganic lead sulfates, carbonates, optical properties such as haze and transparency, and to
or phosphites, mainly used in wire and cable applications) avoid surface defects usually called surface melt fracture or
• Epoxidized vegetable oils (e.g., epoxidized soybean oil sharkshrink in polyolefin films. For that purpose, fluoro­
polymer and so-called fluoroelastomer22 processing aids
(ESO), epoxidized linseed oil, or butyl epoxystearate).1d,19
are traditionally used in blown film extrusion of linear
Primary heat stabilizers may advantageously be used in combi­ low-density polyethylene (LLDPE) and HDPE, usually at
nation with organic co-stabilizers, such as β-aminocrotonates, a very low addition rate between 200 and 1500 ppm in
β-diketones, or β-ketocarboxylic esters, or inorganic weight.23 The most widely used fluoropolymer is a
co-stabilizers, such as zeolites or hydrotalcites. hexafluoropropylene-vinylidene fluoride copolymer
(Figure 4)
Being immiscible with polyolefins, fluoropolymers tend to
build up on metal die surfaces and form a slippery surface
[Link] Acid Scavengers
coating that increases the flow stability.24
Trace amounts of acidic or halogen-containing impurities may
remain in a polymer after manufacturing or processing. Such
impurities may derive from catalysts such as in the case of
polyolefins or from other additives such as flame retardants.
-(CF2-CF)n-(CH2-CF2)m­
Metal soaps such as calcium stearate or calcium lactate,
hydrotalcite [Mg6Al2(CO3)(OH)16•4(H2O)] or hydrocalumite
CF3
{Ca2Al(OH)6[Cl1−x(OH)x]•3(H2O)}, and zinc oxide may be
used as acid scavengers in polyolefins.21 Figure 4 Hexafluoropropylene-vinylidene fluoride copolymer.
374 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives

