Preparation of Polyacetal

Acetal polymers are properly called polyoxymethylene

(POM). This resin is linear unbranched molecular chains derived from
the monomer formal dehyde (anhydrous). The acetal homopolymer is
manufactured by polymerization of formal dehyde, where as its
copolymers is made trioxane, the cyclic trimer of formal dehyde.

HO-(CH2 –0)n – H Linear polymer

nCH2 0
CH3 0 – (CH2 0) n - H High molecular Wt.
polymer
 Manufacturing of Polyacetal

In order to manufacture polyacetal it is first necessary to

produce a very pure form of formaldehyde. This is typically produced
from an alkaline 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
pyrolysed by heating at 150-160°C, and the resultant formal dehyde
passed through a number of cold traps (typically four) at – 15°C.

Some polymerization occur in these traps and undesirable

impurities from the monomer is removed.
 Manufacturing of Polyacetal
•The monomer is then introduced into the polymerization vessel over a rapidly
stirred and carefully dried inert medium such as heptane. A number of
polymerization initiators have been cited in the literature and include Lewis
acids, a mines, phosphines, arsines and stibines.

•A typical initiator is triphenyl phosphine used to the extent of 20 ppm based

on the inert medium. A polymer stabilizer such as diphenylamine may also be
present to a concentration of 100 ppm. Polymerization is carried out untill a
20% solid content is obtained.

•The polymer is then isolated by filtration washed in turn with heptane and
pure acetone and then dried in a vacuum over at 80°C. Control of molecular
weight may be made by adding traces of water which is an effective chain
transfer agent.

•It is because of this particular property of water that it is necessary to work

under conditions where the water content is carefully controlled.
 Manufacturing of Polyacetal

In addition to the above method the resin can be also manufactured by other
methods.

The purified polymer is end capped by acetylating the hydronyl end groups. End
capped polymer is purified by removing excess acetate and end – capping agents dried
and blended with additives.

Acetal copolymer is also produced by a similar procedure. The molecular chains of

polyacetal consists primarily carbon-oxygen bond in the form oxy methylene groups.

-CH2-0-CH2-O-CH2-0-CH2 HOMOPOLYMER

-CH2-O- CH2-CH2-O-CH2 COPOLYMER

The copolymer is prepared by the co-polymerization of trioxane with small amounts of

a comonomer which randomly distributes carbon-carbon bonds in the form of
oxyethylene group in the polymer chain.
 Properties of Polyacetals

The acetal polymer molecules have a shorter backbone (-C-O-)

bond and they pack more closely together than those of PE. The
resultant polymer is thus harder and has a higher melting point (175°C)
for homopolymer. The acetal polymers exhibit a high crystallinity. The
percentage crystallinity will depend on the quench temperature and will
range from about 77% , when quenched at 0°C, to about 80% when
quenched at 160°C. Annealing increases the crystallinity, this being
most marked at 150°C. The greater the percentage crystallinity the
higher the yeild point and tensile modulus. It has also been shown that
by raising the quench temperature the spherulite size is increased and
that this greatly decreases the impact toughness.
 Properties of Polyacetals

The principal features of acetal resins leading to commercial

application may be summarized as follows.
.Stiffness
.Fatigue endurance
.Resistance to creep
.Low co-efficient of friction
.Good appearance
 Properties of Polyacetals

Although in many respects acetal resins are similar to the nylons,

they may be considered to be superior to them in their fatigue
endurance, creep resistance stiffness and water resistance. The
nylons (except under dry conditions) are superior in impact
resistance and abrasion resistance.
 Properties of Polyacetals

