ADDITIVES FOR PLASTICS

Introduction

The term additives are used in the plastics

industry may applied to any substance that is
added generally in small concentration to resins
in order to alter their properties either facilitate
processing or to change the physical, chemical,
electrical properties of end products.

Additives are accepted today as full-

fledged partners of plastics.
 PLASTICS ADDITIVES

Additives to modify plastics Additives achieve their effect

Properties by physical means by chemical reactions

plasticizers heat stabilizers

lubricants antioxidants
impact modifiers UV absorbers
fillers flammable retardants,
pigments, etc. etc.
 REQUIREMENTS OF ADDITIVES

• They should be efficient in their function.

• They should be stable under processing
conditions.
• They should be stable under service
conditions.
• They should not bleed or bloom.
• They should be non-toxic and not impart taste
and odour.
• They should be cheap.
• They should not adversely affect the properties
of polymer.
 ADDITIVES WHICH ASSIST PROCESSING

The factors mostly responsible for product quality and output in plastics
processing are:
a) The resistance of polymer to thermal degradation.
b) Frictional behaviour of melt on the metal surface.
c) Melting viscosity of the polymer.
d) Processing equipment
e) Processing variables

The various types of additives assist processing are:

a) Processing Stabilizers
b) Lubricants and Flow promoters.
c) Thixotropic agents
 Processing Stabilizers
At high temperature, oxygen combines with polymer chain to form
carbonyl compounds which will lead to yellow and brown discoloration.
a) Initiation: Production of free radicals.
R–R -----> 2 R*
b) Propagation step: Radicals interact with polymer chains
R* + O2 -------- ROO*
ROO* + RH ------- ROOH + R*
c) Termination Step: Deactivation of free radicals
R* + R* ------- R R
R* + ROO* --------- ROOR
ROO* + ROO* --------ROOR + O2
Additives exert action:
1. by interacting directly with the degradation reaction to
product inactive species and reduce concentration of
reaction species
2. by removing deactivating or promoting competition for
sources that have a catalytic action in the degradation
process.
Primary Stabilizer: Antioxidants
They inhibit or retard the oxidative degradation of
materials at normal or elevated temperatures, whether
during processing, storage or service.
E.g., Irgonex. They are added to resins generally in very
small quantities, roughly from 0.1 - 0.5%.
Secondary Stabilizer: Peroxide Decomposes
They protect the polymers from degradations by
removing peroxide radicals and decomposing hydro-
peroxides as they are formed.
E. g.: Sulphur and phosphorous compounds as sulphides,
thioethers, tertiary phosphites and phosphorates.

Chelating agents: Metal deactivators

Bulky legends create steric Luidrance around the
metal as and prevents its inter-action with active sites of
polymer chain.
E.g.:Most important class of chelating agents is the
organic compounds, based on melamine, diamines etc.
Special Stabilizers for Halogenated Polymers
E.g., Flame retardant, impact modifiers, etc., which are based on
Halogenated products and may create further processing stabilization
when incorporated into polymers.
Stabilizers for Halogenated compounds must meet the following
requirements:
1. Absorb and neutralize HCl evolved in order to arrest auto catalytic
chain reactions and to prevent corrosion of processing
equipment.
2. Prevent oxidation reactions and other free radical processes.
3. Displace active, labile constituent groups, e.g., tertiary and allytic
Cl atoms with more stable substituents.
4. Disrupt conjugation in the residual polymer chains to prevent the
formation of objectionable discoloration.
FLAME RETARDERS
Flame retardants appear to function one or more of the following mechanism:
• They chemically interfere with the flame propagation mechanism.
• They may produce large volumes of incombustible gases while
dilute the air supply.
• They may react, decompose or change state endothermically, thus
absorbing heat.
• They may form an impervious fire resistant coating preventing access of
oxygen to the polymer.
Typical Flame Retardants used in Plastics
Polymer Flame Retardant
Nylon Red Phosphorus
Polyester Laminates Aluminium Trihydrate
PVC Chlorinated Paraffin &
Phosphates
 Typical Stabilizers for Vinylchloride Polymers

