Instructor: Prof. Ram Nagarajan

Sustainable Additives?
 Polymers are almost never used in their pure form. Additives

improve balance of properties
 Plastics industry as a whole uses about 18% of additives by
weight - $40 billion market! Growing at ~ 4% annually
 Goal of this lecture: review the present use of renewable raw
materials and consider the possibility of increasing the portion
based on renewable raw materials.
Instructor: Prof. Ram Nagarajan

Propagation of Degradation: Cascading cycle
2
Role of Antioxidants
 Antioxidants do not completely eliminate oxidative degradation, but they
substantially inhibit the rate of auto oxidation by interfering with the radical
propagation reaction. Two categories of antioxidants/antiozonants are common
 Chemical protectants
 Physical protectants
 For chemical protectants, in order to inhibit the degradation cycle (cascading

effect) the antioxidants function as follows :
 a) Scavenge the free radicals before they have opportunity to grow in numbers
rapidly
 b) Reduce the peroxides & hydroperoxides to alcohols before they produce
additional radicals.
 Secondary Aryl Amines, Diamines as well as sterically hindered Phenolic
antioxidants act by donating their reactive hydrogen atom to the free radicals

Role of Antioxidants (continued)
 The Antioxidants are categorized as :

 A) Primary Antioxidants (Chain Terminating) e.g. Amines &.
 B) Secondary Antioxidants (Peroxide Decomposers) e.g. Phosphites &
Thioesters
Antioxidants and Antiozonants

Phenolic Antioxidants

Thioesters and aromatic Phosphites

Stabilizers (Antioxidants & Antiozonants)
 Antioxidants and antiozonants are primarily

 Aromatic Phenols (available in nature) – chemical derivatization possible
 Aromatic Amines – not available in nature
 Secondary antioxidants – Dilauryl and distearyl

thiodipropionates are secondary antioxidants and can be
made from C12 and C18 triglycerides
 Phosphate types – primary aromatic, difficult to synthesize

from renewable raw materials

Thermal Stabilizers
 Organotin compounds – strongest but most of the metal
based stabilizers are toxic

Acid Scavengers and Heat Stabilizers
 Acid Scavengers are often calcium and zinc stearates, which are
generally made from natural glyceryl stearate
 PVC heat stabilizers
 Organic salts of Ba, Ca, Zn and Sn
 Anions may be aromatic or aliphatic, depending on solubility and lubricity
requirements
 Aliphatics can be made from natural oils
 Epoxidized soybean oil is an important secondary stabilizer to synergize
the Ba, Ca, Zn salts
 Epoxidized linseed oil is better, but more expensive
 Epoxidized tall oils are also used
 Organic phosphate synergists are also important, but very secretive
 The aliphatic phosphates could be made from natural oils, aromatic
phosphates are more difficult to obtain from natural resources

UV Stabilizers, Biostats and Biocides
 Mostly aromatic and alicyclic compounds

 Difficult to synthesize, especially from natural raw materials
 Plastics waste which will ‘self-destruct’ can be catalyzed by
ferrous laurate, which is made from natural oils. Although
becoming more popular the degradation process is questionable
and the metal impurity left behind is detrimental
 Biostats and biocides are mostly aromatic compounds including
toxic metals or organic groups, and would be difficult to make
from natural materials

Fillers
 Inorganic compounds – some abundantly available; Carbon based filled are still
obtained from crude but can be produced from biobased feedstock
 Particulate Fillers
 Calcium carbonate is by far the most abundant and widely-used
 Alumina Trihydrate is used as a low-cost filler and flame retardant
 Clay is second most-widely used
 Nanoclays provide a combination of reinforcement, barrier and transparency
properties, so they are becoming popular
 Wollastonite and talc are widely available at low cost and offer some
reinforcement and barrier properties
 Wood flour (truly renewable) is of growing interest for wood/plastics composites
 Quartz, silica are abundantly available
 Carbon black is made by thermal decomposition of petroleum and is universally
used for reinforcement of rubber. Although known has organic filler – the organic
entity is ‘baked out’ of it