[Link] Curing Agents they also act as ODSs and their use would be temporary.27
On 1 January 2005 the US Environmental Protection
Whereas thermoplastic resins usually are fully polymerized
Administration (EPA) issued a ‘Use Ban’ regulation on
when submitted to processing, thermosetting resins are pre­
HCFC-141b blowing agent. With the phaseout of HCFC, manu­
pared for processing in an uncured state, and they are
facturers diverged down one of two paths – hydrofluorocarbons
irreversibly cured during the processing stage. The cure (or
(HFCs) or hydrocarbons. Those concerned about the flammabil­
‘cross-linking’) may be done through heat (generally above
ity of hydrocarbons selected one of several HFC options, such as
200 °C), through irradiation, or through a chemical reaction.
hydrofluoroolefins. However, the high global warming potential
Curing initiates a change in the molecular structure or even
(GWP) of the HFCs has continued to raise questions about their
creates a new polymer (curing of a polyol with a polyisocyanate
long-term future as blowing agents, and international agreements
yielding a polyurethane (PUR)). Substances that promote or
on ODSs are the driving force for the conversion to zero
control the cross-linking reaction are called curing agents. An
ozone-depleting hydrocarbon blowing agents such as n-pentane,
agent that does not enter into the reaction is called a catalyst.
isopentane, or cyclopentane.28 Additionally, polymer foams cre­
Curing agents react with molecules and are coupled directly
ated using supercritical carbon dioxide (scCO2) as a processing
into the cured system as a structural moiety of the polymer.
solvent have garnered much interest in recent years.29
Epoxy resins by curing form a three-dimensional and infu­
Chemical blowing agents are solid organic or inorganic
sible network. The choice of the epoxy curing agent (ECA)
compounds that release a propellant gas, usually N2 and/or
depends on the processing method, curing conditions, physical
CO2, at a specific processing temperature. The following pro­
and chemical properties desired, and toxicological and envir­
duct classes are of particular importance:30
onmental limitations. The main chemistries on which ECAs are
based are polyamides and aliphatic amines (Chapter 10.28). Azo compounds
However, a variety of other curing agents containing active • Azodicarbonamide (ADC)
hydrogen atom, such as melamine-formaldehyde, urea- Hydrazine derivatives
formaldehyde, polysulfides, or mercaptans,25 have been used. • p-Toluenesulfonyl hydrazide (TSH)
Polyester resins and UP resins are usually cured by addition
• 4,4′-Oxybis(benzenesulfonyl hydrazide) (OBSH)
of peroxides, which generate free radicals and cause
Semicarbazides
cross-linking. For ambient temperature, cure reducing agents
• p-Toluenesulfonyl semicarbazide (TSSC)
such as tertiary aromatic amines or heavy metal salts of Co, Va,
or Fe are often employed as accelerators. Agents that speed up Tetrazoles
the oxidative drying process of natural drying oils in coating • 5-Phenyltetrazole (5-PT)
technology (Chapter 10.03) are called dryers or siccatives. They Nitroso compounds
are chemically identical to the accelerators for UP resins. • N,N′-Dinitrosopentamethylenetetramine (DNPT)
Carbonates
• Sodium bicarbonate.
[Link] Blowing Agents
Blowing agents are additives used in the manufacture of foamed
plastics, which have the advantage of lightness, contribute to
material and cost savings, and are distinguished by the fact that 10.21.5 Additives for Polymer Properties
they are thermally insulating. Blowing agents usually create fine and Performance
and regular cellular structures during polymer processing. Foam
[Link] Plasticizers
blowing agents encompass a wide variety of applications, includ­
ing refrigerators, building insulation, automobiles, furniture, and As defined by ASTM D 883 and DIN EN 971-1, a plasticizer is
packaging. The applications encompass materials such as rigid an inert liquid or solid organic substance, predominantly an
PUR and polyisocyanurate foams and, to a lesser extent, extruded ester with low volatility incorporated into a plastic or elastomer
PS board foam and phenolic foam. Blowing agents can be divided to increase its flexibility, workability, or distensibility.31 A plas­
into chemical blowing agents that liberate the blowing gas by a ticizer, among other contributions, will reduce the melt
chemical reaction or physical blowing agents, that is, a blowing viscosity, lower the temperature of a second-order glass transi­
gas that is liberated by vaporization or by release of pressure. tion, or lower the elastic modulus of a polymer. This is achieved
Common practice has been to use nonflammable fully by physical interaction with the polymer loosening the strength
halogenated ‘first-generation’ chlorofluorocarbons (CFCs) such of intermolecular forces between macromolecules and result­
as CFC-11, CFC-12, and CFC-113 (Class I substances26) to propel ing in a higher flexibility of the macromolecules or segments of
liquid plastic resin and function as an insulating component of the macromolecules (Figure 5). As the plasticizer molecules are
the foam. The fully halogenated CFCs, however, have been iden­ not chemically bound to the macromolecules, they are free to
tified as ozone-depleting substances (ODSs) and as a self-associate and associate with the polymer molecules. As
consequence the Montreal Protocol and its subsequent amend­ these interactions are weak, there is a dynamic exchange pro­
ments to the Vienna Convention for the Protection of the Ozone cess, whereby as one plasticizer molecule becomes attached at a
Layer have led to the efficient phaseout of these CFCs and their site or center of the macromolecule, it is readily dislodged and
replacement by ‘second-generation’ blowing agents (Class II sub­ replaced by another. At low plasticizer level, the polymer–
stances26) such as hydrochlorofluorocarbon (HCFC)-141b that plasticizer interactions are the dominant interactions, while at
can operate within existing equipment and applications. high plasticizer concentration, plasticizer–plasticizer interac­
However, because HCFCs themselves contain chlorine atoms, tion can become more significant. This can also explain the
 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives 375

