I N T R O D U C T I O N T O P O LY M E R A D D I T I V E S A N D S TA B I L I Z AT I O N

Bobbijo van Beusichem, Ph.D., Senior Staff Scientist, Expert Services, Michael A. Ruberto, Ph.D., Head of Regulatory Services, NAFTA, Expert Services
Ciba Expert Services, Ciba Specialty Chemicals

Introduction Polymer Auto-oxidation Cycle Role of Additives Stabilizers (contd) Phenolic AO Oxidation Chemistry
Melt Processing
R-H O. O
Polymers are used in ALL aspects of our lives, including pharmaceutical packaging and
medical device preparation.
(Polymer) Energy
Catalyst Residues
Additives provide to Plastics: Most polyolefins contain one or more antioxidants
HO
O OH

+ RO + RO
at levels of 0.05 0.10% CH2 CH2 O CH2-]4-C

Oxygen Stabilization Primary antioxidants are generally radical

Irganox 1010
- ROH - ROH

Cycle II Cycle I scavengers or H-donors

R R H R*
R
To retain the original molecular architecture of the Quinonemethide
RO + OH ROO i.e. hindered phenols such as BHT, R R

Irganox 1010, or Irganox 1076

R polymer under the effect heat, light etc. HO C C OH
Coupling
+ Long-term protection for the polymer
ROOH
Path of R Alkyl radical
and Secondary antioxidants are typically O
P
O
+ 2 RO
- 2 ROH
Degradation RO Alkoxy radical hydroperoxide decomposers
Without the use of the proper stabilization package, polymers will degrade. Interaction
with oxygen and light can cause significant degradation of the polymer. These degradation
ROO
ROOH
Peroxy radical
Hydroperoxide Functionalization i.e. trivalent phosphorus compounds
O R R

such as Irgafos 168

O
O
products are potential leachables and extractables. C C

Often, blends of stabilizers will be used to protect the

polymer at various stages throughout the polymer lifecycle.
Auto-oxidation: Most labile hydrogens To provide additional attributes to the polymer which Process stabilization (protects the primary
AO against decomposition during processing)
Irgafos 168
add value for end use application. Stilbenquinone
An organophosphite, may be used as a short-term Polyamide: -CO-NH-CH2- {Bright Canary Yellow}
antioxidant to protect the polymer during the high
temperature and shear conditions of processing.
Polyester: -CO-O-CH2-
Chemistry of Phosphite
A phenolic antioxidant may then be used for long-term
protection. Polyacetal: -O-CH2-O- Extending Beyond Polymer Hydrolysis BHT Oxidation Chemistry
Additives may be incorporated into a product either
as neat material or as a concentrate or masterbatch.
A masterbatch is polymer resin containing a high
Unsaturated system: -CH=CH-CH2- Protection Some additives are designed to react and transform
For example, an active phosphite, such as Irgafos 168,
OH
[Oxid]
OH

[Oxid]
OH

concentration of the additive to be incorporated. Polypropylene/ -CH2-CH-CH2- can undergo hydrolysis:

Polyethylene O
The polymer resin may contain its own stabilization

=
R
package, which may or may not be different than the
Customer Product Properties Antimicrobials O H O OOH
Protection P(OR)3 + H2O (RO)2P-H + ROH
package used in the final product. (More potential Lit.: F. Gugumus in Plastics Additives, Gchter & Mller, Ed., 3rd Ed., Ch. 1 Antistats OH
leachables and extractables!) Colorants OH
O O Oxidative
Some additives are designed to transform during use.
Products of polymer degradation

=
=
Decarboxylation
An organophosphite, for example, will be oxidized to form the phosphate. UV Absorbers (RO)2P-H + H2O RO-P-OH + ROH
Polymer Properties

_
O OH
Anti-
Anti-fogging additives
In this case, BOTH the phosphite and phosphate are potential leachables and extractables. Alcyl radical ( R  ) (carbon centered free radical) Extension H
O
Polymer stabilization is a dynamic process resulting in ever- Optical Brighteners

=
changing transformation and degradation products
Active Peroxy radical (R-OO ) (oxygen centered radical ) Slip Agents - 4H
RO-P-OH + H2O H3PO3 + ROH
O
products:
Light Stabilizers O Diphenoquinone
all potential leachables and extractables.
Alkoxy radical (R-O  )

_
Intermediates Oxidative Coupling
of degradation
Additives can also provide special effects or properties to H
the polymer system. Hydroperoxide (R-OOH R-O  +  OH) Polymer Properties
Plasticizers
(hydroxy radical) Retention
Benzophenones or benzotriazoles can provide
UV protection to a polymer. Inactive
products:
Alcohol (R-OH)
Phenolic
AOs
Organophosphites Relative Discoloration Conclusions
Phenylglyoxylates can serve as photoinitiators in Aldehyde (R-C-H)
a UV curable coating.
Influence
organoleptics O Polymers stabilized with phenolic AOs can be susceptible to discoloration if the system
Ketone (R-C-R) Additives can provide additional properties or effects beyond stabilization. is abused Use of the proper stabilizer package can provide protection to the polymer.
Colorants dyes or pigments used to impart a particular color Modified O
to a polymer system. properties Polymer A combination of short-term and long-term stabilizers may be employed.
Calendered Polyolefin Sheet
Each of these compounds poses the potential for leachables and Primary and secondary antioxidants
extractables.
Polymer Stabilization Stabilizers Additives can also impart particular properties or effects to a polymer system

Degradation of Polyolefins
What are the differences between Additives, Good stabilization will reduce formation of aldehydes, ketones, and color bodies Colorants
Stabilizers, Modifiers and Fillers ?
Some stabilizers, which can terminate alkyl radicals, are especially effective Photoinitiators
Technical preparation of purest polymer is simply not possible! Additives are ingredients added to the polymer to stabilize, (vitamin E, lactone, hydroxyl amine)
Tape

Structural defects and impurities can not be excluded

modify or enhance its performance removed Antistats
Systems for gamma irradiation have been developed
Stabilizers are used to maintain the polymers strength, flexibility Antimicrobials
Organic materials undergo degradation in the presence of Oxygen.
Forming peroxides, alcohols, ketones, aldehydes, acids, peracids... and toughness; in other words, the attributes of the polymers Systems for reduction of organoleptics from slip agents are under development
Many additives will transform and/or degrade during use.
original molecular architecture
Oxidation is assisted by: Energy (e.g. mechanical stress, heat, light)
Auto-oxidation can be suppressed by the use of radical scavengers Outside of Polyolefin Sheet Roll Sample removed from sheet Each of these products must be taken into consideration when evaluating leachables
metals / -ions (catalyst residual, impurities, co-add.) Modifiers improve / alter the polymers performance; e.g., Slip (area where tape held roll together after unrolling a few loops and extractables.
Agents, Antistats, Antiblocks, Processing Aids, Fillers is visible)
Oxidation can affect mechanical properties Stabilization is a dynamic process
Discoloration, rougher surface, decreased tensile strength Fillers, such as SiO2, CaCO3, Talc, or TiO2 are used to improve BHT and Irganox 1076 undergo similar chemical
physical properties, or dilute the matrix with something less Transformation and degradation products must be considered along with the intact
Oxidation of hydrocarboncompounds proceeds autocatalytically expensive than the polymer itself transformations leading to chromophore chemistries. additives as potential leachables and extractables.
Poster prepared at www.SciFor.com