Acetal Resins- Production, Processing and

Application
PE-1406 PLASTICS MATERIALS

BY: Athira Mohan & Arjun Satheesh

 Introduction
❖ Acetal resins are the family of polymers derived primarily from
formaldehyde. Polyoxymethylene; Hermann Staudinger, 1953 Nobel
Prize.
❖ The homopolymers are completely characterized by the (CH2—O)n
repeat unit and the name polyoxymethylene (POM) is more structurally
descriptive
❖ Acetal copolymers have the oxymethylene structure occasionally
interrupted by the comonomer unit.
❖ POM (a.k.a acetal, polyacetal, and polyformaldehyde), is an
engineering thermoplastic used in precision parts requiring high
stiffness, low friction, and excellent dimensional stability.
❖ It is marketed under names as Delrin, Celcon, Ramtal, Duracon,
Kepital, and Hostaform.
Homopolymers Copolymers
❖ The principal method is by ❖ Substitution of about 1–1.5% of
reaction of the aqueous the –CH2O– groups with –
formaldehyde with an alcohol to CH2CH2O–.
create a hemiformal, followed by
❖ Formaldehyde is generally
extraction or vacuum distillation
converted to trioxane. This is
of mixture and release of the
done by acid catalysis followed
formaldehyde by heating the
by distillation and/or extraction
hemiformal.
to remove water and other
❖ The formaldehyde is then active hydrogen containing
polymerized by anionic catalysis impurities
and the resulting polymer
❖ Eg: Hostaform, Ultraform
stabilized by reaction with acetic
anhydride.
❖ Eg: Delrin
Polymerization of Formaldehyde Trace of sulphuric
acid acting on hot
formaldehyde
vapor