category 2 substance (i.e., substances that should be regarded as

Crystalline if they impair fertility in humans) has substantially increased the
area
Polymer market share of DINP and DIDP.
Embrittlement The bulk of ‘aliphatic ester’ plasticizers are derived from
Basic Plasticizer
adipic, sebacic, and azelaic acids esterified with linear or
polymer
branched monofunctional alcohols of short to medium chain
length, for example, dioctyl adipate (DOA; di(2-ethylhexyl)
Anti- adipate), diisononyl adipate (DINA; di(n-butyl)sebacate
Plasticization plasticization (DBS)). These materials are distinguished by their low viscosity,
thus making them particularly attractive to the plastisol sector,
and giving excellent low-temperature flexibility properties. Fatty
acid esters of short-chain monofunctional alcohols can be used
as viscosity depressants for PVC pastes and also as secondary
plasticizers for plasticized PVC compounds. Oligomeric and
polymeric plasticizers (usually polyesters, based on adipic, aze­
laic, glutaric, and sebacic acid) extend the life of PVC end
products considerably. They are nonmigratory, scarcely volatile,
Light Strong and have low dependency on temperature. Some types resist
plasticization plasticization extraction by aliphatic hydrocarbons, mineral oils, or fats.
‘Epoxidized vegetable oils’ and epoxy fatty acid esters (also
Figure 5 Plasticizer action on a molecular basis. Adapted from Höfer, R. called epoxy plasticizers) play a particular role as non-
In Perspektiven nachwachsender Rohstoffe in der Chemie; Eierdanz, H., gelatinizing secondary plasticizers offering properties of migra­
Ed.; VCH: Weinheim, 1996; p 91; Sears, J. K.; Darby, J. R. The Technology tion resistance in PVC compounds, alkyd resins, other chlorine-
of Plasticizers; Wiley: New York, 1983; Brudermanns, K.; Graß, M.; containing polymers, and chlorinated paraffins. Epoxidized
Höfer, R.; et al. In: Lehrbuch der Lacke und Beschichtungen, 2. völlig neu vegetable oils are manufactured by reaction of performic or
bearb, Aufl, Bd. 4; Ortelt, M., Ed.; S. Hirzel: Stuttgart, 2007.14c,31c,d
peracetic acid on soybean or linseed oil (Figure 6). The peracids
are formed in situ by reaction of formic or acetic acid with
observation of ‘antiplasticization’ wherein very low plasticizer hydrogen peroxide. Epoxidized soybean oil (ESO), the most
levels increase the rigidity of the polymer. However, in PVC widely used plasticizer of this group, through the oxirane moi­
plastisols, i.e., a concentrated colloidal dispersion of PVC in a ety additionally functions as a scavenger of labile chlorine
liquid plasticizer, the plasticizer acts as a solvent and makes up atoms and heat stabilizer in PVC compounds.
between 30 and 80 % of the blend. PVC plastisols are used in ‘Trimellitate plasticizers’ are produced by the esterification of
the production of artificial leather, foamed plastics, and coat­ a range of alcohols with trimellitic anhydride (TMA). Esters of
ings for metal surfaces. trimellitic (1,2,4-benzenetricarboxylic acid) anhydride provide
The principal plasticizer application in conjunction with excellent resistance to volatile loss and oxidation under heat
polymers is, by far, the plasticization of PVC resins. aging conditions. Trimellitates are used mostly for PVC cable
The most widely used plasticizers are ‘phthalic acid esters’. and wire. The low volatility of trimellitates is also exploited in
They are usually produced by reaction of phthalic anhydride car interior components. The most important esters are trioctyl
with an excess of alcohol using p-toluenesulfonic acid as catalyst. trimellitate (TOTM) and triisononyl trimellitate (TINTM).
The excess alcohol is recycled. Commercial phthalate esters are ‘Phosphate plasticizers’ are the most important category of
colorless and mostly odorless liquids. Dioctyl phthalate (DOP flame-retardant plasticizers used inter alia for PVC film and
or di-2-ethylhexyl phthalate (DEHP)) has been the international sheet compounds, polyester fibers, nitrocellulose, cellulose
standard PVC plasticizer counting for more than 50% of world acetate, and cellulose acetate butyrate. They are prepared by
plasticizer consumption. Other broadly used phthalate plastici­ reaction of POCl3 with monofunctional alcohols or alkylated
zers are diisononyl phthalate (DINP) and diisodecyl phthalate phenols.
(DIDP). In Europe, increased regulatory scrutiny and classifica­ The increasing concern of the public regarding the environ­
tion of DEHP as a CMR (carcinogen, mutagen, and reprotoxic) mental and health impact of consumer products, and

O o
O C O C(O)
o o
O C(O) O C(O)
o o
O C O C(O)
O
Epoxidized soybean oil Epoxidized linseed oil