Properties Units Values

Homopolymer Copolymer
Specific gravity ---- 1.42 1.41
Tensile strength MPa 69 61
Tensile modulus MPa 3100 2829
Flexural modulus Mpa 2620-2960 2588
Elongation at break % 27-75 40-75
Impact strength izod, Notched, J/m 69-123 53-80
Hardness M92-94 M78-80
Deflection temperature under load 0
C 136 110
(1.82 Mpa)
Vicat softening temperature 0
C 185 167
Coefficient of linear expansion mm/mm/0C 10-15 x 10-5 8.5 x 10-5
Water absorption, 24hrs % 0.25-0.32 0.22
Dielectric strength KV/mm 20 20
Dielectric constant 10-6 Hz 3.7 3.7
Power factor 0.005 0.006
Volume resistivity Ohm.m 10-13 - 10-14 -
Melting point 0
C 175 165
 Properties of Polyacetals

Greater thermal stability and chemical resistance of co-

polymer is obtained at some small sacrifice in short term
mechanical properties. Since the introduction of the oxyethylene
units into the molecular chain lower the crystallinity slightly, the
copolymer is about 10% lower in properties such as stiffness and
tensile strength, which are dependant upon crystallinity.

Under certain conditions of mechanical loading the

copolymers have the ability to absorbs more energy than the
homopolymer
 Properties of Polyacetals

•Most of the properties are dependant upon crystallinity, which is

somewhat lower in the copolymer than in the homopolymer. The
copolymer has greater elongation than homopolymer.

•Over broad ranges of loading conditions, the acetal homopolymer

and copolymer both have excellent resistance to creep. Nearly
equivalent performance at room temperature, but at elevated
temperature the copolymers has a decided advantage.

•Because of high crystallinity the acetals have exceptional resistance

to tensile and flexural fatigue stress. The ability to resist fatigue from
repeated loading is of great importance in the design of items such as
gears, hinges and reciprocating mechanical parts.
 Properties of Polyacetals

Acetals have a heat distortion temperature in

excess of 110°C and can be used in applications upto
this temperature intermittently. However, acetal can
loose strength and toughness after long exposure to hot
environments. Homopolymers resist deterioration upto
one and a half years at 82°C in air while the
copolymers may be used continuously at temperature
upto 104°C in air.
Mouldings of acetal remain dimensionally
stable over the recommended use temperature range.
 Properties of Polyacetals

The electrical insulation properties of the acetal resins

may be described as good but not particularly outstanding.
However, application where impact toughness and rigidity are
required along with good electrical insulation characteristics they
be used.

Both the homopolymer and copolymer of polyacetal have

excellent resistance to many organic chemicals, which cause other
plastics to fail rapidly. Both the homopolymer and copolymer are
attacked by strong acids and oxidizing agents and the physical
properties are affected by phenol and aniline at elevated
temperature over prolonged periods of exposure.
 Properties of Polyacetals

Due to the difference in chemical structure between the

homopolymer and copolymer, the copolymer is hardly affected by long
term exposure to strong bases such as sodium hydroxide and aluminium
hydroxide even at elevated temperature.

The homopolymer suffers severe attack in a relatively short

time in this reagent.

Acetal resins are affected by ultraviolet light. When exposed to

sunlight, natural acetal becomes dull in appearance and a chalk form on
the surface, in time, the material looses much of its tensile strength and
it becomes embrittled. This deterioration of polymer is retarded when
UV- stabilizer is used in their formulation. The detailed characteristics
of polyacetal is summarized below:
 Characteristics of Polyacetals
•Good appearance
•Homopolymer is resistant to mid acids and bases
•Good electrical properties but affected by moisture
•Stiff and rigid
•Good toughness
•Notch sensitive
•Excellent fatigue resistance under repeated load
•Excellent creep resistance under continuous load
•Low coefficient of friction
•Good abrasion resistance
•Maintains the mechanical, chemical and electrical properties over broad temperature range and time
•High resistance to thermal and oxidative degradation
•Very good resistance to stress relaxation
•Excellent dimensional stability
•Good processability
•Copolymers have better thermal stability
•Burn slowly without smoke generation
•Susceptible to UV degradation
•Attacked by phenol and aniline
•Difficult to electroplate
•Degradation at high processing temperature and liberate formaldehyde
 Processing of Polyacetals

The polyacetals are available in the following grades.

