7.

1 Introduction: Additives in Polymers

Significance of Additives

 Additives enhance or modify the bulk properties of polymers, enabling their use in a
diverse range of applications.
 Examples:
o Rubber additives lead to products like tires, latex foam, and erasers.
o PVC additives create items ranging from rigid pipes to flexible baby pants and
insulating cables.

Additive Versatility

 Some additives, such as antioxidants, are broadly applicable across polymers and
applications.
 Others are highly specific, catering to particular polymers or specialized end-uses.

Classification of Additives

1. By Physical Form:
o Solids: Often fillers.
o Rubbers: For elasticity and strength.
o Liquids: Typically plasticizers and softeners.
o Gases: Used for creating cellular or foam-like polymers.
2. By Functionality:
o Fillers: Enhance strength, reduce cost.
o Plasticizers/Softeners: Increase flexibility.
o Lubricants/Flow Promoters: Aid processing.
o Anti-aging Additives: Improve longevity.
o Flame Retarders: Reduce flammability.
o Colorants: Add color.
o Blowing Agents: Create foamed structures.
o Cross-linking Agents: Strengthen polymer structure.
o UV-Degradable Additives: Enable environmental breakdown.

Desirable Properties of Additives

To be effective, additives should:

1. Function efficiently.
2. Remain stable during processing and service.
3. Avoid bleeding (migration into adjacent materials).
4. Avoid blooming (precipitation on the surface after cooling).
5. Be non-toxic and odorless.
6. Be cost-effective.
7. Not adversely affect the polymer’s properties.
Bleeding and Blooming Phenomena

Bleeding:

 Occurs when additives dissolve in both the polymer and adjacent materials, leading to
migration.
 Influenced by:
o Polymer structure (e.g., hole size in the matrix).
o Additive size and concentration.
o Operating above Tg (glass transition temperature) increases bleeding risk.

Blooming:

 Happens when additives are soluble at processing temperatures but not at ambient
conditions.
 Results in additive precipitation or "bloom" on the polymer surface upon cooling.
 Factors influencing blooming:
o Solubility of additives at different temperatures.
o Presence of nuclei, either from other additives or residual material.

Table 7.1 Summary: Blooming Scenarios

Concentration of Solubility at Solubility at

Example Expected Effect
Additive Ambient Temp Processing Temp
1 X 0 0 No blooming
2 X ≤X ≤X No blooming
Blooming unless
3 X ≤X >X
nucleated by additive
4 X >X >X No blooming

7.2 Fillers in Polymers

Definition and Purpose

 Fillers are solid additives incorporated into polymers to enhance their physical
properties, especially mechanical ones.
 Exclusion: Gaseous fillers (used in cellular polymers) are treated separately.

Classification of Fillers

Fillers are broadly classified into:

1. Particulate Fillers:
o Inert Fillers:
  Often termed a misnomer as they influence various properties.
 Examples: Calcium carbonates, china clay, talc, barium sulphate.
 Applications:
 Reduce extrusion die swell in plasticized PVC.
 Improve modulus, hardness, and electrical insulation.
 Act as a base for colorants.
 Reduce tackiness.
 Significantly reduce material costs.
o Reinforcing Fillers:
 Enhance properties like tensile strength, modulus, and abrasion
resistance.
 Examples: Carbon black, fine silicas, aluminum hydroxide.
2. Fibrous Fillers:
o Examples: Wood flour, cotton flock, macerated fabric, asbestos, glass fibers,
and carbon fibers.
o Applications:
 Improve impact strength, rigidity, and heat resistance.
 Create high-strength, high-modulus composites.

Particulate Fillers: Characteristics and Impact

1. Inert Fillers:
o Properties are influenced by:
 Particle size and distribution: Finer particles generally enhance
tensile strength and modulus.
 Particle shape and porosity: Plate-like particles (e.g., china clay) may
induce anisotropy. Porous particles can absorb additives, reducing their
effectiveness.
 Chemical surface properties: Polar surfaces may require treatment
(e.g., stearic acid for calcium carbonate) to improve polymer
compatibility and performance.
2. Reinforcing Fillers:
o Improve tensile strength (e.g., styrene-butadiene rubber tensile strength
increases from 3 MPa to over 20 MPa with carbon black).
o Reinforcement effectiveness depends on:
 Extensity factor: Surface area of filler in contact with polymer.
 Intensity factor: Chemical/physical bonding at the filler-polymer
interface.
 Geometrical factors: Particle aggregation and porosity.

Fibrous Fillers: Applications and Benefits

1. Organic Fibers:
o Examples: Wood flour, nylon fibers.
o Benefits: Enhance impact strength and toughness.
2. Inorganic Fibers:
 Examples: Glass fiber, asbestos.
o
Benefits: Provide heat resistance and strength in thermoplastic and
o
thermosetting resins.
3. Advanced Fibers:
o Examples: Carbon fibers, whiskers (single crystals).
o Applications: Specialized, high-performance uses.
o Benefits: High tensile strength, although interlaminar strength can be a
limitation.

Challenges with Fillers

1. Impurities in Fillers:
o Grit: Creates weak points in soft polymers.
o Trace metals (e.g., copper, manganese, iron): Reduce oxidative stability.
o Lead: Reacts with sulfur-containing additives, causing discoloration.
2. Overloading:
o Excessive filler concentration can reduce the effectiveness of reinforcement
due to a decrease in polymer content.

Composite Applications

 Fibrous fillers are often embedded in laminar forms.

 The fibers bear most of the stress in the plane of the composite, enhancing both
strength and modulus.
 Example: Glass fiber-treated fabrics for high strength in laminates.

7.2.1 Coupling Agents

Overview

Coupling agents enhance the performance of fillers in polymers by improving the adhesion
between the filler and the polymer matrix. This improvement transforms the filler-polymer
interface into a stress-bearing component, reducing mechanical weaknesses.

