Polyoxymethylene

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Polyoxymethylene

Names
Other names
Poly(oxymethylene) glycol; Polymethylene glycol
Identifiers
CAS Registry Number

9002-81-7

ChemSpider
Properties
Chemical formula

(CH2O)n

Molar mass

Variable

Appearance

Colorless solid

Except where otherwise noted, data are given for materials in

their standard state (at 25 C [77 F], 100 kPa).
verify (what is:

/ ?)

Infobox references

Keck Clips made of polyoxymethylene

Polyoxymethylene (POM), also known as acetal,[1] polyacetal and polyformaldehyde, is an

engineering thermoplastic used in precision parts requiring high stiffness, low friction and excellent
dimensional stability. As with many other synthetic polymers, it is produced by different chemical
firms with slightly different formulas and sold variously by such names
as Delrin, Celcon, Ramtal,Duracon, Kepital and Hostaform.
Typical applications for injection-molded POM include high performance engineering components
such as small gear wheels, ball bearings, ski bindings, fasteners, knife handles, and lock systems.
The material is widely used in the automotive and consumer electronics industry.
Contents
[hide]

1Development

2Properties

3Production
o

3.1Fabrication

3.2Machining

3.3Bonding

4Usage

5Degradation

6See also

7References

8External links

Development[edit]

Polyoxymethylene was discovered by Hermann Staudinger, a German chemist who received the
1953 Nobel Prize in Chemistry. He had studied the polymerization and structure of POM in the
1920s while researching macromolecules, which he characterized as polymers. Due to problems
with thermal stability, POM was not commercialized at that time.
Around 1952 research chemists at DuPont synthesized a version of POM, and in 1956 the company
filed for patent protection of thehomopolymer. DuPont credits R. N. MacDonald as the inventor of
high molecular weight POM.[2] Patents by MacDonald and coworkers describe the preparation of high
molecular weight hemiacetal (~O-CH2OH) terminated POM,[3] but these lack sufficient thermal
stability to be commercially viable. The inventor of a heat-stable (and therefore useful) POM
homopolymer was Dal Nagore,[4] who discovered that reacting the hemiacetal ends with acetic
anhydride converts the readily depolymerizable hemiacetal into a thermally stable, melt processable
plastic.
DuPont completed construction of a plant to produce its own version of acetal resin,
named Delrin at Parkersburg, West Virginia, in 1960. Also in 1960, Celanese completed its own
research. Shortly thereafter, in a limited partnership with the Frankfurt firm Hoechst AG, a factory
was built in Kelsterbach, Hessen; from there, Celcon was produced starting in 1962,
with Hostaform joining it a year later. Both remain in production under the auspices of Celanese, and
are sold as parts of a product group now called Hostaform/Celcon POM.

Properties[edit]
POM is characterized by its high strength, hardness and rigidity to 40 C. POM is intrinsically
opaque white, due to its high crystalline composition, but it is available in all colors. POM has a
density of = 1.4101.420 g/cm.[5]
POM homopolymer is a semi-crystalline polymer (7585% crystalline) with a melting point of 175 C
(347 F). The POM copolymer has a slightly lower melting point of 162173 C.
POM is a tough material with a very low coefficient of friction. However, it is susceptible to polymer
degradation catalyzed by acids, which is why it is stabilized - both the homopolymer and the
copolymer have chain end groups (introduced via end capping) that resist depolymerization. With
the copolymer, the second unit is normally a C2 (ethylene glycol) or C4 (1,4-butanediol) unit, which
is introduced via its cyclic acetal (which can be made from the diol and formaldehyde) or cyclic ether
(e.g. ethylene oxide). These units resist chain cleavage, because the O-linkage is now no longer an
acetal group, but an ether linkage, which is stable to hydrolysis. POM is sensitive to oxidation, and
an anti-oxidant is normally added to molding grades of the material.
POM advantages:

