At a conference 'Polyolefins
2005' at Houston, USA, organized by SPE, several
new developments on additives for Polyolefins
were presented. We summarize some of these developments
here:
Coupling Agents for PP- Woodflour composites
Dyenon has developed functional hydrocarbon-based
block copolymers, based on proprietary "controlled-architecture
materials" (called CAM ) for PP woodflour
composites and polymer nanocomposites. These
compatibilizers for wood-plastic composites
(WPC) are aimed to improve processing and surface
aesthetics, reduce edge tear, and raise stiffness
and tensile strength.
Dupont has introduced a new Fusabond coupling
agent W PC-567D for PE/wood composites that
is said to significantly boost strength and
reduce water absorption at very low use levels.
Fusabond W PC-567D is possibly based on ethylene
copolymer with anhydride functionality incorporated
in its backbone.
Crompton has pursued a similar goal of adding
greater MA functionality with its new technology
for producing MA-functionalized PP. With this
process, the company has produced developmental
maleated PP coupling agents that reportedly
overcome the limitations of current commercial
products in that they allow molecular weight
and functionality to be varied independently.
Moreover, the molecular-weight distribution
of the starting resin is more closely preserved
because of reduced chain scission during the
functionalization reaction.
These coupling agents increase flexural properties
almost by 100% compared to the conventional
coupling agents. Coupling agents made with Crompton's
new technology appear to be less adversely affected
by lubricants. PP/wood composites made with
these additives retained 90% of original flexural
strength when a 75/25 blend of fatty acid ester
and fatty acid amide was added, compared with
76% retention for the reactive-extrusion coupling
agents
Nano-compatibilizers
Dyneon is currently exploring "controlled-architecture,"
hydrocarbon-based block copolymers as compatibilizers
and coupling agents for polyolefin and styrenic
nanocomposites made by melt compounding montmorrilonite
clay.
Current additives that enhance the exfoliation
and dispersion of organically modified clays
include copolymers such as MA-grafted polyolefins
for use with organically modified clays. Their
main drawback is inefficiency: A fairly high
level of additive is needed to exfoliate the
clay. Dyneon has been developing a broad range
of new, more efficient block copolymers containing
amine, epoxy, anhydride, and acid functionality
for use with a variety of clays.
For example, composites consisting of 5% of
a CAM coupling agent, 5% of an organoclay (three
were tested), and 90% PP were compounded in
a twin-screw extruder. These nanocomposites
were then compared with similarly prepared blends
of PP with clay and 5% maleated-PP random copolymer.
X-ray diffraction studies reportedly showed
that CAM nanocomposites were more efficient
in aiding exfoliation of the clay and at significantly
lower loadings (only 1%). In addition, the CAM-coupled
compounds had 40-50% higher tensile modulus
than the MA-PP composite.
Fluro surface modifiers
D yneon has also developed migratory additive packages that can modify polyolefin surface properties at low loading levels. These additives include block copolymers of a fluorinated butenesulfonamide ethyl methacrylate, which can render polyolefinic surfaces hydrophobic or hydrophilic to impart anti-fogging, static dissipation, adhesion, compatibilization, paintability, printability, dyeability, and moisture wicking. Applications include carpet fibers, agricultural films, nonwovens, auto bumper fascias, packaging, hygienic products, incompatible resin blends, laminated articles, and eyewear.
Light Stabilizer
Researchers at Cytec have found that recently developed hindered hydroxybenzoate (HB) light stabilizers (non-basic forms of phenolic antioxidant) offer significant advantages in combination with primary and secondary antioxidants plus high-molecular weight (HMW) HALS light stabilizers. These stabilizer systems reportedly give polyolefins long-term thermal stability as well as moderate to very high light stability.
Polynox Corp. has developed a new class of high-performance antioxidants for polyolefins that boast significantly higher activity and lower migration than conventional antioxidants, resulting in longer service life for finished products. Albermale has another novel approach for minimizing phenolic discoloration. Researchers discovered that a small amount (as little as 300 ppm) of Albemarle 's "Poly A" polyhydric alcohol is an effective color-reducing additive when used with phenolic antioxidants in PP and HDPE.
Silicone flow enhancer
A novel pelletized silicone gum from
Wacker Chimie based on an ultra-high-MW (UHMW)
polydimethylsiloxane, is very effective in improving
the processing and flow properties of a range
of thermoplastics, particularly filled polyolefins.
With a higher concentration of UHMW silicone
gum than conventional solid silicone additives,
Genioplast Pellet S has also been shown to improve
impact and tensile strength as well as surface
smoothness and abrasion resistance.
Beta Nucleating Agent for PP
A new type of nucleator masterbatch
for PP has been developed by Mayzo Inc. It produces
unique properties in OPP film and enhances properties
and processability of moulded and extruded products.
The conventional agents nucleate the alpha-crystal
phase, the most common crystal form of PP. In
injection molded or extruded PP, the alpha type
accounts for over 95% of the crystals.
A less common form is the beta crystal form,
which produces improved impact strength and
ductility but lower tensile yield strength.
While there are many commercially available
grades of alpha-nucleated PP, there are no beta-nucleated
PP resins commercially available in the U.S.
and only two fractional-MFR grades are produced
in Europe for pipe.
Mayzo introduced two commercial beta-nucleant
masterbatches last year. Both have a PP homopolymer
carrier and contain only ingredients acceptable
for food contact. They are priced competitively
with high-performance alpha-nucleating agents.
One grade, BNX BetaPP-LN, contains a lower level
of the company's proprietary beta nucleating
agent and is suitable for non-pigmented film
and thermoformable sheet. It is typically added
at a 2% to 3% loading.
The other grade, BNX BetaPP-N, contains a higher
level of beta-nucleant and is also designed
for use at 2% to 3% in situations where weak
alpha-nucleating agents, such as certain pigments
and additives, may be present in the PP and
could interfere with beta-nucleation. This product
is also suitable for compounders and polymer
prod ucers.
Extruded PP sheet containing this masterbatch
has very high levels of beta crystallinity.
When subsequently stretched into monoaxial or
biax film, the beta crystals transform into
alpha crystals and develop microvoids. These
microvoids scatter light, resulting in an opaque
film whose density is reduced by 12% to more
than 40%, depending on process conditions.
In thermoforming, beta-crystalline PP sheet has a broader processing window than conventional PP sheet, according to Jacoby. Beta-nucleated sheet has been formed into white/ opaque containers (Fig. 6), which are advantageous for dairy products because less TiO2 is needed to produce a uniform white color.
FR additive
J.M Huber Corp. has been developing new grades of magnesium hydroxide (abbreviated MDH) with various particle characteristics and surface treatments to optimize low-smoke, non-halogen, flame retardant polyolefin compounds such as EVA wire and cable jacketing. One new grade is Vertex 100, a 0.8-micron MDH with an intermediate particle-size distribution. When treated with a vinyl silane and used in EVA cable jacketing, the product reportedly outperforms existing MDH products with either silane or fatty-acid surface treatment.
Competitors that were tested include a 1-micron grade with narrow particle-size distribution, a 1.5-micron MDH with broad particle-size distribution, and a 4.5-micron size with intermediate particle-size distribution. All were compared by measurement of heat-release rate in a cone colorimeter (ASTM E1354)
In these tests, the Vertex 100 compound displayed a lower heat-release profile and also showed a later and lower second heat-release peak, suggesting more potent FR efficacy.
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