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Chemical Name Structure Comments

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Basic Lead Carbonate Pbo.PbCO3 Low cost and efficient toxic

Tribasic Lead sulphate 3 PbO.PbSO4H2O Low cost and efficient

Used in cable formulation
Dibasic lead phosphite 2PbO.PbHPO3 Good heat stabilizer offer
1/2H2O synergism in ageing
stabilization and chelation
towards metal impurities
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Co precipitated cadmium/barium
Laureates Cd(OCOC11H25)2 Susceptible to
sulphide Staining
Ba(OCOC11H25)2

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Organotin stabilizers (C4H9)2 SnOCOH Good high
Dibutyltin meleates temperature
stabilizer

Dibutyltin bis (Lauryl) (C4H9)2 Sn (SC12H25)2 Excellent for clear

Application.
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Lubricants & Flow Promoters

There are three major friction problems encountered in plastics

processing:
a) Interparticle friction between polymer powders or granules
which impairs their free-flowing characteristics, hence
creating difficulties in conveying operations such as their
feeding into processing equipment.
b) Friction between the polymer melt and the metal surface of
the processing equipment which can seriously impair the
flow of the melt and therefore produce undesirable effects,
such as low output and poor surface quality of finished
products.
c) Friction in finishing operations. E.g., printing and
packaging.
Lubricants are widely used in the Plastids Industry to facilitate the
processing of a variety of polymers. They are classified as external
and internal lubricants depending on their mode of action; internal
lubricants act. Within the polymeric material itself, by producing the
cohesive forces acting as molecular interfaces within the resin, while
external lubricants act by reducing the adhesion of the polymeric
material to the hot metallic surface of the processing machinery.

Polymeric flow promoters have been developed to the greatest extent

for Unplastisized PVC and transparent PVC compounds.

E.g.: Ethylene Vinyl Acetate, Styrene Acrylonitrile, Chlorinated

Polyethylene etc.
 Lubricants

Lubricant or Formula Polymer for which omments

Processing aid the additives are
Recommended

1. Monoglyceryl Chain C14 – 18 PVC Internal

esters Lubricant

2. Waxes Chain C16 - 18 PVC Polyolefins Internal/

external slip
additives.
3. Hydrocarbon waxes PVC External
Lubricant
4. Soaps Metal stearates PVC Polyolefins External
Lubricants
Zinc stearate Polypropylene
Calcium stearate phenolic resins
Melamine, PVC
Magnesium ABS resins,
stearate Cellulosic Polyamides
5. Acrylates Terpolymers PVC Flow promoter
based on:
methyl acrylate-
butadiene-styrene
and acrylonitrile-
butadiene styrene.
Thixotropic Agents / Antisag Agents
In the processing of fluid systems such as pastes, liquid, resins,
very low viscous melts etc., it is desirable to have pseudoplastic or
thixotropic behaviour.
Common Thixotropic agents / Antisag Agents

Cellulodial asbestos Hydrophylic systems, e.g., Nylons, Polyesters

Magnesium oxide Polyester resins

Clays Polyester, PVC Pastes

Silica flour Polyester

PVC pastes
ADDITIVES WHICH MODIFY THE MECHANICAL PROPERTIES

Plasticizers
A plasticizer may be defined as a substance which when
incorporated in to a polymeric material improves flexibility
and processability, alters temperature dependent properties
such as softening point and low temperature flexibility and
has a significant effect on tensile strength elongation at
break and impact properties.

The Plasticizer reducing physical intermolecular forces

between the polymer chains, thereby increasing chain
mobility, which results softening.
 COMMERCIAL PLASTICIZERS FOR PLASTICS MATERIALS
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Plasticizer Polymer Plasticizer Type
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Di-octyl phathalate (DOP) Polyvinyl Chloride and General purpose primary
Copolymers. Plasticizers.