High abrasion resistance

Low coefficient of friction

High heat resistance

Good electrical and dielectric properties

Low water absorption

Production[edit]

Different manufacturing processes are used to produce the homopolymer and copolymer versions of
POM.
Homopolymer
To make polyoxymethylene homopolymer, anhydrous formaldehyde must be generated. The
principal method is by reaction of the aqueous formaldehyde with an alcohol to create a hemiformal,
dehydration of the hemiformal/water mixture (either by extraction or vacuum distillation) and release
of the formaldehyde by heating the hemiformal. The formaldehyde is then polymerized by anionic
catalysis and the resulting polymer stabilized by reaction with acetic anhydride. Due to the
manufacturing process, large diameter cross sections may have pronounced centerline porosity.[6] A
typical example is DuPonts Delrin.
Copolymer
To make polyoxymethylene copolymer, formaldehyde is generally converted
to trioxane (specifically 1,3,5-trioxane, also known as trioxin). This is done by acid
catalysis (eithersulfuric acid or acidic ion exchange resins) followed by purification of the trioxane by
distillation and/or extraction to remove water and other active hydrogen containing impurities. Typical
copolymers are Hostaform from Celanese and Ultraform from BASF.
The co-monomer is typically dioxolane but ethylene oxide can also be used. Dioxolane is formed by
reaction of ethylene glycol with aqueous formaldehyde over an acid catalyst. Other diols can also be
used.
Trioxane and Dioxolane are polymerized using an acid catalyst, often boron trifluoride etherate,
BF3 OEt2. The polymerization can take place in a non-polar solvent (in which case the polymer forms
as a slurry) or in neat trioxane (e.g. in an extruder). After polymerization, the acidic catalyst must be
deactivated and the polymer stabilized by melt or solution hydrolysis to remove unstable end groups.
Stable polymer is melt compounded, adding thermal and oxidative stabilizers and optionally
lubricants and miscellaneous fillers.

Fabrication[edit]
POM is supplied in a granulated form and can be formed into the desired shape by applying heat
and pressure. The two most common forming methods employed are injection
molding and extrusion. Rotational molding and blow molding are also possible.
Typical applications for injection-molded POM include high performance engineering components
(e.g. gear wheels, ski bindings, yoyos, fasteners, lock systems) and the material is widely used in
the automotive and consumer electronics industry. There are special grades that offer higher
mechanical toughness, stiffness or low friction/ wear properties.
POM is commonly extruded as continuous lengths of round or rectangular section. These sections
can be cut to length and sold as bar or sheet stock for machining.

Machining[edit]
When supplied as extruded bar or sheet, POM may be machined using traditional methods such as
turning, milling, drilling etc. These techniques are best employed where production economics do not
merit the expense of melt processing. The material is free-cutting, but does require sharp tools with a
high clearance angle. The use of soluble cutting lubricant is not necessary, but is recommended.
POM sheets can be cut cleanly and accurately using an infrared laser, such as in a CO2 laser cutter.
Because the material lacks the rigidity of most metals, care should be taken to use light clamping
forces and sufficient support for the work piece.
Machined POM can be dimensionally unstable, especially with parts that have large variations in
wall thicknesses. It is recommended that such features be designed-out e.g. by adding fillets or

strengthening ribs. Annealing of pre-machined parts before final finishing is an alternative. A rule-ofthumb is that in general, small components machined in POM suffer from less warping.