Evaporation of
aqueous solutions
of formaldehyde
Evaporation of In the presence of
methanol solution lime water
Manufacture of Acetal
Resins
Homopolymer Acetal Resins
 Typically produced from an alkali-precipitated low molecular weight
polyformaldehyde which has been carefully washed with distilled
water and dried for several hours under vacuum at about 80°C.
 The dried polymer is then pyrolyzed by heating at 150-160°C, and the
resultant formaldehyde passed through a number of cold traps at -
15°C.
 Monomer is then introduced into the polymerization vessel over a
rapidly stirred and carefully dried inert medium such as heptane,
containing the required initiators and stabilizers.
 Lewis acids, amines, phosphines, arsines and stibines; typically used is
triphenylphosphine at 20ppm.
 Typically used stabilizer include diphenylamine at a concentration of
100 ppm.
 Polymerization is carried out until a 20% solids content is obtained.
 The polymer is then isolated by filtration, washed in turn with
heptane and pure acetone and then dried in a vacuum oven at
80°C.
 Control of molecular weight may be made by adding traces of water,
which is an effective chain transfer agent.
 However, it was shown that the diacetates of low molecular weight
polyoxymethylenes (I) (polyformaldehydes) were more stable than
the simple polyoxymethylene glycols (II)
 Esterification reaction is carried out with acetic anhydride. The
reaction is catalyzed by amines and the soluble salts of the alkali
metals. Reaction temperatures may be in the range of 130-200°C.
 Esterification at 139°C, the boiling point of acetic anhydride, in the
presence of 0.01% sodium acetate catalyst is found to complete
within 5 minutes. In the absence of such a catalyst the percentage
esterification is of the order of only 35% after 15 minutes.
 Copolymer Acetal Resins
 An alternative approach to the production of thermally stable
polyoxymethylenes, was made by the Celanese Corporation.
 Copolymerization of trioxane with cyclic ethers or formals is
accomplished with cationic initiators (Boron trifluoride dibutyl
etherate); ethylene oxide (II) and 1.3-dioxolane (III).
 Molten trioxane, initiator, and comonomer fed to the reactor; a chain-
transfer agent included if desired. Polymerization proceeds in bulk
with precipitation of polymer and the reactor must supply enough
shearing to continually break up the polymer bed, reduce particle
size, and provide good heat transfer.
 Raw copolymer is obtained as fine crumb or flake containing imbibed
formaldehyde and trioxane which are substantially removed in
subsequent treatments which may be combined with removal of
unstable end groups.
Factors affecting stability of
copolymer polyacetal
 It is to be noted that there appear to be four
processes which lead to degradation of
polyacetals
 Stepwise thermal- or base-catalyzed hydrolytic
depolymerization initiated from the hemi-formal chain
end with the evolution of formaldehyde.
 Oxidative attack at random along the chain leading to
chain scission and subsequent depolymerization.
Factors affecting stability of
copolymer polyacetal
 Acid-catalyzedcleavage of the acetal linkage. Traces of
acid may arise as residues from polymerization and
end-capping stages and through oxidation of
formaldehyde to formic acid.
 Thermal depolymerization through scission of C-0
bonds can occur catastrophically above 270°C and care
must be taken not to exceed this temperature during
processing.
Properties Of Polyacetals
 Shorter backbone of –-C—O bond and close packing imparts high
stiffness and a higher M.P.
 Good staining resistance.
 Low coefficient of friction.
 Resistance to inorganic reagents is not very good & they should
not be used in strong acids, strong alkalis or oxidizing agents.
 Acetal homopolymer resins show outstanding resistance to
organic solvents, (below 70°C). Above this temperature some
phenolic materials are effective.
Properties Of Polyacetals
 Prolonged exposure to ultraviolet light induces surface
chalking reducing molecular weight, resulting in gradual
embrittlement.
 The copolymer has better thermal stability, better hydrolytic
stability at elevated temperatures, easier moulding and
better alkali resistance. The homopolymer has slightly better
mechanical properties, e.g. higher tensile strength, higher
flexural modulus and greater surface hardness.
Processing
 Overheating leads to the production of HCHO gas and if this is
produced within the confines of an injection cylinder or extruder
barrel the gas pressure may become sufficiently high that there is a
risk of damage or injury.
 Although less hygroscopic than the nylons, acetal resins must be
stored in a dry place.
 Apparent viscosity is less dependent on temperature and shear stress,
simplifying die design.
 Low melt strength, blow moulding problems; extensive drawing down
of the parison under gravity. To overcome these problems copolymers
have become available with slightly branched molecules which have a
greater melt elasticity and tenacity.
 Processing
 Low glass transition temperature; crystallizes rapidly at room
temperatures and after-shrinkage is usually complete within 48 hours
of moulding or extrusion. In processing operations injection moulds,
blow moulds and sizing dies should be kept at about 80-120°C in order
to obtain the best results.
 Because of the low glass transition temperature it is not possible to
make clear film, stable at room temperature
 Applications
 Due to light weight, mouldability into intricate shapes in one piece,
low coefficients of friction etc. acetal resins find use as bearings.
 Plumbing components such as valve stems and shower heads.
 conveyor belts, molded sprockets and chains, blower wheels, cams,
fan blades, check valves, pump impellers, carburetor bodies, blow-
moulded aerosol containers.
 Acetal resins application as gears, competing with nylons. Acetal gears
are superior to those made from nylon in fatigue resistance,
dimensional stability and stiffness.
 References
 http://onlinelibrary.wiley.com/doi/10.1002/0471440264.pst001/
 http://www.dupont.co.in/products-and-services/plastics-polymers-
resins/thermoplastics/brands/delrin-acetal-resin.html
 https://en.wikipedia.org/wiki/Polyoxymethylene
 “PLASTICS MATERIALS” Seventh Edition- J.A Brydson, Butterworth-
Heinemann Publication
 “Kirk-Othmer Encyclopedia of Chemical Technology”- Jacqueline I.
Kroschwitz, John Wiley & Sons Inc