Tricresyl phosphate (TCP) Polyvinyl Chloride and Flame Retardant, Primary

Copolymers. Plasticizers.

Tricresyl phosphate (TCP) Cellulose Nitate Flame Retardant, Primary

Plasticizers.

Di-octyl adipate (DDA) Polyvinyl chloride cellulose LowtemperaturePlasticizers

Acetate butyrate.
Di-octyl sebacarte (DOS) Polyvinyl chloride cellulose Secondary
plasticizers Acetate butyrate.

Adipic acid polyester Polyvinyl chloride Non-migratory

(MW-1500-3000)
secondary plasticizer
Sebacic acid polyester Polyvinyl chloride Non-migratory
(MW-1500-3000) secondary plasticizer

Chlorinated paraffins Most polymers Flame retardant,

(%C l = 40 - 70) plasticizer extenders
MW = 600 – 1000

N-ethyl. o.p. toluene Polyamides General purpose

Sulphonamide primary plasticizers

Sulphonamide formaldehyde Non-migratory

Resin Polyamides secondary plasticizers
 Reinforcement for Composites
The term reinforcement is normally used to denote the increase in
modulus and in strength obtained when a second phase intrinsically
much stiffer and stronger than the base polymer is dispersed in the
polymer matrix. The properties of plastics are enhanced by
incorporates of short fibers a particulate reinforcing fillers (5 - 25%
V/V) or long fibers. (50 - 80% V/V) Typical reinforcing materials
available are Glass fiber, asbestos, boron, carbon fiber etc.

Commonly coupling agents:

Coupling agent Recommended resin
Vinyltrichlore silane Polyesters
Vinyltriethoxy silane Polyesters
Aminopropyl triethoxysilane Epoxides
Methacrylo-chromium complex Polyesters
Allytrichloro silane resorcinol Univesal
Toughening Agents

The most commonly used toughening agents are

acrylics and acrylates. ABS modifiers also used as
toughening agent. Chlorinated polyethylene is used in
PVC films. Impact modifier improves I.S. as the
expense of rigidity.
ADDITIVES USED TO REDUCE FORMULATION COST
Fillers
Fillers are classified as inorganic, mineral natural and synthetic. They are
more commonly used with the thermosetting resins such as the phenolies,
melamines, although they fill some thermoplastics as well.
Purpose Fillers
Bulk Wood flours, sawdust, wood pulp,
sisal, jute, purified cellulose, mica-rock.
Reinforcement Glass fibres and spheres, asbestos
fibres, cellulosic fibres, Cotton fabric,
paper synthetic fibres.
Hardness Inorganic pigments, mineral powders,
metallic oxides, Powder metals graphite
and silica.
Chemical Resistance Glass fibres and fabrics synthetic fibres
and fabrics, Graphite, metallic oxides.
Appearance Color pigments, dyestuffs carbon blacks
powdered Metals and phosphorescent
minerals woven fabrics.
 Factors for choosing the fillers are:
- Cost, availability and uniformity
- Compatibility or wettability with the resin moisture
absorption
- Physical properties
- Thermal stability to mould temperature
- Resistance to chemicals
- Abrasiveness
- Effect on plastics flow characteristics
 SURFACE PROPERTIES MODIFIERS

The surface properties of polymers have great

technological importance in three areas:

 Friction phenomena
 Adhesion to metals and other substrates in
laminar composite products.
 Surface conduction of electrical changes.
Anti-static Agents:
Chemical added to plastic to reduce builded of
electrostatic charges on the surface of material are called
antistatic agents. The most sensitive material to static
buildup are polyolefins, nylon, polyesters, urethanes,
cellulosics, acrylics and acrylonitrides. They are selected on
the basic of application, durability necessary concentration,
federal approval (for food packaging) and effectiveness at
low humidity, particularly below 25% when the hydrophilicaity
of agents, though always significant, becomes critical.
Anti-static agents for plastic are amines or quarternary
compounds, although some phosphate esters and
polyethylene glycol are also in use.
 Slip and Anti-block Additives in Polyolefin's
Slip agents are materials added to reduce the
coefficient of friction of the surface of films. Anti-block
agents are materials added to prevent the adhesion of
the surface of films to each other or to surfaces. Slip
agents - high molecular weight fatty alcohols
(concentration - 0.05%)
Specific requirements
1. They must not spoil the optical properties of the film
2. They must not interfere with the adhesion of
printing ink to the film
3. They must be colorless and non-toxic
Anti-block and slip agents in PVC
CaCO3, Waxes etc., are used as anti-block agents.
High molecular weight alcoholic as Slip agents.