Plasticizers
 Organic liquids that are miscible with polymers and are used to increase melt flow
and/or softness, flexibility, extensibility, adhesion, transparency and permeability
 They are used mainly in PVC, cellulosics – polarity, hydrogen bonding and hence
solubility parameter determines compatibility
 Mainly alkyl esters of phthalic acid – but toxicity is driving a shift away from
phtalates
 Phthalic acids are made from crude oil or coal
 Alkyl alcohols can be made from vegetable oils
 Length of alkyl group determines properties
 Epoxidized soybean (ESO) oil is used as a secondary heat stabilizer and plasticizer
in PVC
 ESO adipates, citrates and glycollates are made from vegetable oils and are non-
toxic
 Rubber is usually plasticized using petroleum oils
Other Commercially available alternatives
 Adipates - expensive, secondary plasticisers
 Benzoates - mixtures
 Citrates - expensive
 Specialties (ESO, polyesters)- expensive, secondary plasticisers
 Plasticizers based on sorbitol or isosorbide:

OH OH O O O
HO Performance
OH - excellent
+ 2 HO R R O
R + 4 H2O
catalyst O
OH OH O
 Raw materials: sorbitol, prepared by reduction Oof starch: cheap and abundant
Lubricants
 Cover a range of specific functions during manufacture and use of plastic
products
 They decrease friction, viscosity and adhesion during processing and of finished
goods. They are practically miscible in the polymer, but tend to exude to the
surface during processing and/or in the finished product
 The degree of partial miscibility is controlled by the difference in polarity
between the polymer and the surface in contact with it.
 Aliphatic chains produce low polarity, aromatic groups somewhat higher, ethers,
esters, amides and acids increasingly higher. Strong ionic groups give higher
polarity
 Most lubricants use alkyl groups based on vegetable oils: Fatty amides: Oleic,
ethylene-bis-stearamide, metal stearates Ca, Zn, Mg
 Ester waxes, Fatty alcohols, Fatty acids
 Lubricants not based on veg. oils include paraffin and PE waxes, fluoropolymers,
silicones and some inorganic powders Instructor: Prof. Ram Nagarajan
Flame Retardants (please read book Chapter)
 Organic phosphorus very effective. Does not cause problems of smoke or

corrosion. Expensive and the process used to produce involves toxics
 Phenolics are being explored as well
 Clays and inorganic fillers
 Antimony oxides are fairly scarce and expensive. Used mainly as a
powerful synergist for halogenated FR. Again worries about smoke, toxicity
and corrosion are of concern. All made from non-renewables
 ATH and Magnesium compounds occur in nature and available in good
supply. Some of them have large water of hydration. However they have to
be used in large quantities for being effective as FR. Mechanical properties
are adversely affected!

Antistats
 Polymers are electrical insulators, so when they develop a static charge,
it does not bleed off to ground
 This causes problems in processing, collection of dust, unsightly
packaging, cling and discomfort of clothing and upholstery, shock, dust
explosion, ‘noise’ in sound recording, damage to electronics, EMI

Antistats
 Resistivity of 1010-14 Ohm cm is enough to solve minor problems; 102-10 Ohm Cm
solves many intermediate problems. 10-2 to 102 prevents EMI. Resistance lower
than that – semiconducting polymers
 Conductive Fillers such as metals and elemental carbon, and highly conjugated
polymers can give high conductivity, but they require particle-to-particle contact and
involve difficult processing
 For many plastic products, moderate antistatic conductivity is achieved by adding
polar organic compounds
 These must be semi-miscible, so that they migrate gradually to the surface of the
product to produce surface conductivity during the use of the product
 For different polymer and product lifetimes, the degree of semi-miscibility is
adjusted by the balance of polar and non-polar groups in the additive
 Generally, aliphatic hydrocarbon chains, derivable from vegetable oils, provide the
low-polarity groups, and ethers, esters, amines and amides, provide the polar groups

Antistats Continued
 Quaternary ammonium compounds are the strongest but suffer from
instability and toxicity problems
 Ethoxylated amines are almost as strong and suffer from similar problems
 Ethoxylated fatty esters and ethers are less efficient, but have better stability
and are non-toxic
 Glycerol mono-and di-esters are derived from vegetable oils can function as
antistats
General Considerations:
End of life – integration with the disposal environment and/or recycling
Ensure non-accumulation of toxics when disposed
Cost versus sustainability balance

Instructor: Prof. Ram Nagarajan

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Sustainable Additives?

 Polymers are almost never used in their pure form. Additives