Mechanism of Action

1. Improved Wetting:
o Fillers are coated with compounds having dual compatibility:
 One part interacts with the filler.
 The other part interacts with the polymer.
 o Example: Calcium carbonate coated with stearic acid improves compatibility
with hydrocarbon rubbers.
2. Covalent Bonding:
o Coupling agents create covalent links between fillers and polymers, greatly
enhancing adhesion and mechanical properties.
o Early Example: Methacrylato-chrome chloride (used with glass fibers in
polyester-glass reinforced plastics).

Types of Coupling Agents

1. Silane Coupling Agents:

o Form siloxane linkages (Si-O-Si) with glass surfaces.
o React with unsaturated polymers via functional groups like vinyl, epoxy, or
amino groups.
o Applications:
 Bonding glass fibers to unsaturated polyester resins.
 Coupling particulate fillers like silicas and clays to rubber.
2. Titanium Coupling Agents:
o General formula: (RO)n−Ti−(OX−R−Y)m(RO)_n-Ti-(OX-R-Y)_m(RO)n
−Ti−(OX−R−Y)m.
o Benefits:
 Reduce viscosity in filled PVC plastisols.
 Increase impact strength in polypropylene and high-density
polyethylene with filler loadings up to 70%.
 Improve melt flow properties.
3. Specialized Agents for Rubber:
o Example: Silane groups pre-coupled to natural rubber molecules, which then
bind to filler particles during compounding.

Examples of Coupling Agents

Name Composition Applications

CH2=CH−SiCl3CH_2 = CH - SiCl_3CH2
Trichlorovinylsilane Polyester
=CH−SiCl3
CH2=CH−Si(OC2H5)3CH_2 = CH -
Triethoxyvinylsilane Polyester
Si(OC_2H_5)_3CH2=CH−Si(OC2H5)3
CH2−CH−O−(CH2)3−Si(OCH3)3CH_2 -
γ\gammaγ-
CH - O-(CH_2)_3-Si(OCH_3)_3CH2 Epoxide
Glycidoxypropyltrimethoxysilane
−CH−O−(CH2)3−Si(OCH3)3
γ\gammaγ- HS−(CH2)3−Si(OCH3)3HS-(CH_2)_3- Epoxide,
Aminopropyltrimethoxysilane Si(OCH_3)_3HS−(CH2)3−Si(OCH3)3 diene rubbers
[(3,4(3,4(3,4-Epoxycyclohexyl)- Epoxide,
OOO-Epoxide-functional silane
ethyl]trimethoxysilane phenolics
Applications

1. Glass Fiber Reinforcement:

o Silanes and methacrylato-chrome chlorides bond glass fibers to polymers.
o Widely used in laminates with polyester resins.
2. Rubber Compounding:
o Silica, silicates, and clays are treated with coupling agents to improve rubber
properties.
o Examples: Tire manufacturing and elastic components.
3. Filled Thermoplastics:
o Coupling agents improve the adhesion and mechanical performance of fillers
like calcium carbonate in polypropylene or PVC.

Innovations in Coupling Agents

1. Ene Molecular Reactions:

o Example: Silane pre-coupled to natural rubber before filler addition.
o Benefits: Ensures strong coupling between rubber and filler.
2. Titanium-Based Agents:
o Enhance flow properties and impact strength in highly filled polymers.

Key Benefits

 Enhanced mechanical properties of filled polymers.

 Improved processing characteristics (e.g., reduced viscosity and better melt flow).
 Broadened application range for polymers with fillers.

7.3 Plasticisers and Softeners

Introduction

Plasticisers have been an essential component of the plastics industry since the introduction
of Parkesine by Alexander Parkes. Initially, their primary role was to lower the viscosity of
polymers, making them easier to process. Over time, their function has expanded to enhance
the softness, flexibility, and processing characteristics of polymers.

Primary Functions of Plasticisers

 1. Molecular Spacing:
o Plasticisers insert themselves between polymer molecules, reducing the energy
required for molecular bond rotation.
o This allows polymers to flow at lower temperatures without decomposing.
2. Lower Melt Viscosity:
o Plasticisers help in reducing the melt viscosity, improving processability in
manufacturing.
3. Physical Property Modification:
o Increase Softness and Flexibility: Plasticisers make polymers more pliable.
o Lower Cold Flex Temperature: Reduces the temperature at which a polymer
loses flexibility.

Commonly Used Polymers

Plasticisers are typically used with the following polymers:

 Polyvinyl acetate
 Acrylic polymers
 Cellulose acetate
 Poly(vinyl chloride) (PVC): The most important polymer for plasticiser usage.

Plasticiser Characteristics

 Solubility and Molecular Weight:

o Plasticisers must have a solubility parameter similar to the polymer to ensure
effective blending.
o They generally have a molecular weight of at least 300.
 Crystallisation Tendency:
o Plasticisers must interact specifically with the polymer if either the polymer or
the plasticiser tends to crystallize.

Plasticiser Theories

1. Polar Theory:
o Plasticisers act not just as spacers but can form temporary links with the
polymer molecules.
o Dipole interactions between polar groups in the polymer and plasticiser create
these links.
o For example, in PVC, a chlorine atom can form a dipole with a polar ester
group in the plasticiser.
o This can lead to a form of "polar cross-linking" where the plasticiser connects
to two or more polymer molecules.
2. Hydrogen Bonding Theory:
 o This theory suggests that plasticisers form hydrogen bonds with the polymer
molecules.
o In PVC, the hydrogen on the carbon adjacent to the chlorine can act as a
proton donor, while certain groups in the plasticiser (such as phosphates,
esters, and ethers) can act as proton acceptors.
o This interaction is stronger with phosphates and aromatic esters compared to
aliphatic ethers.

Plasticiser Examples

 Tritolyl phosphate: A highly polar and polarisable plasticiser that leads to stronger
interactions with the polymer, resulting in higher modulus and hardness, and a higher
cold flex temperature.
 Dioctyl sebacate: A less polar plasticiser, which has a more significant spacing effect
and leads to softer compounds with a lower cold flex temperature.

