P. Nagaraj, M.

Ferrandino*

into the prepolymer to achieve a stable mix-

Adiprene Duracast –
An easy to use high performance
urethane system
Adiprene Duracast is a novel two component urethane system that offers a unique combination
of processing, performance and total cost in use advantages versus other two component
urethanes currently available in the market place. The new system is based on a MDI pre-
polymer with reduced monomer content and a blocked amine curative compound. Adiprene
Duracast prepolymers are cured with Duracure to off-
set the processing issues with amines (such as
4, 4’ methylene bis (2-chloroaniline)-MBOCA)
and diols. Duracast/Duracure systems
offer some unique processing and
productivity improvements includ-
ing extremely long pot life and a
quick de mould time. Duracast
Fig. 1:
Wheel for earth-
systems can thus be used to
moving machines cast very large (fig. 1) (in the
made out of 100 % order of tons) or very intricate
Adiprene Duracast:
Weight app. 4 tons, parts. Along with processing
height app5 meters advantages the urethane offers
excellent physical and engineer-
ing properties, including cut and
tear resistance, flex fatigue, low
temperature flexibility, dynamics and
high temperature properties. It also
offers EH&S advantages as it is based
on low free monomer technology and is a
MBOCA free system.
ture. Conventional urethane systems have a
pot life of minutes whereas the Duracast-
Duracure mix has a pot life of several hours
and in many cases (mix held at lower tem-
peratures such as 50 – 60 °C) the pot life is
in the order of 24 – 48 hours. The mix can be
heat activated by pouring into a hot mould
(115 – 140 °C) which leads to irreversible
deblocking of the curative. The chain exten-
sion reaction is rapid once the deblocking
temperature is reached, leading to a high
performance urethane.
Duracure C3 is a blocked amine compound
dispersed in a plasticizer. The ease of use,
reduced risk of exposure to amines, extend-
ed pot life and quick de mould time are the
primary reasons for choosing the blocked
curative (tab. 2).
Exposure to the amine compound is signifi-
cantly reduced since the curative is blocked
and is liquid at room temperature. In a batch
process, once Duracure is mixed with Du-
racast prepolymer, the system is designed
to immediately consume any liberated free
amine. However, most of the amine is
blocked leading to a stable mixture. Another
safety feature is the reduced free monomer
content of the Duracast MDI prepolymers.
This is beneficial in the management and
control of worker exposure to Isocyanates.

1. Introduction conventional two component systems. The 2. Experimental

Duracast-Duracure systems utilize similar
polyurethane and polyurethane-urea chemis-
try as traditional two component systems,
but provide unique processing and perform-
ance advantages in comparison to other
* Phani Nagaraj,
Phaniraj.Nagaraj@chemtura.com
Global Marketing Manager,
Performance Speciality-Urethanes
Mark Ferrandino
Chemtura Corporation, Middlebury, CT, USA
processing of Duracast systems is signifi-
cantly simplified in comparison to conven-
tional two component systems (tab. 1).
These advantages include easy 4 step
processing, virtually unlimited pot life, quick
de mould time, better ratio control, reduced
exposure to isocyanate monomers and
amine curatives and the ability to use a hand
batch process, batch process using a day
tank or a two component machine.
Similar to other two component urethanes,
Duracast prepolymer systems consist of an
isocyanate capped polyol. However, the
critical difference is that the curative is
blocked to prevent the occurrence of chain
extension. The curative can thus be mixed
The Duracure curative was rolled overnight.
The particles in the plasticizer blocked cura-
tive dispersion blend can tend to settle over
time leading to differences in activity at the
top and bottom of the container. It is there-
fore important to roll/tumble the Duracure
container at least 5 hours for a pail and
12 hours for a drum. All the Duracast pre-
polymers were melted overnight at 70 °C.
Appropriate amount of Duracast prepolymer
was weighed in a container. Three different
methods were used to process Duracast:
• Hand batch process
• Drill mix and
• Batch process using a reactor.