Molecular weight 935 960

Epoxy value 6–7 8.5–9.5
Viscosity (20 °C, MPa s) 550–600 800–1200
Figure 6 Epoxidized vegetable oils.
376 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives

particularly of plasticizers because of their widespread propa­ used with PC and PBT, especially for low-temperature
gation in many articles of daily use including toys has created a impact modification.
need for all manufactures to provide products with reduced ‘ABS’ graft copolymers provide better clarity and transpar­
environmental impacts, and to especially consider the carbon ency than normally available from MBS-type modifiers. Such
load on the atmosphere.1d Accordingly, ‘safer plasticizers’ with ABS impact modifiers may be prepared by graft polymerizing
better biodegradability and less biochemical effects, which styrene and acrylonitrile (SAN) as grafting monomers by emul­
additionally do not contribute to greenhouse gas emissions sion polymerization in the presence of a butadiene-based or
during production or degradation are desirable. styrene/butadiene-based rubber substrate.41
Some such plasticizers are as follows: ‘AIMs’ are eventually the most broadly used class of impact
modifiers as they overcome the limitations of MBS and ABS
• Acetylated monoglycerides; these can also be used as food with regard to weather resistance, particularly in the case of
additives rigid PVC in building applications. AIMs are also used in engi­
• Alkyl citrates, used in food packagings, children toys, and neering thermoplastics such as PC, PBT, and PET. AIMs are
medical products such as PVC blood containers32 typically methacrylate/butyl acrylate/styrene core-shell graft
• 1,2-Cyclohexanedicarboxylic acid diisononyl ester terpolymers. They are generally made by first preparing a rub­
(i.e., hydrogenated DINP), used in food packaging, medical bery phase based on cross-linked n-butyl acrylate or n-butyl
devices, toys, and child-care articles. It is compatible with a acrylate/butadiene. The hard shell is commonly methyl metha­
wide range of polymers including PVC33 crylate polymerized onto the rubbery core.42
‘EVA’ copolymer impact modifiers for PVC in practice are
• Mono- and diesters of biologically derived succinic acid34
EVA/VC graft polymers. They are prepared by suspension poly­
• Isosorbide esters.35
merization of a solution of EVA in vinyl chloride monomer.
‘CPE’ impact modifiers are prepared by chlorination of
HDPE. These have commonly been used in PVC extrusion
and injection molding applications including siding and win­
[Link] Impact Modifiers dow profiles.43
In general terms, impact modifiers are polymeric additives,
usually composed of a rubber or a polymer containing a rub­
bery phase, built into a polymer matrix to absorb mechanical [Link] Antiblocking Agents
energy and to improve the impact resistance of finished arti­ The self-adhesion or sticking together of plastic films when, for
cles.36 More particularly, vinyl chloride and styrene example, opening fresh plastic garbage bags is called ‘blocking’.
homopolymers are typical examples of materials that show a Blocking is especially severe with polyolefin, polyester, and
certain propensity for brittle fracture at low temperatures or polyamide film after production and/or during prolonged sto­
high deformation rates and need an impact modifier to rage. Therefore, antiblocking additives are used to minimize
improve toughness. Also wood plastic composites37 and engi­ the adhesion and reduce the blocking force between film layers.
neering plastics such as polycarbonate (PC), polybutylene It is anticipated that this is done by creating a microrough
terephthalate (PBT), or PC/PBT alloy primarily applied in surface, thereby reducing the contact area and self-adhesion
shaped articles for automobiles and outdoor sports equipment between film layers. Antiblocking agents are suitable inorganic
may need impact modifiers. For effective use, the impact modi­ filler materials such as natural silica, synthetic silica gel, talc,
fier rubber particles must be larger than a critical size for each of zeolites, or limestone as well as special organic compounds
the matrix polymers. A critical volume fraction of the rubber such as cross-linked polymethylmethacrylates.44
phase is also required in order to achieve significant improve­
ments in toughness relative to that of the matrix polymer, and
adhesion between the rubber phase and the brittle matrix is [Link] Slip Additives
required. Grafting of the rubber phase with the matrix mono­
mers typically leads to the required adhesion between the Slip additives are used to reduce friction between films and
rubber particles and the matrix.36,38 between film and converting equipment, which improves
Impact modifiers include39 movement through extrusion lines and downstream packaging
operations and enhances processing or end applications. Fatty
• methacrylate butadiene styrene (MBS) polymers acid amides, including primary and secondary amides, are the
• ABS copolymers most commonly used slip additives. Similar to external lubri­
• all acrylic impact modifiers (AIMs) cants, they migrate or bloom to the surface where they form a
• EVA copolymers microcrystalline structure that decreases friction. Primary, unsa­
• chlorinated polyethylene (CPE). turated fatty acid amides such as erucamide (Figure 7) and
oleamide migrate quickly and are the most efficient slip agents
Typically, ‘MBS’ polymers are prepared in two or more for polyolefins. Secondary amides, for example, oleyl palmita­
stages where the core is about 90–50 parts of polybutadiene mide, are less volatile at the higher process temperatures with
or butadiene copolymers and the shell is about 10–50 parts very slow migration rates. They may be used in multilayer films
of a lower alkyl methacrylate, especially methyl methacry­ and in engineering plastics.45
late. Besides MBS, AIM and ABS impact modifiers are also Manufacture of fatty acid amide slip agents is carried out by
grafted rubber thermoplastics with core-shell structure.40 reacting a fatty acid or a fatty acid methyl ester and ammonia at
MBS impact modifiers find application in PVC and are high temperature and pressure (e.g., 240 °C and 136 atm).46
 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives 377

