Polymerisation

inhibitor

Polymerisation inhibitors (US: polymerization inhibitors) are chemical compounds added to

monomers to prevent their auto-polymerisation. Unsaturated monomers such as acrylates, vinyl
chloride, butadiene and styrene require inhibitors for both processing and safe transport and
storage. Many monomers are purified industrially by distillation, which can lead to thermally
initiated polymerisation. Styrene for example is distilled at temperatures above 100 °C
whereupon it undergoes thermal polymerisation at a rate of ~2% per hour.[1] This polymerisation
is undesirable, as it can foul the fractionating tower, it is also typically exothermic which can lead
to a runaway reaction and potential explosion if left unchecked. Once initiated polymerisation is
typically radical in mechanism and as such many polymerisation inhibitors act as radical
scavengers.

Inhibitors vs Retarders

The term 'inhibitor' is often used in a general sense to describe any compound used to prevent
unwanted polymerisation, however these compounds are often divided into 'retarders' and 'true
inhibitors'. A true inhibitor has a well defined induction period during which no noticeable
polymerisation takes place. They are consumed during this period and once gone
polymerisation occurs as normal. Retarders display no induction period but provide a permanent
decrease in the rate of polymerisation, while themselves being degraded only slowly. Attempts
have been made to define the difference quantitatively in terms of reaction rate.[2] In an industrial
setting compounds from both classes will usually be used together, with the true inhibitor
providing optimal plant performance and the retarder acting as a failsafe.

Inhibitors for processing

True inhibitors

Radical polymerisation of unsaturated monomers is generally propagated by C-radicals. These

can be effectively terminated by combining with other radicals to form neutral species and many
true inhibitors operate through this mechanism. In the simplest example oxygen can be used as
it exists naturally in its triplet state (i.e. it is a diradical). This is referred to as air inhibition and is
a diffusion-controlled reaction with rates typically in the order of 107–109 mol−1 s−1,[3] the
resulting peroxy radicals (ROO•) are less reactive towards polymerisation. However air
stabilisation is not suitable for monomers with which it can form explosive peroxides, such as
vinyl chloride. Other stable radicals include TEMPO and TEMPOL, which are exceedingly
effective radical scavengers. Certain compounds marketed as true inhibitors, such as p-
phenylenediamines, phenothiazine and hydroxylamines like HPHA and DEHA, are also thought to
react through the intermediary of aminoxyl radicals. Not all inhibitors are radicals however, with
quinones[4] and quinone methides[5] being important examples.

Retarders

Certain hydroxylamines[6] and p-phenylenediamines, may act as retarders. For styrene,

nitrophenol compounds such as dinitro-ortho-cresol and di-nitro-sec-butylphenol (DNBP) have
long been the important,[7] however they are coming under regulatory pressure due to their high
toxicity.

Inhibitors for transport & storage

Purified monomers stored at ambient temperatures are of less risk of polymerising and as such
the most highly reactive inhibitors are rarely used at this stage. In general compounds are
chosen which can be easily removed immediately prior to industrial polymerisation to make
plastics. Compounds bearing a hydroxy group, which can be removed by an alkali wash, tend to
dominate. Examples include 4-tert-butylcatechol (TBC), 4-methoxyphenol (MEHQ), butylated
hydroxytoluene (BHT) and hydroquinone (HQ).
See also

Anti-skinning agent - These agents prevent polymerisation in paints and varnishes by binding
to, and thus inhibiting, the action of oil drying agents

Tubulin polymerisation inhibitors - chemotherapy drugs that interfere with the tubulin system

References

1. Khuong, Kelli S.; Jones, Walter H.; Pryor, William A.; Houk, K. N. (February 2005). "The Mechanism of the
Self-Initiated Thermal Polymerization of Styrene. Theoretical Solution of a Classic Problem". Journal of
the American Chemical Society. 127 (4): 1265–1277. doi:10.1021/ja0448667 (https://doi.org/10.1021%2
Fja0448667) .

2. TUDOS, F; FOLDESBEREZSNICH, T (1989). "Free-radical polymerization: Inhibition and retardation".

Progress in Polymer Science. 14 (6): 717–761. doi:10.1016/0079-6700(89)90008-7 (https://doi.org/10.10
16%2F0079-6700%2889%2990008-7) .

3. Ingold, Keith U. (May 2002). "Peroxy radicals". Accounts of Chemical Research. 2 (1): 1–9.
doi:10.1021/ar50013a001 (https://doi.org/10.1021%2Far50013a001) .

4. Becker, H.; Vogel, H. (October 2006). "The Role of Hydroquinone Monomethyl Ether in the Stabilization of
Acrylic Acid". Chemical Engineering & Technology. 29 (10): 1227–1231. doi:10.1002/ceat.200500401 (htt
ps://doi.org/10.1002%2Fceat.200500401) .

5. Pospíšil, Jan; Nešpůrek, Stanislav; Zweifel, Hans (October 1996). "The role of quinone methides in
thermostabilization of hydrocarbon polymers —II. Properties and activity mechanisms". Polymer
Degradation and Stability. 54 (1): 15–21. doi:10.1016/0141-3910(96)00108-5 (https://doi.org/10.1016%2
F0141-3910%2896%2900108-5) .

6. Ohkatsu, Yasukazu; Baba, Rie; Watanabe, Keiji (2011). "Radical Scaveging Mechanism of Distearyl
Hydroxylamine Antioxidant" (https://doi.org/10.1627%2Fjpi.54.15) . Journal of the Japan Petroleum
Institute. 54 (1): 15–21. doi:10.1627/jpi.54.15 (https://doi.org/10.1627%2Fjpi.54.15) .

7. Jackson, R. A.; Waters, William A. (1960). "332. Properties and reactions of free alkyl radicals in solution.
Part XIII. Reactions with aromatic nitro-compounds". Journal of the Chemical Society (Resumed): 1653.
doi:10.1039/JR9600001653 (https://doi.org/10.1039%2FJR9600001653) .
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