The
United Nations Recommendations on the Transport of Dangerous
Goods, Model Regulations, Rev.19 (2015) has a new requirement for
the determination of the SAPT (Self-Accelerating Polymerization Temperature)
for polymerizing substances. Accordingly, polymerizing substances
may be subject to temperature monitoring or temperature control depending
upon their SAPT and type of transportation packaging. The requirement
states the SAPT shall be determined in accordance with test procedures
established for SADT (Self Accelerating Decomposition Temperature)
for self-reactive substances. There are several SADT methods which
differ in their measurement techniques. Recent work has shown that
SADT results for materials with autocatalytic or autoaccelerated reactions
can differ significantly depending upon which SADT method was applied.
To ensure consistent SAPT values for safe transportation, several
industry consortia committees (Basic Acrylic Monomer Manufacturers,
European Basic Acrylate Manufacturers, and Methacrylate Producers
Association), of which Dow is a member, met in a joint session and
agreed to an intercompany effort to identify the best method on the
basis of good science, readily available technology, and flexibility
in packaging applications. This study highlights the technical approach
developed and validated at Dow for inhibited methyl methacrylate (MMA)
using isothermal micro calorimetry, modeling, simulations, and SADT
H1 testing. In this paper, several calorimetric methods were evaluated
and the corresponding kinetic equations describing the monomer polymerization
were established. Isothermal experiments performed in micro calorimeters
with a well-controlled temperature and high sensitivity were determined
as the best method for estimating the polymerization kinetics. The
studied monomer was methyl methacrylate, and the effect of inhibitor
concentration, headspace volume, and mixing during sample preparation
on PIT were carefully examined.