Softeners in the Rubber Industry

 Softeners: Used in the rubber industry, these materials primarily provide spacing
effects to reduce the hardness and facilitate processing. They have minimal interaction
with the polymer.
 Hydrocarbon oils: Often used as softeners in rubbers.
 Plasticisers in Rubbers: Phthalates, phosphates, and sebacates are commonly used in
more polar rubbers, similar to their role in plastics.

Extenders

 Role of Extenders: Extenders are materials that are not plasticisers themselves but
can be added to a plasticiser-polymer system to reduce costs while maintaining some
of the desired properties.
 Common Extenders:
o Refinery oils and chlorinated waxes are frequently used in PVC. Chlorinated
waxes can also act as flame retardants.

Key Takeaways

 Plasticisers play a vital role in reducing the viscosity, increasing flexibility, and
improving processability of polymers.
 The interaction between plasticisers and polymers is complex and can be explained
through theories of polarity and hydrogen bonding.
 Softeners, commonly used in the rubber industry, have a similar function but with less
chemical interaction than plasticisers.
  Extenders provide cost-effective alternatives in plasticiser formulations without
significantly altering the polymer's properties.

7.4 Lubricants and Flow Promoters

Lubricants and flow promoters are additives used to improve the processing and performance
of polymers. These agents serve various functions, and they can be classified into three main
types based on their role:

1. Lubricants for Finished Products (External Lubricants)

o These lubricants reduce the friction of molded or finished products when they
come into contact with other materials, whether they are the same polymer or
different.
o Examples: Graphite and molybdenum disulfide are often used in nylons and
other thermoplastics, particularly in gear and bearing applications (typically in
quantities of 1-2%).
o Their primary function is to reduce wear and friction, enhancing durability in
applications that involve movement or contact with other surfaces.
2. External Lubricants in Processing
o These lubricants exude from the polymer during processing and create a thin
film at the interface between the molten polymer and the metal surfaces of
processing equipment (e.g., extruders and calenders).
o This thin film prevents the polymer from sticking to the equipment, which
facilitates smooth processing.
o Examples: Stearic acid, stearate salts (e.g., calcium, lead, barium),
hydrocarbons (e.g., paraffin wax, low molecular weight polyethylene), and
certain esters (e.g., ethyl palmitate).
o Challenges: Overuse of external lubricants can lead to contamination of the
processing equipment, which may result in color or quality issues in
subsequent batches. Excessive lubrication can also affect the clarity and
printability of the polymer, particularly with PVC.
3. Internal Lubricants (Flow Promoters)
o These are low molecular weight materials that help promote the flow of
polymer during melt processing. Unlike plasticizers, they have minimal
impact on the solid-state properties of the polymer.
o Examples: Amine waxes, montan wax ester derivatives, glyceryl esters (e.g.,
glyceryl monostearate), and long-chain esters (e.g., cetyl palmitate).
o Role: They facilitate the smooth flow of the polymer through the processing
equipment without significantly altering the final polymer properties. They are
essential in applications like extrusion and injection molding where uniformity
and ease of flow are critical.

Polymeric Flow Promoters

 A newer class of additives, polymeric flow promoters, function similarly to internal

lubricants, but their chemical nature is different. These are polymers that are
 compatible with the base polymer and have lower viscosity at processing
temperatures, making them more effective at enhancing flow without compromising
the final properties of the polymer.
 Examples: Ethylene-vinyl acetate (EVA) copolymers, styrene-acrylonitrile (SAN)
copolymers, styrene-methyl methacrylate (SMMA) copolymers, and chlorinated
polyethylenes.
 Application: These are often used in applications like unplasticized and transparent
PVC compounds, where good flow is critical for high-quality output. Interestingly,
some of these polymeric flow promoters may also be used as impact modifiers in
other PVC formulations, enhancing the impact strength.

Summary

 Lubricants are essential for reducing friction in finished products, preventing

sticking during processing, and improving flow properties during molding or
extrusion.
 Flow promoters (both internal and polymeric) enhance the flow of the polymer
during processing without significantly altering its final properties, and they are
particularly useful in applications where smooth processing and high-quality output
are required.
 The selection of lubricants and flow promoters depends on the specific polymer,
processing conditions, and desired properties of the final product.

7.5 Anti-Aging Additives

The properties of plastics typically degrade over time due to various structural changes.
These changes usually result in negative consequences for the material's strength, flexibility,
color, and electrical properties. The main types of structural modifications leading to aging
are:

1. Chain Scission:
o This process breaks the polymer chains, leading to a loss in strength and
toughness. Chain scission occurs due to chemical reactions such as oxidation
or high-energy radiation exposure.
2. Cross-Linking:
o Cross-linking involves the formation of bonds between polymer chains, which
can cause hardening, brittleness, and changes in solubility. Cross-linked
polymers often become more rigid and may lose their ability to dissolve in
solvents.
3. Development of Chromophoric Groups:
o These groups (often due to oxidation or exposure to UV light) result in color
changes, leading to discoloration of the plastic. This is often seen as yellowing
or darkening over time.
4. Development of Polar Groups:
 o For example, the formation of carbonyl groups in polyolefins can deteriorate
their electrical insulation properties and increase their chemical reactivity.
This can make the material more prone to further degradation.

These structural changes occur due to several chemical reactions, primarily:

 Oxidation: The reaction of polymers with oxygen, often exacerbated by heat or UV

light, leading to chain scission, cross-linking, or the formation of polar groups.
 Ozone Attack: Ozone in the atmosphere can react with certain polymers, especially
rubbers, causing cracking and degradation.
 Dehydrochlorination: This occurs in chlorinated polymers, such as polyvinyl
chloride (PVC), where hydrochloric acid (HCl) is released, causing chain degradation.
 Ultraviolet (UV) Attack: UV radiation breaks down polymer chains, leading to the
formation of chromophoric and polar groups, as well as oxidation and other
degradation processes.