Bonding[edit]
POM is typically very difficult to bond. Special processes and treatments have been developed to
improve bonding. Typically these processes involve surface etching, flame treatment or mechanical
abrasion.
Typical etching processes involve chromic acid at elevated temperatures. DuPont uses a patented
process for treating acetal homopolymer called satinizing that creates a surface roughness sufficient
for micromechanical interlocking. There are also processes involving oxygen plasma and corona
discharge.[7][8]
Once the surface is prepared, a number of adhesives can be used for bonding. These
include epoxies, polyurethanes, and cyanoacrylates. Epoxies have shown 150500 psi (1,000
3,400 kPa)[citation needed] shear strength on mechanically abraded surfaces and 5001,000 psi (3,400
6,900 kPa) on chemically treated surfaces. Cyanoacrylates are useful for bonding to metal, leather,
rubber and other plastics.
Solvent welding is typically unsuccessful on acetal polymers, due to the excellent solvent resistance
of acetal.
Thermal welding through various methods has been used successfully on both homopolymer and
copolymer.

Usage[edit]

Mechanical gears, sliding and guiding elements, housing parts, springs, chains, screws,
nuts, fan wheels, pump parts, valve bodies.

Electrical Engineering: insulators, bobbins, connectors, parts for electronic devices such
as televisions, telephones, etc.

Vehicle: Fuel sender unit, Light stock (including shifter for light, turn signal), power windows,
door lock systems, articulated shells.

Model: Model Railway parts, such as trucks (bogies) and hand rails (handle bars). POM is
tougher than ABS, comes in bright translucent colors, and is not paintable.

Hobbies: Radio-controlled helicopter Main gear, landing skid, yo-yos, vaping drip tips, etc.

Medical: insulin pen, Metered dose inhalers (MDI), dental veneers, dental removable denture
(snap on smile)

Food industry: Food and Drug Administration has approved some grades of POM for milk
pumps, coffee spigots, filter housings and food conveyors.[9]

Furniture: hardware, locks, handles, hinges.

Construction: Structural Glass - pod holder for point

Packaging: aerosol cans, vehicle tanks.

Sports: Paintball accessories. It is often used for machined parts of paintball markers that do
not require the strength of aluminum, such as handles and reciprocating bolts. POM is also used
in airsoft guns to reduce piston noise.

Longboarding: Puck material for slide gloves help the rider touch the road and lean on their
hand to slow down, stop, or perform tricks.

Clothing: zippers.
Music: picks, Irish flutes, Bagpipes, Practice chanters, harpsichord plectra, tuba
mouthpieces, tips of some drum sticks.[10]

Dining: Fully automatic coffee brewers; knife handles (particularly folding knives)

Horology: Watch bracelets (e.g. IWC Porsche Design 3701)

Electronic Cigarettes (e.g. Drip Tips)

Degradation[edit]

chlorine attack of acetal resin plumbing joint

Acetal resins are sensitive to acid hydrolysis and oxidation by agents such as mineral acids
and chlorine. POM homopolymer is also susceptible to alkaline attack and is more susceptible to
degradation in hot water. Thus low levels of chlorine in potable water supplies (13 ppm) can be
sufficient to cause stress corrosion cracking, a problem experienced in both the USA and Europe in
domestic and commercial water supply systems. Defective mouldings are most sensitive to cracking,
but normal mouldings can succumb if the water is hot. Both POM homopolymer and copolymer are
stabilized to mitigate these types of degradation.
Widespread failure of acetal mouldings in potable and hot water supplies resulted in one of the
largest class actions in the USA when acetalplumbing fittings cracked and caused flooding of homes,
a problem exacerbated by similar problems with polybutylene pipework. The acetal fittings tended to
fail first, followed by the pipework.[citation needed]
In chemistry applications, whilst the polymer is often suitable for the majority of glassware work, it
can succumb to catastrophic failure. An example of this would be using the polymer clips on hot
areas of the glassware (such as a flask to column, column to head or head to condenser joint during
distillation). As the polymer is sensitive to both chlorine and acid hydrolysis, it may perform very
poorly when exposed to the reactive gases, particularly hydrogen chloride. Failures in this latter
instance can occur with seemingly unimportant exposures from well sealed joints, and do so without

warning and rapidly (the component will split or fall apart). This can be a significant health hazard as
the glass may open or smash. Here, PTFE or a high grade stainless steel may be a more
appropriate choice.