The first quarter of 2005 will see the first commercial production of a dramatically
new family of resins that offer the processing advantages of liquid thermosets
plus the properties and recyclability of engineering thermoplastics. Cyclics
Corp., a company formed in 1999 to acquire patented technology developed by
General Electric Co., is about to open a 5.5-million-lb/yr plant to produce
its first CBT resins. These low-molecular-weight PBT oligomers are solids that
melt at relatively low temperatures to yield a water-like viscosity that readily
impregnates fiber reinforcements or accepts high loadings of fillers. Upon
further heating, the liquid polymerizes into a normal PBT polyester.
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| Wind-turbine blades and automotive composites are some of the applications
being actively investigated for new in-mold polymerized PBT resins. These
thermoplastic composites would be recyclable. |
This new
type of material leaps previous hurdles to high-performance thermoplastic
composites and also has broad potential in rotomolding, casting, injection
molding, and powder coatings. For example, CBT resin has been demonstrated
in “thermoplastic
RTM” molding, in which glass mat or fabric reinforcements were impregnated
by drawing the liquid resin through the mold using vacuum alone. Impregnation
is said to be easier than with epoxy. A hockey stick containing more than
75% carbon fiber has been impregnated with CBT. In addition, continuous-fiber
prepregs can be made with CBT by melting, impregnation, and cooling again
to a solid without curing. CBT can also be compounded without curing at low
temperatures with pigments or other additives to make masterbatches for use
in thermoplastics. Also, company sources report that low-viscosity CBT resins
show advantages in preparing nanocomposite compounds, because the CBT resins
facilitate exfoliation (delamination) of the nanoclay particles.
Gearing up
for growth
Cyclics’ first commercial plant is located on the grounds of a BASF
facility in Schwartzheide, Germany. Cyclics will take standard PBT resin
produced by BASF there and partially depolymerize it into lower-MW CBT
resin. Cyclics says half its plant capacity is already committed to certain
customers, so the company is planning to double its capacity to 11 million
lb this year. The company is also searching for a location for a world-scale
plant of 55 million to 110 million lb that could be up and running as early
as 2009.
In high volumes, CBT resins will cost around $6/lb initially. However,
once the world-scale plant is operating, prices should be very close
to that of standard PBT.
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| Carbon-fiber prepreg tapes impregnated with CBT resin could be used as a reinforcing wrap for older concrete structures such as bridges. The thermoplastic tape can be heated and bent around corners. |
Cyclics has concluded a number of agreements with partners
in application development. For example, Dow Automotive has a long-term exclusive
right to develop five areas of car, truck, bus, and rail applications. Dow
is said to be interested in developing injection molding, RTM, and
SMC applications in areas like body panels, truck boxes, load floors, and
bumper beams.
Meanwhile, Alcan Composites, a unit of Alcan Inc., has
exclusive rights to develop architectural, display, and graphic-arts markets,
as well as general industry infrastructure applications—such as carbon-fiber
tapes for reinforcing bridges. Gaoth Tec Teo of Galway, Ireland, is working
with Cyclics and Mitsubishi Heavy Industries of Nagasaki, Japan, to develop
composite wind-turbine blades. These blades are expected to use epoxy prepregs
co-laminated on top of CBT prepregs. Cyclics also has an R&D agreement
with Ahlstrom Glassfibre Oy of Helsinki, Finland, to develop wind-turbine
and marine applications using Ahlstrom’s
reinforcements.
In addition, Cyclics named the P-Group of Ferrara,
Italy, as the sole compounder of CBT resin for the European rotomolding
market. (Cyclics also recently appointed an account manager, Barry Aubrey,
specifically for rotomolding.) And the first actual commercial
application for CBT is a tough, heat-resistant material for thermoforming plug
assists. Called Eccolite Ultra Syntactic Foam, it is supplied in
machinable rods, blocks, and sheets—all filled with hollow
microspheres—by
Emerson & Cuming Composite Materials.
Two grades to start
Cyclics initially is launching two grades of PBT precursors, though
its technology is applicable to other polyesters such as PCT,
PTT, and polycarbonate. CBT also has potential for copolymerization
with epoxy and other resins—a
developmental TPE has already been prepared by reactive extrusion.
PROPERTIES OF
POLYMERIZED CBT RESIN |
| Density, g/cc |
1.31 |
| Tensile Yield Str., psi |
7800 |
| Yield Elongation, % |
3.2 |
| Ultimate Elongation, % |
>50 |
| Tensile Modulus, psi |
392,000 |
| Flexural Modulus, psi |
345,000 |
| Flexural Strength, psi |
10,700 |
| Notched Izod, kJ/m2 |
6.7 |
| Unnotched Izod |
No Break |
| Mold Shrinkage, % Flow Direction, 0.16 in. |
1.5 |
The
two initial grades are CBT 100 and CBT 200. The first is aimed
at injection molding, rotomolding, compounding, nanocomposites,
and thermoplastic masterbatches. It melts at around 180 C (356
F) and can be processed between 190 and 240 C (374 to 464 F).
It has a fast-acting catalyst that cures in a few seconds to
a minute,
depending on temperature.
CBT 200 is designed for longer working
times in composites, casting, and coatings. It melts at about
160 C (320 F) and is processed at 170 to 240 C (338 to 464 F).
Cure times can range from a few minutes to more than an hour.
Both resins have initial melt viscosities of about 10 to 40 cps
over a temperature range of 170 to 220 C. Both materials yield
identical PBT resins with properties at least as good as those
of standard PBT (see table). Company sources note that CBT-based
resins usually have twice the molecular weight of standard PBT
without affecting processability. Higher MW reportedly confers
advantages in weathering and wear resistance.
Both CBT grades
can be supplied in one-component or two-component forms. CBT uses standard
tin and titanate catalysts used to polymerize polyesters. These materials
are said to present no toxic hazard to processors.
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