To combat these aging processes, various additives are used to prevent or slow down
degradation. These additives are introduced to plastics to protect against the chemical
reactions that lead to aging:

 Antioxidants: These inhibit oxidation reactions, preventing chain scission and the
formation of polar groups that degrade the material's properties.
 Antiozonants: These additives protect against ozone-induced degradation,
particularly in rubbers and elastomers, by preventing ozone from attacking the
polymer structure.
 Dehydrochlorination Stabilizers: In chlorinated polymers like PVC, these additives
prevent or slow the release of hydrochloric acid, thereby preserving the polymer's
integrity.
 Ultraviolet Absorbers: These protect the polymer from the harmful effects of UV
radiation by absorbing UV light and preventing it from breaking down the polymer
chains.

7.5.1 Antioxidants

Oxidation of hydrocarbons, including hydrocarbon-based polymers, typically occurs via a

free-radical chain reaction. This reaction is initiated by various mechanisms such as
mechanical shearing, exposure to ultraviolet (UV) radiation, or attack by metal ions (e.g.,
copper and manganese). The breakdown of a hydrocarbon molecule leads to the formation of
free radicals:

R−R→mechanical,UV,metalionR∗+R∗R-R \xrightarrow{mechanical, UV, metal ion} R* +

R* R−Rmechanical,UV,metalionR∗+R∗

These free radicals (denoted as R∗R*R∗) rapidly react with oxygen to form peroxide
radicals:
R∗+O2→R−O2∗R* + O_2 \xrightarrow{} R-O_2*R∗+O2R−O2∗

This peroxide radical can then propagate the chain reaction by reacting with another
hydrocarbon molecule, forming a hydroperoxide and regenerating the free radical:

R−O2∗+RH→ROOH+R∗R-O_2* + RH \xrightarrow{} ROOH + R*R−O2∗+RH

ROOH+R∗

The hydroperoxide formed can decompose through several pathways, which may result in
chain extension or cross-linking. Some of these reactions are:

ROOH→RO∗+OHROOH \xrightarrow{} RO* + OHROOHRO∗+OH

2ROOH→RO∗+R−O2∗+H2O2ROOH \xrightarrow{} RO* + R-O_2* + H_2O2ROOH
RO∗+R−O2∗+H2O ROOH+RH→RO−+R∗+H2OROOH + RH \xrightarrow{} RO- + R* +
H_2OROOH+RHRO−+R∗+H2O

The chain reaction can be terminated by various mechanisms, such as:

2R−O2∗→non-radical product2R-O_2* \xrightarrow{} \text{non-radical product}2R−O2∗

∗+R∗R−O2−R R∗+R∗→R−RR* + R* \xrightarrow{} R-RR∗+R∗R−R

non-radical product R−O2∗+R∗→R−O2−RR-O_2* + R* \xrightarrow{} R-O_2-RR−O2

If these termination reactions occur multiple times, the polymer can undergo chain extension
or cross-linking, potentially leading to material degradation.

Types of Antioxidants:

Antioxidants function by interrupting the oxidation chain reaction. There are two main types
of antioxidants:

1. Preventive Antioxidants: These prevent the formation of radicals by inhibiting

reactions like the formation of free radicals (equations 7.1 and 7.3).
2. Chain-Breaking Antioxidants: These interrupt the propagation cycle by reacting
with radicals R∗R*R∗ and R−O2∗R-O_2*R−O2∗, introducing new termination
reactions.

Some additives, called oxidation retarders, may also slow down the chain reaction by
introducing new propagation reactions, making the oxidation process slower.

Chain-Breaking Antioxidants:

The most common chain-breaking antioxidants are amines and phenols. Phenolic
antioxidants are generally preferred in polymers due to their lower tendency to cause staining
or discoloration. Amines are more commonly used in rubbers (e.g., in tires), where the
advantages of cost and effectiveness outweigh the potential for discoloration.

Some general reactions of antioxidants are:

 Reaction with O2O_2O2 and peroxide radicals:

 AH+O2→A∗+HO2∗AH + O_2 \xrightarrow{} A* + HO_2*AH+O2A∗+HO2∗
AH+R−O2∗→A∗+ROOHAH + R-O_2* \xrightarrow{} A* + ROOHAH+R−O2∗
A∗+ROOH A∗+RH→A−OH+R−O2∗A* + RH \xrightarrow{} A-OH + R-
O_2*A∗+RHA−OH+R−O2∗

o These reactions aim to break the chain of oxidation by consuming the radicals.
 Termination Reactions:

2A∗→A−A2A* \xrightarrow{} A-A2A∗A−A A∗+R−O2∗→AOORA* + R-O_2* \

xrightarrow{} AOORA∗+R−O2∗AOOR

For chain-breaking antioxidants to be effective, reactions that terminate the chain reaction
(e.g., equations 7.8b and 7.9) should be favored over reactions that propagate the reaction
(e.g., equation 7.8a).

Preventive Antioxidants:

Preventive antioxidants function by preventing the initial formation of free radicals, or by

decomposing peroxides before they can form radicals. Common types include:

1. Peroxide Decomposers: These substances prevent the formation of radicals by

decomposing hydroperoxides into stable products. Examples include mercaptans,
sulphonic acids, and various phosphites.
2. Metal Deactivators: These are used to prevent metal ions (e.g., copper, manganese,
iron) from catalyzing oxidation reactions. Chelating agents can form stable complexes
with metal ions to deactivate them, though their effectiveness may vary depending on
the metal involved.
3. Ultraviolet (UV) Absorbers: UV radiation can initiate oxidation reactions in
polymers, so UV absorbers are often used to prevent the degradation caused by
exposure to sunlight.