•Improved processability grade.

•Low areas/low foliation grade.
•Glass filled grade
•Mineral filled grade
•UV-Stabilized grade
 Processing of Polyacetals

Polyacetal resin may be processed by injection moulding,

extrusion, injection & extrusion blow moulding and rotational blow
moulding techniques.

Injection moulding conditions required for the acetal

homopolymers and copolymers resins are very similar with the exception
on melt temperatures. Due to its higher melting point (175°C vs 165°C for
the copolymer) and its slightly different flow characteristics, the
homopolymer is generally moulded at melt temperature 6-10°C higher than
the copolymer.
 Processing of Polyacetals

The homopolymer is moulded at melt temperature of

205-215°C while the copolymer would be moulded at melt
temperature of 190-205°C.

A mould temperature of 93°C is recommended for most

acetal mouldings, but mould temperature as high as 107-
110°C are some times used to obtain optimum surface
appearance particularly with the glass fibre reinforced
grades.
 Processing of Polyacetals

While processing poly acetal following precautions to be taken.

.Stepwise thermal or based catalyzed hydrolytic

depolymerization initiated from the hemiformal chain end with
the evolution of formaldehyde.

.Oxidative attack at random along the chain leading to chain

scission and subsequent depolymerization.

.Acid catalysed cleavage of the acteal linkages.

.Thermal depolymerization through scission of C-O bonds can

occur catastrophically above 270°C and care must be taken not
to exceed this temperature during processing.
 Processing of Polyacetals

The 1st step is minimized by end capping and co-polymerization

mechanism of polyacetal during manufacturing.

The 2nd step is minimized by adding antioxidants during manufacturing

steps.

The third step can be eliminated by adding acid acceptors, which are
nitrogen-containing compound and this material is not at all processed in
machine which is used for PVC. However, with proper cleaning it can
be used.
 Serviceability of acetal plastics

Superior properties of highly crystalline acetal in term of

strength, stiffness and toughness makes it an engineering
thermoplastic. It is more dense than nylon but in many respects their
properties are similar and they can be used for the same types of light
engineering applications. In some cases a factor that may favour acetal
is its relatively low water absorption. Acetal homopolymer and
copolymer grades offer features to the designer that have made them
prime contenders for applications based on metal, primarily die-cast
metals.
 Serviceability of acetal plastics

Properties includes good fatigue life exceptional dimensional

stability resiliency, and toughness, good tensile strength and creep
resistance under a wide range of temperature and humidity conditions,
solvent resistance excellent electrical properties etc. Abrasion
resistance is also generally superior to most thermoplastics. Its
coefficient of friction on steel is very low. Its low dissipation factor
and dielectric constant are maintained over a wide range of frequencies
and upto temperature of 121°C. The acetals are available in various
colors.
 Acetal homopolymers

Acetal homopolymers modified deliver upto seven times

greater than unmodified in izod impact tests and upto 30 times greater
toughness as measured by gardner impact testing technique. The
general purpose types can be used over a wide range of environmental
conditions.
 Acetal homopolymers

Special UV- stabilized grades are used when requiring long-

term exposure to weathering. Prolonged exposure to strong acids and
bases outside the range of PH 4 to 9 is not recommended.
Homopolymer have the highest fatigue endurance of any unfilled the
thermoplastics. Under complete reversed tensile and comprehensive
stress and with 100% relative humidity at 22.8°C, fatigue endurance
limit is 31 Gpa at 106 cycles. Resistance to creep is excellent. Moisture,
lubricants, and solvents including gasoline have little effect on this
property, which is important in parts incorporating self-threading
screws and interface fits.
 Acetal homopolymers

Melting points of homopolymers are higher and

they are harder, have higher resistance to fatigue are more
rigid and have higher tensile and flexural strength will
generally lower elongation. Some high-molecular weight
homopolymers are extremely tough and have higher
elongation than copolymers. Grades are available that are
modified for improved hydrolysis resistance to 82°C
similar to co-polymer
 Acetal Copolymers

Acetal copolymer have an excellent balance of properties and

processing characteristics. Melt temperature can range from 182 to
232°C with little effect on part strength.