Adhesion Promoters
Adhesion promoters reduces the surface tensions or
increases the magnitude of forces or bonds.
These are useful in bonding applications like
Sandwich of film/polymer/paper lamination, polymer metal
laminations, heat sealing of films etc. Some of the adhesion
promoters used are Phosphorous Containing Compound,
Steric acid Salicetic acid, piperidene derivative etc.
 OPTICAL PROPERTY MODIFIERS
Additives which alter the light transmission characteristics, Light transmission
properties are mainly a function of the difference in density of crystalline or
amorphous.
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Material Crystalline Amorphous region Optical
regions density density Transmission
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Polyethylene 1.01 0.84 Opaque/translucent

Polypropylene 0.94 0.836 Translucent

Poly 3, M-butene - 1 0.90 0.836 Translucent/Transparent

Poly 3, M-Pentene 1 0.83 0.83 Transparent

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Blowing Agent

A blowing or foaming agent is to produce a cellular structure in a plastic.

The basic requirements for an ideal chemical blowing agent are:

• Gas-release temperature must be within a narrow range

• Release rate must be controllable but rapid.
• Gas must not be corrosive
• Compound must be stable in storage
• Residue should be colorless non-staining and free of
unpleasant odors
• Compound and residue must be non-toxic
 TYPICAL PHYSICAL BLOWING AGENTS

Boiling range at
atmospheric
Pressure (o C) Comments Typical uses

Pentane 30 - 38 Non-Toxic Polystyrene foams

(Mainly by expandable
bends route)

Heptane 65 - 70 Non-Toxic Polystyrene foams

(Mainly by expandable
(bends route)
 Boiling range at
atmospheric
Pressure (o C) Comments Typical uses

Methelene chloride 40 Toxic, Flexible PVC and

Non-Flammable
Trichlorofluro 24 Non-Toxic Most widely used
Non-Flammable foaming agents. Major
Applications include
Polyurethane (Flexible)
And rigid (foams and
PVC) flexible foams.
Also used as auxiliary
to chemical blowing
Agents.
 TYPICAL CHEMICAL BLOWING AGENTS FOR CELLULAR PLASTICS
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Name Decomposition Comments
Range (o C)
Maximum rate
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Azodicarbolamide 160 - 200 Non-toxic, suitable
for polymers
Processed at fairly
High temperature
Can be activates.
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Azobisbutyronitrile Gives toxic residues
90 - 115 can activated or
inhibited
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Name Decomposition Comments
Range (o C)
Maximum rate
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Benzenesulphonuylh 90 - 100 Limited
ydrazone applications.
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P-tolune Sulphyonyl 210 - 270 Suitable for
semicarbe thermoplastics
processed at high
Temperature e.g.,
Nylon,
Polypropylene etc.
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COLORANTS
There are four methods used for colouring Polymers:
a) Surface Coating (Painting)
b) Surface dyeing
c) Introduction of colour forming groups into
Polymer molecules
d) Mass Colouration.

Colours are introducing into Polymer molecule through the

addition of colour master batch. Also, various types of
additive master batches are available for various
applications.
CONCLUSION

This brief-out line of the major categories of plastics

additives available, their nature, mode of activity and
disadvantages will serve as an initial guide to the
materials available and their efficiency in over coming
certain drawbacks inherent in many of the more widely
used plastic materials. Continuous improvement in
currently available additives is taking place and many
materials are in the final stages of development
throughout the world.