Synergism in Antioxidants:

Synergism occurs when two or more antioxidants work together to produce a greater
protective effect than they would individually. For example, a combination of peroxide
decomposers and chain-breaking antioxidants can work together effectively, as the
peroxide decomposer reduces the number of radicals, which can then be more efficiently
neutralized by the chain-breaking antioxidants.

Commonly used combinations include 4-methyl-2,6-di-t-butylphenol (a phenolic

antioxidant) and dilauryl thiodipropionate (a peroxide decomposer).

Assessment of Antioxidants:

Antioxidants are assessed by their ability to delay oxidation. Common methods include
evaluating the induction period (time before oxidation begins) and the rate of oxidation in
petroleum fractions, as well as measuring changes in physical properties like flow
properties, embrittlement, and tensile strength in various polymers like polyethylene,
polypropylene, and natural rubber.
In conclusion, antioxidants are crucial for preventing the degradation of polymers by
oxidation. The use of chain-breaking antioxidants, preventive antioxidants, and the
combination of different types can significantly enhance the durability of materials by
slowing or halting the oxidative degradation process.

7.5.2 Antiozonants

Diene rubbers are highly susceptible to degradation when exposed to ozone, especially under
stress. The ozone interacts with the rubber, causing cracks to form that are perpendicular to
the direction of stress. This cracking occurs only when the rubber is under stress in the
presence of ozone, as ozone does not cause cracking in unstressed rubber or when rubber is
stressed after the ozone has been removed.

In the past, waxes were used to protect diene rubbers from ozone-induced degradation. These
waxes would bloom to the surface of the rubber and form an impermeable film. This
approach was effective for static applications, but it was less successful under dynamic
conditions, where the rubber was subjected to continuous mechanical movement. The wax
layer would break down, reducing its protective effectiveness.

Since the 1950s, a number of materials have been found to be effective in preventing ozone-
induced degradation. One key group of materials is p-phenylenediamine derivatives, which
have proven successful in combating ozone-related degradation, particularly in rubber
materials. The choice of antiozonant depends on the type of polymer and whether the rubber
will experience dynamic stressing during use.

It is important to note that antiozonants are not typically used in plastics, including those that
may incorporate rubber particles for toughening. Thus, antiozonants are more relevant to
rubber materials, and they will not be discussed further in the context of plastics. For further
details on antiozonants in rubber, one should consult specialized references on the topic.

7.5.3 Stabilisers Against Dehydrochlorination

Stabilisers against dehydrochlorination are crucial additives primarily used in chlorine-

containing polymers, especially in poly(vinyl chloride) (PVC). Dehydrochlorination is a
degradation process where the polymer loses hydrogen chloride (HCl), which can lead to a
breakdown of the polymer's structure and a loss of its properties.

These stabilisers help prevent this degradation by inhibiting or slowing down the
dehydrochlorination process, thus prolonging the material's useful life. Since their primary
application is in PVC, these stabilisers are often used in formulations of this polymer to
maintain stability during processing and in its end-use applications.
Further details on these stabilisers and their role in enhancing the longevity of chlorine-
containing polymers will be covered in Chapter 12.

7.5.4 Ultraviolet Absorbers and Related Materials

Exposure to ultraviolet (UV) light, particularly in the presence of oxygen, can lead to
physical and chemical degradation of polymers. These effects include discolouration, surface
cracking, hardening, and changes in electrical properties. The severity of these effects varies
depending on the chemical composition of the polymer, but for most applications, such
degradation is undesirable. However, in some cases, the degradation effects may be
intentionally induced, such as to promote cross-linking or controlled degradation.

The most damaging UV radiation has wavelengths shorter than 400 nm, with the range
between 300–400 nm being the primary source of damage in terrestrial applications, as the
Earth's atmosphere absorbs most light below 300 nm (Figure 7.8).

UV-Absorbing Mechanisms

When a molecule absorbs UV light, it is activated to an electronically excited state (A →

A*), and a number of processes can follow:

1. Photophysical processes:
o Emission of energy (e.g., phosphorescence or fluorescence): The molecule
releases energy in the form of light.
o Generation of heat (radiationless conversion): The molecule dissipates the
absorbed energy as heat.
o Energy transfer: The excited molecule can transfer energy to other
molecules.
2. Photochemical processes:
o Energy transfer: Excited molecules may transfer energy to other molecules,
causing further reactions.
o Chemical reaction of excited molecules: The excited molecule may undergo
chemical reactions similar to those induced by thermal excitation, leading to
degradation of the polymer.

To protect polymers from UV damage, there are three primary strategies:

1. Light Screens
2. Ultraviolet Absorbers
3. Quenching Agents

Light Screens

Light screens function by absorbing damaging UV radiation before it reaches the polymer
surface or by limiting its penetration into the polymer mass. For example, coatings or
pigment-loaded paints have been used to protect natural materials like wood, and similar
methods can be applied to protect polymers. Another method involves coating polymers with
a layer containing a high concentration of UV absorbers. Carbon black, a common material
used in light screens, works effectively as it absorbs UV radiation and serves as a thermal
antioxidant. For optimal effectiveness, carbon black must be fine-particle-sized (15-25 nm)
and used at concentrations of at least 2%, ensuring good dispersion.

Ultraviolet Absorbers

UV absorbers are specific types of light screens that primarily absorb UV radiation,
particularly in the harmful UV range (300–400 nm). These absorbers should have minimal
absorption in the visible spectrum to prevent undesirable colour formation in the polymer.
Commercially important UV absorbers, such as o-hydroxybenzophenones, o-
hydroxyphenylbenzotriazoles, and salicylates, function by converting absorbed UV energy
into heat, thus preventing the polymer from undergoing damaging reactions.

Quenching Agents

Quenching agents are not strong UV absorbers, but they interact with the excited polymer
molecules to de-excite them and prevent further degradation. The quenching process occurs
through the following mechanisms:

1. A* + Q → A + Q* (De-excitation by photophysical process)

Here, A represents the excited polymer molecule, Q is the quenching agent, and A...Q*
represents the excited complex formed by the interaction. Quenching agents, such as
nickel(II) chelates and hindered amines, help prevent UV-induced degradation by stabilizing
the excited state of the polymer molecules.