2 PU MAGAZINE – VOL. 5, NO. 6 – DECEMBER 2008

Duracast E950 (MDI/PTMEG) prepolymer
was heated to 90 °C and degassed in a
vacuum chamber at < 30 mm Hg. Duracure
C3 curative was degassed in the vacuum
chamber at similar conditions. Duracure C3
curative was added to Duracast E950 while
agitating the prepolymer using a spatula. It
is critical to add the Duracure while agitat-
ing the prepolymer. If this is not done, white
irreversible specks form in the final product.
The mixing was done in circular and figure
eight fashion to ensure uniform mixing. The
mixture was then degassed in the vacuum
chamber. The material was then poured into
two heated moulds one at 120 °C and the
other at 140 °C. It is important to note that
▼ Tab. 1: Comparison of processing steps of Duracast and traditional two component urethanes
Duracast-Duracure system
• Heat activated curing.
Mix stable at 50 – 70 for prolonged period.
• No curative melting.
• No curative dust issues.
Easy handling at room temperature.
a minimum mould temperature of 115 °C is
required to deblock Duracast-Duracure sys-
tems. The sheet and buttons were de
moulded from 120 °C mould in 15 minutes
and 140 °C moulds indicating very quick de
mould. The castings were then post cured
at 120 °C and 140 °C for 16 hours and al-
lowed to age at room temperature for two
weeks before testing. The physical proper-
ties were measured using standard ASTM
methods.
Similar steps were used with a drill mixer
(such as a Jiffy or Hanson Plunge mixer) ex-
cept for the mixing process which was done
using a drill mixer. The drill mixer ensures a
Typical Two Component system
• Cure reaction begins as soon as curative is added.
• MBOCA has to be melted at > 90 °C.
• Dust issues with MBOCA.
more uniform mix and is quicker than a hand
batch process.
The next type of process employed was a
batch process using a reactor. This process
was used to simulate a tank that can be used
to mix and hold large quantities of Duracast-
Duracure mix. The prepolymer was held at
lower temperature compared to hand batch
and drill mix process. The prepolymer was
held at 50 °C for ethers such as Duracast
E900/Duracast E950 and 70 °C for esters
& caprolactone such as Duracast S900/ Du-
racast S930/Duracast C930. Vacuum was
applied to degas the prepolymer followed by
addition of Duracure at a very slow rate to
the vortex of the blend under agitation. The
batch was held under vacuum during the mix-
ing. The mix was ready to use in 1 hour. The
mix was stable and could be used for
24 – 48 hours as long as the temperature on
the reactor was maintained at 50 °C or 70 °C
depending on type of the system. The three
different processes are shown in figure 2.

• Quick mould fill is not required. • Quick mould fill is required to prevent gel formation.
The non-blocked systems, such as TDI pre-
• Better ratio control. • Much more difficult to control ratio (especially polymers (Adiprene L167 and Vibrathane
in Butanediol (BD) cured systems)
8090) and MDI prepolymers (Vibrathane
• Quick de mould time (10 – 20 minutes). • Longer de mould time (30 – 60 minutes)
B836 and Vibrathane 8590) cured with MBO-
• Easy 4 step processing. • Processing expertise required with MDI/BD systems. CA and Butanediol (BD) respectively, were
Can use batch process in a day tank or a machine. Machine required for high productivity.
heated to 70 °C and degassed in a vacuum
chamber at < 30 m bar. For the TDI systems
▼ Tab. 2: A comparison of curative characteristics the MBOCA was melted at 115 °C. TDI pre-
Duracast MDI Prepolymer TDI Prepolymer TDI Prepolymer polymers were mixed with MBOCA using a
Urethane systems
Duracure Butanediol (BD) MBOCA MCDEA speed mixer at 2500 rpm for 30 seconds.
Physical state of curative (at 30 °C) Liquid Liquid Solid Solid
This was followed by pouring the viscous mix
Pot life (minutes) 300 – 1500 3 – 10 3 – 10 2–4
into heated moulds at 100 °C. The castings
De mould (minutes) 5 – 30 20 – 60 20 – 40 10 – 30
were cured at 115 °C for 16 hours. Similarly
the MDI prepolymers and BD were mixed in
▼ Fig. 2: Three different ways of processing Duracast-Duracure a speed mixer at 2500 rpm for 30 seconds.
This was followed by pouring the mix into
N2 in / N2 out heated moulds at 100 °C. The castings al-
Vacuum lowed to age at room temperature for two
weeks before testing. The physical proper-
ties were measured using standard ASTM
Vacuum rated
holding/blend tank methods.

