ANTI-OXIDANTS

PRASHANT SONI
12 OIL 1005

INTRODUCTION
Industrial lubricants have to prevent damage to the machinery which arises

from friction between moving parts in service.

Oxidation stability is one of the key requirements of the lubricant because

the oxidation degradation products, e.g. peroxy radicals, hydroperoxides

and organic acids as well as sludge and deposits, are detrimental to the
equipment.

The important role of antioxidants, to protect the various types of base oil

under different operation conditions.

OXIDATION PROCESS

 use of additives to control lubricant degradation requires a focus on alkyl

radicals

(R), alkylperoxy radicals (ROO) and hydroperoxides (ROOH).

three additive types have proven to be successful in controlling the

degradation of lubricating oils:

1.

radical scavengers,

2.

hydroperoxide decomposers,

3.

synergistic mixtures of these.

RADICAL SCAVENGERS
phenolic and aminic antioxidants most widely used types of radical

scavengers

use of organometallic complexes of transition metals as antioxidants is

becoming more prevalent, especially in engine oils; organomolybdenum

compounds are of particular importance.

1.) Sterically hindered phenols: Phenols substituted at the 2- and 6-positions

by tertiary alkyl groups are called sterically hindered phenols, the most
common substituent is the tertiary butyl group.
For e.g. 2,6-di-tertiary-butyl-p-cresol is used as a additive in turbine

lubricating oil

2.) Aromatic amines: Secondary aromatic amines are another important

class of antioxidants used in lubricants.
The principal substituents of the nitrogen atom are either two aryl or one

phenyl and a naphthyl group.

For e.g. diphenylamine, -naphthylamines,

under high-temperature conditions, aromatic amines are far superior to

their phenolic counterparts

 Organometallic complexes of transition metals:

since transition metals can exist in more than one oxidation state, which

gives them catalytic activity to inhibit autoxidation and stabilisation of

hydrocarbons such as mineral oil
For e.g. organo opper compounds used in engine oils are capable of

catalytically scavenging free radicals.

HYDROPEROXIDE
DECOMPOSERS
These compounds convert hydroperoxides into non-radical products,

thereby preventing the chain propagation reaction.

organosulphur and organophosphorus additives have been used for this

purpose.

The reaction mechanism to eliminate hydroperoxides is their acid-catalysed

decomposition.

The catalysts are protic (RSO2H) or Lewis acids (SO2).

 Zinc dialkyldithiocarbamates: These compounds are mainly used as

antioxidants although, like the ZnDTPs, they also have extreme pressure
activity.

Organophosphorus compounds: Phosphites are the main

organophosphorus compounds used to control oxidative degradation of

lubricants

SYNERGISM BETWEEN
ANTIOXIDANTS
effectiveness of one class of antioxidant may be enhanced by combining it

with another type of stabilizer

combining two different peroxy radical scavengers in a lubricant gives

improved oxidation stability compared with either alone

The aminic antioxidant reacts faster than the phenolic antioxidant with the

peroxy radical. The less efficient sterically hindered phenol then regenerates
the more effective aminic antioxidant. For eg, using a synergistic
combination of an aminic antioxidant and an organosulphur hydroperoxide
decomposer

Working: organosulphur compound decomposes the majority of

hydroperoxides. Fewer radicals which initiate chain reactions are formed, and
therefore less aminic antioxidant is consumed by the peroxy radical
scavenging process.

COMMERCIAL
ANTIOXIDANTS
Product

Company

Chemical

Additin 7115

Rhein Chemie

phenol derivative sterically

hindered

Hitec 4703

Ethyl

2,6-di-t-butyl-alphadimethylamino-pcresol

Irganox L 57

Ciba

butylated, octylated
diphenylamine

Naugard PANA

Crompton

phenyl-alpha-napthylamine

Vanlube 849 RT

Vanderbilt

alpha methyl styrenated

DPA

 Chemistry and Technology of Lubricants By R. M. Mortier, S. T. Orszulik

Lubricants and Special Fluids By V. Stepina, V. Vesely
Developments in Lubricant Technology By S. P. Srivastava