These materials provide significant protection against UV degradation, extending the life and
maintaining the properties of polymers used in environments exposed to sunlight or other
sources of UV radiation.

7.6 Flame Retarders

Flame retarders are chemicals added to polymers to reduce their flammability or delay the
ignition and spread of fire. These retardants are particularly important in applications where
fire resistance is crucial, such as in building materials, furniture, and fittings. However, there
are some applications, such as in disposable packaging, where it is desirable for plastics to
burn easily. For materials like unplasticized PVC, phenolic resins, and aminoplastics, fire
resistance is naturally high, but other polymers like polyolefins, polystyrene, and
polyurethanes tend to be more flammable. This has driven the increasing use of flame
retardants.

Mechanisms of Flame Retardants

Flame retardants can work by one or more of the following mechanisms:

1. Chemical Interference: They can chemically interfere with the propagation of the
flame.
 2. Generation of Incombustible Gases: By producing non-flammable gases, they dilute
the oxygen supply, slowing combustion.
3. Endothermic Reactions: They absorb heat through decomposition or state changes,
thus cooling the polymer.
4. Formation of Fire-Resistant Coatings: Some flame retardants form protective
coatings that block oxygen from reaching the polymer.

Types of Flame Retardants

1. Phosphates:
Phosphate-based flame retardants are widely used, with tritolyl phosphate and
trixylyl phosphate being popular as plasticizers in PVC, maintaining its flame
resistance. However, for even better performance, halophosphates like
tri(chloroethyl) phosphate, in combination with antimony oxide or triphenyl stibine,
are more effective.
2. Halogenated Compounds:
Chlorinated paraffins are used in PVC and polyesters, and brominated compounds
are often more effective than chlorine-based ones. Bromine compounds, such as
tribromotoluene and pentabromophenyl allyl ether, are widely used. These
compounds function by releasing halogen gases (HCl or HBr) during combustion,
which dilutes the flammable gases and slows down the fire.
3. Antimony Oxide:
Antimony oxide is a widely used additive for flame retardancy, although on its own, it
has limited effectiveness. It works synergistically with both halogen and phosphorus
compounds, enhancing their performance. Other oxides like titanium dioxide, zinc
oxide, and molybdic oxide are sometimes used as alternatives or partial
replacements.
4. Aluminum Trihydrate:
Aluminum trihydrate is used in polymers that do not require high processing
temperatures, such as polyester laminating resins. When heated, it releases water,
which helps in cooling and suppressing flames.
5. Red Phosphorus:
In nylons, red phosphorus has been successfully used as a flame retardant, providing
a V-0 rating under UL 94 specifications. It has a minimal impact on electrical
properties and toughness, although it can discolor the material.
6. Melamine Salts:
Melamine salts are used in nylons, particularly when bright colors are required.
These salts do not negatively affect electrical properties and are also used in
polyurethane foams. They decompose at around 320°C.

Environmental and Safety Considerations

The use of flame retardants has become more complex due to the realisation that smoke and
toxic combustion products cause more fatalities than fire itself. The suppression of fires may
lead to smouldering fires that produce significant amounts of smoke and toxic gases like
carbon monoxide, hydrogen cyanide, and hydrogen halides, which can be highly
poisonous and corrosive, especially in confined spaces like submarines or aircraft. This has
raised concerns about the safety of halogen-containing flame retardants, leading to
restrictions on their use in certain polymers.
In response, there is growing interest in alternative flame retardant approaches, such as:

 Intumescent Materials: These materials expand when heated to form a protective

layer that shields the polymer from fire and oxygen.
 Ablative Char Formation: Polymers like phenolic resins can form a hard char when
burned, which protects the underlying material from further combustion.

Overall, while flame retardants are essential for fire safety in many applications, their
environmental and health impacts have prompted a shift towards safer alternatives.

7.7 Colorants

Coloring polymers is an essential part of many plastic and rubber products. There are four
primary methods for coloring polymers:

1. Surface Coating:
This method involves applying a layer of colorant (such as paint) to the surface of the
polymer. While effective, it adds extra processing steps and increases costs, so it is
typically avoided unless necessary, such as in the case of fibers.
2. Surface Dyeing:
Surface dyeing is useful for some polar polymers like nylons, where only a small
quantity of material needs to be colored. However, this method is generally less
common for mass applications.
3. Introduction of Chromophoric Groups:
Introducing color-forming groups (chromophores) directly into the polymer structure
can create color. However, this method is usually expensive and inflexible, making it
less popular for most practical applications.
4. Mass Coloration:
This is the most common and cost-effective method for coloring rubbers and plastics,
where colorants are uniformly mixed into the polymer during the production process.

Types of Colorants

Colorants are generally divided into two categories:

 Insoluble Colorants (Pigments):

Pigments are colorants that do not dissolve in the polymer but instead remain
dispersed within it. They are often used because they are stable and can provide
strong covering power.
 Soluble Colorants (Dyestuffs):
Dyestuffs are colorants that dissolve in the polymer and create more transparent
colors. Many colorants, however, have a low but finite solubility, which can
sometimes lead to issues like blooming (the migration of colorant to the surface).

Although this classification is useful, many colorants can have both soluble and insoluble
properties, so the distinction is not always clear-cut. To avoid issues like blooming, high
molecular weight colorants are often preferred, as they are less likely to migrate to the
surface.