The stability studies for the Duracast-Duracure

premix was done by taking assays. The vis-
cosities of samples were measured at regular
Mold filling intervals using a Brookfield viscometer with a
1) Hand Batch 2) Drill Mixer 3) Batch Tank number 27 spindle. The pot life of a standard
two component system was also measured

PU MAGAZINE – VOL. 5, NO. 6 – DECEMBER 2008 3

using a Brookfield viscometer using a number better annealing of the hard segment at improvement in elongation and tensile
7 spindle to understand the differences in higher post cure temperature. strength. The Duracast ether system also
cure characteristics of traditional two compo- has comparable properties as TDI/PTMEG/
nent and Duracast systems. Table 4 indicates a similar trend with Du- MBOCA systems and the MDI/PTMEG/BD
racast ether system. The trouser tear system when post cured at lower tempera-
strength improves almost 65 % along with ture.
3. Results and discussion
Tab. 4: Physical property comparison of Adiprene Duracast ether systems with
In table 3, a 90A Shore A hardness, Adi- ▼ standard two component urethane systems
prene Duracast Ester material is compared Duracast E950/ Duracast E950/ Adiprene L167/ Vibrathane
Material
with a standard 90A two component system Duracure C3 Duracure C3 MBOCA B836/BD
% NCO of Prepolymer 5.0 5.0 6.3 8.85
based on TDI/Ester/MBOCA (Vibrathane
Type LF MDI/Ether/Amine LF MDI/Ether/Amine TDI/Ether/MBOCA MDI/Ether/BD
8090/MBOCA) and MDI/Ester/BD (Vibrathane
Pot Life (70C) Several hours Several hours <20 minutes <20 minutes
8590/BD) to illustrate the performance ad-
Pot Life (>70C) > 10 minutes (90 °C) > 10 minutes (90 °C) 6 minutes (85 °C) 5 minutes (80 °C)
vantages of Duracast. A 95 Shore A hard-
Post Cure (°C) 120 140 100 100
ness, Adiprene Duracast PTMEG material is
Hardness, Shore A 96 – 97A 96 – 97A 95 95A
compared with a standard 95 Shore A two
100 % Modulus, psi 1700 1841 1800 1345
component systems based on TDI/PTMEG/
300 % Modulus, psi 2250 2000 3400 2365
MBOCA (Adiprene L167/MOCA) and MDI/
Tensile Strength, psi 4200 6300 5000 5460
PTMEG/BD (Vibrathane B836/BD) to illus-
Elongation at Break, % 480 550 400 460
trate the performance advantages of the new
Tear Strength, Split, pli 155 180 150 155
Duracast systems in table 4.
Tear Strength, Trouser, pli 200 330 – –
Bashore Rebound, % 57 57 40 60
Adiprene Duracast materials were post cured
at two different temperatures to observe the Comp. Set, Method B
28 32 40 30
(22 hrs. @ 70 °C), %
effect of temperature on physical properties.
From table III it can be observed that Adi-
prene Duracast S900 has better engineering ▼ Tab. 5: Viscosity profiles of Adiprene Duracast/Duracure blends versus time
properties. Compression set which can be Viscosity @ 50 °C, cps Duracast E950/ Duracast E900/ Duracast S930/ Duracast C930/
an important factor in tires and wheel is sig- Duracure C3 Duracure C3 Duracure C3 Duracure C3
0 hrs 5925 5125 2925 2275
nificantly lower than conventional two com-
4 hrs 5975 6850 3200 3650
ponent urethane systems. Another interest-
24 hrs 6725 7900 4200 4150
ing feature of Adiprene Duracast ester mate-
rials is the high Bashore rebound. Esters are
usually characterized by low rebound in com- Tab. 3: Physical property comparison of Adiprene Duracast ester systems with standard two component
parison with ether based urethanes because ▼ urethane systems
of decreased phase segregation due to hy- Duracast S900/ Duracast S900/ Vibrathane Vibrathane
Material
drogen bonding of ester linkages. The supe- Duracure C3 Duracure C3 8090/MBOCA 8590/BD
% NCO of Prepolymer 3.5 3.5 4.5 8.05
rior MDI-Amine-MDI hard segment offers im-
Type LF MDI/Ester/Amine LF MDI/Ester/Amine TDI/Ester/MBOCA MDI/Ester/BD
proved phase segregation leading to im-
Pot Life (70C) Several hours Several hours < 20 minutes < 20 minutes
proved properties.
Pot Life (90C) >10 minutes (90 °C) >10 minutes (90 °C) 5 minutes (90 °C) 5 minutes (90 °C)
Post Cure (°C) 127 140 100 100
It was also found that tear properties are
Hardness, Shore A 89 89 90 91
comparable to other urethanes when Adi-
100 % Modulus, psi 900 980 1100 1170
prene Duracast materials are post cured at
300 % Modulus, psi 1290 1390 2200 2860
lower temperatures. However, by increasing
Tensile Strength, psi 5200 5700 7300 7300
the post cure temperature it is possible to
Elongation at Break, % 550 650 530 490
significantly increase the tear strength. From
Tear Strength, Split, pli 125 135 155 120
table III it can be observed the trouser tear
Tear Strength, Trouser, pli 210 390 – –
(indicative of resistance to tear propagation)
Bashore Rebound, % 55 58 28 30
of Adiprene Duracast can be increased al-
most 100 % just by increasing the post cure Comp. Set, Method B
25 22 32 26
(22 hrs. @ 70 °C), %
temperature. This is believed to be due to