O photooxidation in the presence of oxygen or ozone. Both

effects lead to discoloration and reduction of polymer’s Mw
NH2 followed by embrittlement and loss of tensile, impact, and
elongation strength of the polymer, and eventual degradation.
While antioxidants inhibit the formation of hydroperoxides in
the photooxidation process, pigment light absorbers and
photostabilizers minimize photooxidation.
CH3(CH2)7CH=CH(CH2)11C(O)-NH2 A material can be protected against the effect of UV radiation
by use of suitable pigments that have UV screening effect.
Figure 7 Erucamide.
Particularly, the white pigments CaCO3 and TiO2 provide UV
screening, and so does carbon black. The protective effect of UV
10.21.6 Stabilization against Polymer Degradation absorbers is based essentially on the absorption of UV radiation
and its dissipation as heat by reversible intramolecular proton
[Link] Antioxidants transfer. Typical UV absorbers are oxanilides (such as
Heat, ultraviolet (UV) radiation, mechanical shear, or metallic N-(2-ethoxyphenyl)-N′-(2-ethylphenyl)ethanediamide), benzo­
catalyst residues create free radicals in synthetic as well as in phenones, benzotriazoles, and hydroxyphenyl-benzotriazoles.48
natural polymers. Such free radicals react with molecular oxy­ Additives that convert the energy absorbed by chromophores by
gen in a process called autoxidation to form alkyl peroxy excited state quenching into heat or fluorescence or phosphor­
radicals. Peroxy radicals react with an available hydrogen escence before it can break any molecular bond and generate free
atom to form a hydroperoxide and another free radical. The radicals are called deactivating metal ion ‘quenchers’. Nickel (II)
free radicals can, in turn, react to cause the polymer to degrade. chelates, such as Ni-dibutyldithiocarbamate, act as quenchers.
Compounds that retard the oxidative degradation of a plastic They are more particularly used in polyolefin agricultural
by deactivating peroxy radicals or by ‘scavenging’ free radicals films that are expected to survive for several years, during
are referred to as antioxidants. Antioxidants are used in every which they may be exposed to severe climate conditions and
kind of plastic, but polyolefins account for about 60% of global pesticides.
demand. Degradation of polymers that have already formed free
Antioxidants are of two basic types: Primary antioxidants radicals is inhibited by radical scavengers, more particularly
intercept and stabilize free radicals by donating active hydrogen by hindered amine light stabilizers (HALS). Since the arrival
atoms. Secondary antioxidants prevent formation of additional of Tinuvin® 770 the first HALS UV stabilizer (Figure 8), HALS
free radicals by decomposing the unstable hydroperoxides into have proved to be extremely efficient stabilizers against
a stable product. light-induced degradation of most polymers. They do not
Butylated hydroxytoluene (BHT) and other hindered phe­ absorb UV radiation, but act to inhibit degradation of the
nols and aromatic amines represent the main types of primary polymer with a broad range of applicability, including poly-
antioxidants. Phosphites (e.g., tris(nonylphenyl)phosphite olefins, PS, PUR, ABS, SAN, acrylonitrile styrene acrylate
(TNPP)) and thioesters are secondary antioxidants that react (ASA), polyamides, and polyacetals, and favorable perfor­
with hydroperoxides to produce nonradical products, thus pre­ mance in fibers and films as well as molded and extruded
venting free radical formation. They are therefore often termed shapes.
‘hydroperoxide decomposers’. Primary and secondary antioxi­ In order to overcome photooxidation and material degrada­
dants are commonly used in combination, and in PVC tion caused by ozone in the air (ozone cracking, facilitated by
phosphites are also frequently employed as co-stabilizers. UV radiation), ‘antiozonants’ are used as additives to plastics
Synthetic antioxidants such as BHT are not only used in and rubbers, especially in tire manufacturing.
polymers but also in food to protect fats and oils against Common antiozonants include:
oxidative deterioration noticeable by rancid odors and fla­
vors. On the other hand, natural antioxidants47 are not only • paraffin waxes that form a surface barrier
becoming of interest in food but also in polymers, more • p-phenylenediamines such as 6PPP (N-(1,3-dimethylbutyl)­
particularly for applications in contact with food. For that N′-phenyl-p-phenylenediamine) or IPPD (N-isopropyl-N′­
purpose, both the FDA and BGA also recommend antioxi­ phenyl-p-phenylenediamine)
dants based on vitamin E (vitamin E, in its bioactive form, is • ethylene diurea (EDU).
α-tocopherol).1a