Properties of Ideal Colorants

For a colorant to be effective in a polymer, it must meet several criteria:

 Covering Power:
Colorants should have strong covering power, meaning they can effectively hide the
polymer’s natural color. However, in some cases, a colorant with lower covering
power may be chosen if it is much cheaper, as more of the colorant can be
incorporated to maintain cost efficiency.
 Stability to Processing:
The colorant should be resistant to the processing conditions, including heat and shear
forces. Some colorants may break down under intense shearing, resulting in color
changes. It is also important that the colorant does not interfere with the
polymerization process or react with other additives used in the polymerization.
 Blooming and Bleeding:
Some colorants may migrate to the surface (blooming) or leach out of the polymer
(bleeding), which can be undesirable in certain applications. These issues can be
mitigated by using colorants with higher molecular weight.
 Impact on Polymer Properties:
Some colorants can negatively affect the properties of the polymer, such as its
oxidation resistance or electrical insulation behavior. Therefore, the choice of colorant
should not compromise the overall performance of the polymer.
 Anisotropic Effects:
Certain pigments can become oriented during processing, creating unusual visual
effects (anisotropy) in the final product. This can be either beneficial or detrimental
depending on the desired outcome.

In conclusion, while colorants are essential for creating visually appealing products, their
choice and application require careful consideration of the material properties, processing
conditions, and the intended use of the polymer.

7.8 Blowing Agents

Blowing agents are substances used to create a cellular structure in polymers by introducing
gas-filled cells within the polymer matrix. These agents can be categorized based on their
method of operation:

1. Chemical Blowing Agents:

These agents decompose during processing to produce volatile reaction products
(gases) that create bubbles or cells in the polymer. This process is typically controlled
to ensure consistent results.
2. Volatile Blowing Agents:
These are low boiling liquids that vaporize during processing, creating gas bubbles
 within the polymer. They are commonly used with materials like polystyrene and
polyurethanes.
3. Gas Diffusion:
This involves diffusing a gas into the polymer under pressure, followed by expansion
at elevated temperatures once the pressure is reduced. This process can be used with a
wide range of polymers.
4. Solid Carbon Dioxide:
In this method, powdered solid carbon dioxide is incorporated into the polymer. The
CO₂ volatilizes when heated, causing the polymer to expand. This technique is used
with materials such as PVC pastes.
5. Polymer Intermediate Reactions:
Chemical reactions occurring during polymerization or cross-linking can also create
cellular structures. This is particularly important with polyurethanes.
6. Mechanical Whipping:
In this method, polymers in a liquid state are mechanically whipped to introduce air or
gas bubbles, which are then stabilized as the polymer sets. Latex rubber foam is a
well-known product of this method.
7. Expandable Spheres:
Hollow or expandable microballoons made of resin or glass can be incorporated into
the polymer to create a cellular structure when they expand during processing.
8. Leaching Soluble Additives:
This method involves the use of soluble additives that are later leached out, leaving
behind voids that create a cellular structure.

Cellular Plastics Production and Control

The production of cellular plastics is extensive, and the texture and properties of these
materials can be carefully controlled by adjusting factors like:

 Average Cell Size: The size of individual cells in the foam.

 Cell Size Distribution: The range of cell sizes, which can include some large cells
within a matrix of smaller cells.
 Intercommunication Between Cells: Whether the cells are interconnected, which
affects the foam's properties.
 Non-Cellular Skins: Some cellular plastics have solid, non-cellular outer layers,
which can be used for structural strength or aesthetic purposes.

These variables are controlled by processing conditions and the use of cell nucleating agents,
cell stabilizers, and blowing agents.

Requirements for Chemical Blowing Agents

Chemical blowing agents must meet several special requirements in addition to the general
properties required for all additives:

1. Defined Temperature Range:

The gases must be released within a narrow and controlled temperature range,
ensuring consistent cell formation.
2. Decomposition Temperature:
The decomposition temperature of the blowing agent must be suitable for the polymer
 being processed. For instance, a blowing agent for PVC should decompose below the
maximum processing temperature to avoid polymer degradation.
3. Non-Corrosive Gases:
The gases produced by the decomposition of the blowing agent should not corrode
processing equipment.

While many materials have been tested as potential blowing agents, only a small number are
used in practice. The specific materials used are summarized in Table 7.8 and Figure 7.9,
which provide details of their chemical structures and characteristics.

.9 Cross-Linking Agents

Cross-linking is a crucial process for producing thermoset plastics or vulcanized rubbers. It

involves the formation of covalent bonds between polymer chains, creating a three-
dimensional network structure that is heat-resistant and insoluble. Cross-linking agents are
substances that facilitate this bonding by reacting with the polymer chains to create these
links. There are several types of cross-linking agents:

1. Bridging Agents

These molecules physically connect two polymer molecules, creating cross-links between
them. Examples include:

 Sulphur, selenium, and sulphur monochloride: Used in the vulcanization of diene

rubbers (like natural rubber).
 Formaldehyde: Used to cross-link phenolic resins.
 Di-isocyanates: React with hydrogen atoms in polyesters and polyethers to create
cross-links.
 Polyamines: Used for cross-linking in fluoroelastomers and epoxide resins.

2. Cross-Linking Initiators

These agents start the cross-linking reaction by initiating the polymerization of unsaturated
bonds. One of the most common initiators is peroxides, which initiate double-bond
polymerization in unsaturated polyesters. Other examples include:

 Peroxides: They are highly effective at initiating cross-linking in unsaturated

polyesters.

3. Catalytic Cross-Linking Agents

Catalysts facilitate the cross-linking process without directly participating in the formation of
covalent bonds. They accelerate the rate of cross-linking reactions. Some examples include:

 Acids: Used in the cross-linking of phenolic resins and aminoplastics.

 Certain amines: Used for cross-linking in epoxide resins.

4. Active Site Generators

These agents generate active sites on the polymer chain that can initiate cross-linking. A good
example is peroxides, which abstract protons from the polymer chains, resulting in either
scission (breaking of chains) or cross-linking depending on the polymer.