4 PU MAGAZINE – VOL. 5, NO. 6 – DECEMBER 2008

The data in table 5 illustrates the viscosity
profiles of Adiprene Duracast- Duracure
blends versus time. It is observed that Du-
racast systems have extremely long pot life
(in the order of days) when held at tempera-
tures between 50 – 70 °C. At higher mix tem-
peratures such as 90 °C, the pot life is re-
duced but is considerably long compared to
conventional systems cured with either MBO-
CA or BDO. It is thus possible to pour ex-
tremely large parts (several tons) or fill
moulds which require a greater fill time due
to intricate part design.
4. Conclusions
Adiprene Duracast systems are novel high
performance, easy processing hot cast ure-
thane elastomers. The advantages of the
new Adiprene Duracast systems include
tighter ratio control, no curative melting or
dusting, extremely long pot life, very quick
de mould time, versatile processing tech-
niques, low/minimal capital investment for
processing equipment, the ability to cast
extremely large or intricate parts and lower
exposure to Isocyanates & amines. Further-
more, the technology can reduce costs due
to ease of automation, reduced worker
training time and reduced scrap. Adiprene
Duracast is available as ether based, ester
based and caprolactone based prepoly-
mers. These systems can be cured with
Duracure C3 or Duracure C2 although Du-
racure C2 can only be used while process-
ing with a machine. Currently 5 products are
available (tab. 6) with more in the pipeline.
Lower hardness products will be commer-
cialized in the future, although it can also be
achieved by processors in the short term
simply by addition of a plasticizer such as
Benzoflex.
5. Acknowledgements
We would like to thank Richard Palinkas (Re-
search Fellow), Ian Laskowitz (Senior Engi-
neer), Ron Emanuel (Senior Chemist) and
Harish Chandra (Senior Engineer) for their
research and development work on the Du-
racast-Duracure systems.
■

▼ Tab. 6: Adiprene Duracast product range

Duracast E900/ Duracast E950/ Duracast S900/ Duracast S930/ Duracast C930/
Material
Duracure C3 Duracure C3 Duracure C3 Duracure C3 Duracure C3
% NCO of Prepolymer 3.0 5.0 3.5 4.5 4.5
Type LF MDI/Ether/Amine LF MDI/Ether/Amine LF MDI/Ester/Amine LF MDI/Ester/Amine LF MDI/PCL/Amine
Post Cure (°C) 140 140 140 140 140
Hardness, Shore A 89-91 96-97 89 91-93 93-95
100 % Modulus, psi 1074 1841 980 1150 1400
Tensile Strength, psi 5650 6300 5700 5550 6100
Elongation at Break, % 790 550 650 550 600
Tear Strength, Split, pli 140 180 135 145 160
Tear Strength, Trouser, pli 230 330 390 340 465
Bashore Rebound, % 65 57 58 53 61
Comp. Set, Method B (22 hrs. @ 70 °C), % 22 32 22 22 23

PU MAGAZINE – VOL. 5, NO. 6 – DECEMBER 2008 5