[Link] Light Stabilizers CH3 CH3

CH3 CH3
Light stabilizers (including photostabilizers, UV stabilizers, or O O
UV absorbers) protect polymers against degradation caused by H N O C (CH2)4 C O N H
exposure to sunlight. Particularly in outdoor applications, the
UV spectrum of sunlight in the range of 290–400 nm is CH3 CH3 CH3 CH3

absorbed by polymers containing chemical groups called chro­

mophores. Bonds within the polymer can be broken and a free Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate

radical chain reaction can be initiated. UV radiation also facil­ Figure 8 Hindered amine light stabilizer Tinuvin® 770 (introduced 1976
itates weathering, i.e., the degradation of a polymer surface by by Ciba-Geigy).
378 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives

[Link] Flame Retardants [Link].2 Organic additive flame retardants

‘Halogenated hydrocarbons’ comprise chlorinated paraffins53 and
Since the discovery of fire, man has balanced fire’s utility with its
a relatively large variety of brominated aromatic or cycloaliphatic
destructive power with varying degrees of success. Fire prevention
hydrocarbons, phenols, ethers, or polyols (Figure 9). Their degree
methods, including the use of flame retardants, have been around
of bromination varies from 45% to 80% bromine. Bromine con­
since ancient times.49 The inherent flammability of natural and
taining flame retardants act primarily by a chemical interfering
synthetic organic polymers because of their high carbon content
on the one side, and their ubiquity in the form of plastics, compo­ with the radical chain mechanism taking place in the gas phase
sites, textiles, foams, timber, adhesives, and paints on the other, for during combustion. High-energy OH and H radicals formed dur­
example, in household appliances, car and aircraft interiors, cable ing combustion are removed by bromine released from the flame
insulation, and computer casings, requires that measures be taken retardant. In general, aliphatic bromines have less thermal stabi­
to allow their safe use where the potential for fire exists. lity than aromatic bromine compounds. Hence, aromatic
Consequently, flame retardants fulfill a vital function: they act to bromine compounds are used extensively as flame retardants all
retard ignition, slow down the combustion process, reduce smoke over the world.55 Consequently, a considerable spread of these
evolution, or even make the material self-extinguishing. They, compounds has been found worldwide in biological and in sedi­
therefore, play a crucial role in fire protection, as they not only ment samples.56 Their distribution throughout the environment
reduce the risk of a fire starting, but also the risk of the fire spread­ and their toxicity has created concerns in view of bioaccumulation
ing – so leaving more time for people to escape. The term ‘flame and conceivable parallels with polychlorinated biphenyls (PCBs)
retardant’ is generally used to indicate that a product has been and DDT,57 especially since model laboratory studies have hinted
treated to improve or modify its response to a fire environment that pyrolysis of brominated flame retardants results in the for­
and is not meant to imply that the product will not burn given mation of polybrominated dibenzo-p-dioxins (PBDDs) and
sufficient heat and oxygen.1b Flame retardants are used to interfere polybrominated dibenzofurans (PBDFs).54
with the combustion process, both chemically and physically. The ‘Phosphorus compounds’ (organophosphates) such as
use of flame retarded, or ignition resistant, plastics may be required tri-o-cresyl phosphate (TOCP or TCP) or halogenated com­
by regulation; however, it is vital that flame retardants do not pounds such as tris(2,3-dibromopropyl)phosphate (TRIS), bis
produce toxic, dense, or noxious smoke and fumes. The behavior (2,3-dibromopropyl)phosphate, tris(1-aziridinyl)phosphine
during combustion but also with regard to exposure of workers in oxide (TEPA), and others are commonly used in thermoset
recycling and processing plants and to emissions in the indoor resins particularly in rigid and flexible PUR foams, but also
environment has created concern and regulations are also being find application in making fire-retardant cellulosic composi­
issued on the grounds of health, safety, and the environment.50,51 tions including cotton. They have been used both as a physical
Flame retardants may be inorganic or organic chemicals, additive and as a reactive flame retardant. Additionally, bridged
and there are two basic types of flame retardants that, to aromatic diphenyl phosphates, especially resorcinol bis(diphe­
some extent, are assigned to different groups of plastics. nyl phosphate) and bisphenol-A bis(diphenyl phosphate) have
‘Additive flame retardants’ are usually applicable to found broad application because of their good thermal stabi­
thermoplastics such as ABS plastics, polycarbonates, high impact lity, high efficiency, and low volatility.58 Another actively
polystyrene, polyolefins, polyamides, or polybutylene ter­ reported group of compounds is the metal salts of dialkylpho­
ephthalate. They are introduced by mixing the components sphonic acid as well as calcium hypophosphite, which have
directly or by compounding with a flame-retardant masterbatch. recently been found to be particularly effective in PBT and
Reactive flame retardants are usually introduced by a chemical PC. Acidic retardants produce char by a dehydration
reaction with a resin precursor. They are commonly used process and this brings about the final fire retardancy in
for thermoset plastics such as epoxy, PUR, or UPs. Some non­
reactive additive flame retardants are also used in thermosets,
and concentrations of inert fillers and other additives in
the plastic product affect the level of flame retardant required. Br Br
Additionally, the contributions that nanoparticles could make to O Br Br
flame retardancy are under scientific investigation.52