Types of Cross-Linking Agents (Figure 7.10)

 (a) Bridging Agents: These form links between two polymer chains.
 (b) Cross-Linking Initiators: These kick-start the cross-linking reaction.
 (c) Catalytic Cross-Linking Agents: These accelerate the cross-linking process
without becoming part of the final product.
 (d) Active Site Generators: These create reactive sites on the polymer chain that lead
to cross-linking.

The specific applications of cross-linking agents for different polymers are addressed in more
detail in their respective chapters, providing insights into the variety of reactions and
processes they can trigger in thermoset plastics and rubbers.

7.9 Cross-Linking Agents

Cross-linking is a crucial process for producing thermoset plastics or vulcanized rubbers. It

involves the formation of covalent bonds between polymer chains, creating a three-
dimensional network structure that is heat-resistant and insoluble. Cross-linking agents are
substances that facilitate this bonding by reacting with the polymer chains to create these
links. There are several types of cross-linking agents:

1. Bridging Agents

These molecules physically connect two polymer molecules, creating cross-links between
them. Examples include:

 Sulphur, selenium, and sulphur monochloride: Used in the vulcanization of diene

rubbers (like natural rubber).
 Formaldehyde: Used to cross-link phenolic resins.
 Di-isocyanates: React with hydrogen atoms in polyesters and polyethers to create
cross-links.
 Polyamines: Used for cross-linking in fluoroelastomers and epoxide resins.

2. Cross-Linking Initiators

These agents start the cross-linking reaction by initiating the polymerization of unsaturated
bonds. One of the most common initiators is peroxides, which initiate double-bond
polymerization in unsaturated polyesters. Other examples include:

 Peroxides: They are highly effective at initiating cross-linking in unsaturated

polyesters.
3. Catalytic Cross-Linking Agents

Catalysts facilitate the cross-linking process without directly participating in the formation of
covalent bonds. They accelerate the rate of cross-linking reactions. Some examples include:

 Acids: Used in the cross-linking of phenolic resins and aminoplastics.

 Certain amines: Used for cross-linking in epoxide resins.

4. Active Site Generators

These agents generate active sites on the polymer chain that can initiate cross-linking. A good
example is peroxides, which abstract protons from the polymer chains, resulting in either
scission (breaking of chains) or cross-linking depending on the polymer.

Types of Cross-Linking Agents (Figure 7.10)

 (a) Bridging Agents: These form links between two polymer chains.
 (b) Cross-Linking Initiators: These kick-start the cross-linking reaction.
 (c) Catalytic Cross-Linking Agents: These accelerate the cross-linking process
without becoming part of the final product.
 (d) Active Site Generators: These create reactive sites on the polymer chain that lead
to cross-linking.

The specific applications of cross-linking agents for different polymers are addressed in more
detail in their respective chapters, providing insights into the variety of reactions and
processes they can trigger in thermoset plastics and rubbers.

7.10 2-Oxazolines: Multifunctional Additives

2-Oxazolines were introduced in the 1990s as materials that do not fit neatly into traditional
additive categories. They are used for three distinct purposes:

1. To Produce Viable Blends of Incompatible Polymers

2-Oxazolines can be used to facilitate the blending of polymers that are typically
incompatible. This is achieved by forming chemical bonds between the polymers,
making them mix more easily and improving their blend properties.
2. To Protect Condensation Polymers from Hydrolysis
Specifically, 2-oxazolines can be used to protect condensation polymers, such as
polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), against
hydrolysis. This is done by reacting with terminal groups to "cap" them, preventing
hydrolysis from breaking down the polymer.
3. To Increase the Molecular Weight of Recycled Polymers
2-Oxazolines can also be used to increase the molecular weight of recycled polymers
that have suffered degradation. This helps improve the properties of recycled plastics,
restoring some of their original characteristics.
Synthesis and Structure

2-Oxazolines are typically prepared by reacting a fatty acid with ethanolamine, as shown in
Figure 7.11. For example, isopropenyl-2-oxazoline (IPO) was one of the first developed
materials in this category, and ricinoloxazolinmaleinate is another example, as illustrated in
Figure 7.12.

Polymerization and Grafting

Polymers containing oxazoline groups can be obtained by:

1. Grafting the 2-oxazoline onto an existing polymer: Such as polyethylene or

polyphenylene oxide.
2. Copolymerizing a monomer: Such as styrene or methyl methacrylate with a small
amount (<1%) of a 2-oxazoline.

The grafting reaction is typically carried out in an extruder at temperatures around 200°C,
using a peroxide initiator like di-t-butyl peroxide, as shown in Figure 7.13. The polymer
formed can then react with various functional groups like carboxyls, amines, phenols,
anhydrides, or epoxides from other polymers. This allows the formation of links between
polymers without producing gaseous by-products, as illustrated in Figure 7.14. This results in
intimate mixing of otherwise incompatible polymers, improving their blend properties.

Applications and Advantages

 Improved Properties in Polymer Blends

The blending of polymers like ABS (Acrylonitrile Butadiene Styrene) and PET
(Polyethylene Terephthalate) shows significant improvements in mechanical
properties when 2-oxazolines are used. For instance, the impact strength of
ABS/PET blends increased from 80.1 J/m to 170.8 J/m when 2-oxazoline was added,
and the tensile strength increased from 41.4 MPa to 55.6 MPa.
 Hydrolysis Resistance in Condensation Polymers
2-Oxazolines help cap terminal groups on condensation polymers like PET, protecting
them from hydrolysis, which can degrade their molecular structure over time.
 Chain Extension in Recycled Polymers
Bis-2-oxazolines, with molecular weights greater than 1000, are particularly useful
for chain extension in recycled condensation polymers. They can react with terminal
groups to help restore molecular weight, which can have been reduced during
degradation. This is especially useful for improving the properties of recycled
materials.

Summary

2-Oxazolines serve as multifunctional additives that enhance the properties of polymers by

facilitating the blending of incompatible materials, protecting against hydrolysis, and
improving the molecular weight of recycled polymers. They are particularly useful in
improving the stability and processability of polymers like PET and PBT.