overview of maleic -anhydride-grafted polyolefin coupling · pdf file ·...
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Overview of Maleic-Anhydride-Grafted Polyolefin Coupling Agents
A guide to understanding their uses, benefits, functions, selection, and developments
Louis W. Martin, Addcomp North America Inc.
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Fundamentals of polyolefin coupling agents
The primary functions of coupling agents • Connect olefinic polymers to dissimilar materials
• Connect (not compatibilize) olefinic polymers with dissimilar polymers
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Fundamentals of polyolefin coupling agents
Connect polymers to dissimilar materials • Inorganic materials:
−Glass fiber − Carbon fiber −Metals
• Organic materials −Wood − Flax − Cotton −Hemp
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Fundamentals of polyolefin coupling agents
Connect different polymers • Join olefinic resin film with other film
• Not intended to compatibilize incompatible polymers within the same bulk − Polyolefins and polyamides
−HDPE and PP
−Others
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Fundamentals of polyolefin coupling agents
Major uses for coupling agents • Couple reinforcing fibers to polymer matrix
−Glass, carbon, hemp, wood, flax, cotton
• Connect polymer with substrate − Coatings or linings for metal containers
−Overmolded polymers on metal structures
• Tie layers between polymer films
• Adhesives
• Emulsions
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Fundamentals of polyolefin coupling agents
Benefits of coupling agent use • Reduction in fiber pullout
− Increase impact strength
− Increase tensile strength
• Reduction of water absorption − Prevent degradation in natural fibers
− Prevent corrosion in metals
• Create tie layer between dissimilar materials − Provide strength for multilayer polymer films
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Fundamentals of polyolefin coupling agents
Major classes of coupling agents • Parts produced using melt compounding only
− Polyolefins grafted with maleic anhydride
• Parts requiring reactive extrusion during production − Silanes
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How coupling agents work
Polar group (B) grafted onto olefin group (A) • A is polypropylene
• B is maleic anhydride
A
B
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Two-part molecule • Polar group
− Creates chemical bond with substrate – Sizing on reinforcing glass fiber
– Metal
– Wood or other natural material
– Polar resin
• Olefin section − Forms hair-like structure that becomes part of resin bulk
– Mechanical entanglement with resin chains
How coupling agents work
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Schematic of coupling
How coupling agents work
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Influences on selection of coupling agent
Balance of polyolefin chain lengths • Longer chain length provides strength
−Greater mechanical entanglement with resin
• Shorter chain length provides mobility −Greater number of polar groups reach substrate
− Increases melt flow
Percentage of olefin molecules with grafted polar groups
Amount of free MAH
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Various combinations of molecular weight and percentage of grafted polar group are appropriate for different applications
Influences on selection of coupling agent
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Process influences on performance
Inventory of reaction products • Ungrafted PO
−Unbroken chains, shortened chains
• PO-MAH − 1:1 grafted molecules
• MAH-PO-MAH − 2:1 grafted molecules
• Free MAH
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Process influences on performance
Typical level of free MAH in standard coupling agents • 0.2% to 0.25% (2000 to 2500 ppm)
• This can be 50% of total MAH in coupling agent
Process improvements currently in production can lower this to 0.005% or 0.6%
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Process influences on performance
Higher concentrations of free MAH • Outgassing from materials and finished parts
−Unacceptable odor
− Fogging of proximate surfaces
− Potential impact on color
− Potential reduction of UV resistance
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Process influences on performance
Optimum constituent levels • 1:1 grafted MAH-PO molecules
−No ungrafted PO molecules
−No multi-grafted PO molecules
• Minimal free MAH − 20-50 ppm (0.002 - 0.005%) free MAH possible
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Process influences on performance
Influence on tensile strength in fiber-reinforced polymers • [Need to insert graph from 2009 short-fiber
study here]
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Influence on application suitability
Process influences on performance
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Next generation PO-MAH coupling agents • Higher Mw PO @ constant grafted MAH %
− Stronger mechanical entanglement with polyolefin
– Higher tensile strength materials
• Lower % free maleic anhydride
− Lower emissions of volatile organic compounds (VOCs) – Less fogging from applications in use
− Less pollution of possible sites for bonding with substrate – Higher tensile strength
Development trends
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Higher Mw polyolefins
Development trends
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Lower % free maleic anhydride
Development trends
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Lower VOCs and fogging
Development trends
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Higher tensile strength
73.6 75.1 75.1 70.9 73.2
22 22 23 22 18
0102030405060708090
Reference Old Technology Source Reduction
New Tech 1: Stripping Agent
New Tech 2: Adsorbent
Tensile Strength Flow
Izod Notched @ -40C flow
Development trends
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Fundamentals of polyolefin coupling agents
Discussion and Questions