Brx Bry
[Link].1 Inorganic additive flame retardants
x + y = 1–10 Br Br
‘Aluminum trihydrate’ (ATH) is often used as the sole flame
retardant. At high loading as a flame retardant and smoke (1) (2)
suppressing filler/extender; it can act synergistically with Br Br
Sb2O3, zinc borate, or phosphorus-containing flame retardants CH3

for increased flame retardancy. HO OH

‘Magnesium hydroxide’ (Mg(OH)2) acts similar to ATH as Brx Bry

Br CH3 Br x + y = 1–10
flame retardant and smoke and toxic gas suppressant.
‘Antimony oxide’ (Sb2O3) is widely used synergistically (3) (4)
with ATH or halogenated flame retardants. Figure 9 Typical commercial brominated flame retardants: chemical
‘Zinc borate’ (xZnO·yB2O3·zH2O) can replace Sb2O3 as a structures of (1) polybrominated diphenyl ethers (PBDEs), (2) hexabro-
synergist in both halogen-based and halogen-free flame- mocyclododecane (HBCD), (3) tetrabromobisphenol A (TBBPA), and
retardant systems. It catalyzes formation of char and creates a (4) polybrominated biphenyls (PBBs). De Wit, C. A. Chemosphere 2002,
protective layer of glass. 46 (5), 583–624.54c
 Polymer Processing: Environmentally Benign & Safe | Processing and Performance Additives 379