It is available in its translucent natural white and in a wide

range of colors and dimensionally stable, low warpage grades.

They have high tensile and flexural strength fatigue resistance

and hardness. They retain much of their toughness through a broad
temperature range and are among the most creep resistant of the
crystalline TPs. Strength of copolymer is only slightly reduced after
aging for one year in air at 116°C.
 Acetal Copolymers

Impact strength holds constant for the first six

months and falls of about one third during the next six
months

Aging in air at 82°C for two years has little or no

effect on properties and immersion in water for one year at
82°C leaves most properties virtually unchanged. Samples
tested in boiling water retain nearly original tensile
strength after nine months.
 Acetal Copolymers

Good electrical properties combined with high

mechanical properties and UL- electrical rating of 100°C
qualify these plastics for electrical parts requiring long
time stability. Copolymer have excellent resistance to
chemicals and solvents. For example, samples immersed
for 12 months at low temperature in various inorganic
solution were unaffected except by strong mineral acids,
sulfuric, nitric and hydrochloric. Most organic reagents
tested have no effect, not do mineral oil, motor oil or break
fluids. Resistance to strong alkaline is exceptionally good.
 Acetal Copolymers

The copolymers remain stable in long term high

temperature service and after exceptional resistance to the
effects of immersion in water at high temperatures. Neither
type resists strong acids and the copolymer is virtually
unaffected by strong bases. Both types are available in a
wide range of melt flow grades. unreinforced and
reinforced grades PTFE or silicone filled grades. Several
grades of homo or copolymers types comply with the FDA
for repeated contact with food at 120°C.
 Application of Polyacetal

•Appliances
•Agriculture & Irrigation
•Consumer Products
•Industrial
•Electrical
•Plumbing & Hardware
 Application of Polyacetal

Appliances: Housing for business machine, gears, cams, friction pads,

rollers, pulleys, nuts, chain links and shelf support brackets, detergent
pumps, refrigerator clips and brackets, bearing, wear strips and
instrument housing in washers and dryers, spray nozzies and soap
dispensers in dishwares , bowls, mixing blades and bearings in counter-
top appliance bodies, tops and cups in water boilers.

Fig. 29. Detergent pumps

 Application of Polyacetal

Agriculture & Irrigation: Pop-up sprinklers (nozzles

arms, gears, housing and water ways),
pumps(housing, impellers, pistons) metering valves,
tractor components (shift lever housing, hydraulic
connectors, seed applicators, bearings and gears)
 Application of Polyacetal

Automotive: Fuel level indicators, pump components, gas caps,

cooling fans, trip clips, colour co-ordinated bucket housings, window
cranks, shift lever handles, knobs, lever and mounting brackets,
instrumental cluster gears, bearings, housing and dials, exterior door
pulls, mirror housing and brackets

Fig. 30. Automotive parts

 Application of Polyacetal

Consumer Products : Toys soap dispensers , combs,

filter bodies and valves, aerosol containers and
valves, pen and pencil barrels and tips, mascara
wands & containers, sprayer pumps, nozzles and
pump components for dental cleaners.
 Application of Polyacetal

Industrial: Valves, springs, bearings, cams, material

handling components such as conveyors, chain links gears,
pumps and hose connectors

Fig.31. Conveyor
Fig.32. Gears
 Application of Polyacetal

Electrical: Key tops pluggers, switches, buttons,

cassette tape rollers and hubs, base plates in
computer keyboards, springs in telephones and
connectors in modular components.
 Application of Polyacetal

Plumbing & Hardware: Water –meters, cams, gears,

dials and pressure plates, pressure regulator valves,
drapery and venetian blind guide rollers, furniture ,
casters, slid plates and locks, tool holders, bearing in
adapters, shower heads, sprayers, garden hoses and
nozzles, irrigation gates, impellers, pumps and
hangers.