phosphate-containing composition. High efficiency of phos­ (b) Lindner, R. A.; Worschech, K. In Encyclopedia of PVC, 2nd ed.; Nass, L. I.;
phorus fire retardants in PUR foam has also been suggested to Heiberger, C. A., Eds.; Marcel Dekker: New York, 1988; Vol. 2. (c) Höfer, R. In
Perspektiven nachwachsender Rohstoffe in der Chemie; Eierdanz, H., Ed.; VCH:
be the result of stable char formation. The char affects the
Weinheim, 1996; pp 91–106.
flammability in the following three ways: reduction of flam­ 15. [Link]
mable fuel, insulation by the char, and coating by the (retrieved 12.03.2011).
nonvolatile thermally stable phosphorous acids that screen 16. Goss, B. Reinf. Plast. 2004, 48 (8), 24–26.
the hot carbon from the oxygen.59 17. Shidaker, T. A.; Bareis, D. W. WO 00/5524, 2000 (Huntsman ICI Chemicals).
18. Frye, A. H.; Horst, R. W. J. Polym. Sci. 1959, 40, 2119; Frye, A. H.; Horst, R. W. J.
Polym. Sci. 1960, 45, 1; Frye, A. H.; Horst, R. W.; Paliobagis, M. A. J. Polym. Sci.,
[Link].3 Reactive flame retardants 1964, A2, 1765, 1785, 1801.
Reactive flame retardants are mainly relevant to thermosetting 19. Starnes, Jr., W. H.; Jenings, T. C.; Krauskopf, L. G. In Plastics Additives Handbook;
Zweifel, H.; Maier, R. D.; Schiller, M., Eds.; Carl Hanser Verl.: München, 2009.
resins, such as UPEs, PURs, or epoxies. They become part of the
20. Naqvi, M. K. Polym. Degrad. Stab. 1985, 13, 161–166.
polymer network through copolymerization or cross-linking 21. Holzner, A.; Chmil, K. In Plastics Additives Handbook; Zweifel, H.; Maier, R. D.;
with a flame-retarding unit either in the chain or as a pendent Schiller, M., Eds.; Carl Hanser Verl.: München, 2009.
group. Reactive flame retardants are often used also as 22. Améduri, B.; Boutevin, B.; Kostov, G. Prog. Polym. Sci. 2001, 26 (1), 105–187.
flame-retardant additives. Typical examples are polybromi­ 23. Dubrocq-Baritaud, C.; Darque-Ceretti, E.; Vergnes, B. J. Non-Newtonian Fluid
Mech. 2011, 166 (1–2), 1–11.
nated diphenyl ethers (PBDEs), tetrabromobisphenol A 24. Tolinski, M. In Additives for Polyolefins; Tolinski, M., Ed.; Elsevier: Oxford,
(TBBPA), tris-(3-aminophenyl)phosphate (TAPP),60 or reactive Burlington, 2009.
hydroxy aryl phosphonates61 for epoxy systems, dibromoneo­ 25. Frihart, C.; Natesh, A.; Singhal, S.; et al. Mercaptane als Härter und Beschleuniger in
pentyl glycol (DBNPG) for thermosetting polyesters and rigid Epoxidharzen, Welt der Farben, 9/2001, 9–14.
26. Ozone Layer Protection Glossary, [Link]
PUR foams, and 1,4,5,6,7,7-hexachloro-5-norbornene-2,3­
27. Derwent, R. G.; Simmonds, P. G.; Greally, B. R.; et al. Atmos. Environ. 2007, 41 (4),
dicarboxylic acid (HET acid) for UP resins cured with styrene.62 757–767.
Moreover, cyclotriphosphazenes with skeletal nitrogen and 28. Deutsche Gesellschaft für Technische Zusammenarbeit (GTZ)/Programme Proklima,
phosphorus atoms are subject of research because of their Natural Foam Blowing Agents Sustainable Ozone- and Climate-Friendly Alternatives
favorable thermal properties such as phosphorous and nitro­ to HCFCs, Eschborn (2009), [Link]
[Link] (retrieved 17.03.2011); Caleb Management Services,
gen flame-retardant synergy and self-extinguishability when UNEP Guidance on the Process for Selecting Alternatives to HCFCs in Foams,
integrated in the network of thermosetting polymers.63 United Nations Environment Programme (2010), [Link]
39827966/UNEP-Guideance-on-the-Process-for-Selecting-Alternatives-to-HCFCs­
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Biographical Sketch
Rainer Höfer graduated in Inorganic Chemistry with Professor Oskar Glemser at the Georg-August-Universität Göttingen in
1973 with work on sulfur-nitrogen-fluorine chemistry. He spent 3 years at the Technical University of Oran (ENSEP),
Algeria, as Maître de Conférences and Directeur de l’Institut de Chimie before joining Henkel in Düsseldorf. With Henkel
KGaA and then as vice president Research & Technology with Cognis GmbH in Monheim, he has assumed global research
and development, application technology, technical sales service, strategic business development, and technology scouting
responsibilities in oleochemistry, polymer chemistry, and surfactant chemistry for the polymerization, coatings, graphic
arts, adhesives, engineering plastics, agrochemical, synthetic lubricants, mining, and pulp and paper markets.
He is founder of Editorial Ecosiris with consultancy and publishing activities in the domains of green chemistry,
renewable resources, sustainable development, and interculturation.