Block Copolymers for Epoxy Toughening
Robert Barsotti, Arkema Inc., 900 1st Avenue, King of Prussia, PA, 19406, USA
Due to their high strength, excellent high temperatureproperties and good adhesion to many surfaces, epoxiesare extremely valuable engineering materials incomposite, adhesive, coating, and electronic applications.Epoxies, however, suffer from a very low toughness.Arkema’s controlled radical and anionic polymerizationtechnology has been used to synthesize block copolymersadditives, which provide excellent toughening to epoxieswithout sacrificing modulus or glass transitiontemperature. By incorporating functionality into the epoxymiscible block of the polymer, nanostructuration of thesepolymer additives are achieved in a wide range of epoxysystems, resulting in excellent thermal and mechanicalproperties.
Due to their high strength, excellent hightemperature properties and good adhesion to manysurfaces, epoxies are extremely valuable engineeringmaterials in composite, adhesive, coating, and electronicapplications. Epoxies, however suffer from a very lowtoughness. One approach to improve the toughness of epoxies is via flexibilization. Monofunctional or highMW difunctional epoxy molecules can react directly intothe epoxy matrix, lowering its crosslink density. Thisimproves the toughness of the material but does so bysacrificing strength and lowering the glass transitiontemperature of the network. Similarly, reactive rubbermodifiers, such as carboxy-terminated butadieneacrylonitrile (CTBN), can react into the surroundingepoxy matrix. Again toughness is increased but with thesacrifice of strength and thermal properties.
A second approach to toughening is the inclusion of softerphase material which does not react into the matrix, eithercore-shell particles, typically with a PMMA shellsurrounding a low T
or thermoplasticspheres such as polysulfone (PSU). In core shells, uponan impact event or an approaching crack tip front, stress isconcentrated in the low T
rubber core, causing cavitationof the core. This cavitation then causes subsequent plasticdeformation of the surrounding matrix (often referred to asshear banding), absorbing energy from the impact or crack front and thus toughening the epoxy. The difficulty withthe use of core shells in epoxies relates to the problems of achieving a uniform dispersion; the highly cross-linkedrubber cores do not allow for their dissolution in epoxyresins. (Core shells are typically used to toughenthermoplastics where extremely high shear and hightemperatures aid dispersion during extrusion.)Thermoplastic spheres suffer from having a much highermodulus. Thus, they are not effective as stressconcentrators and cannot easily cavitate. They can onlytoughen the epoxy by physical mechanism such as crack pinning or crack deflection, less efficient mechanisms thanthe previously described cavitation and shear bandformation mechanism. Due to this poor efficiency, theyare often used at high concentrations, where they can havea detrimental effect on properties critical to processingsuch as viscosity.In order to overcome the deficiencies associated with theaforementioned types of epoxy toughening agents,controlled radical polymerization and anionicpolymerization has been used to design acrylic block copolymers under the trade name of Nanostrength
block copolymers. The structure of these block copolymers canbe tuned to give excellent toughening to a wide range of epoxy systems without sacrificing strength or thermalproperties.
Block Copolymers – A Self AssemblingTechnology
One family of block copolymers useful in epoxies aretriblock polymers consisting of polymethylmethacrylate-b-polybutylacrylate-b-polymethylmethacrylate (MAM)family. The PMMA blocks give compatibility to epoxyresin, while the PBuA blocks provide an immisicible softrubber phase for toughening. The MAM products (e.g.M51, M52 and M53) can easily be dissolved in a typicaldiglycidyl ether of bisphenol A (DGEBA) resin with theapplication of heat and a low amount of shear. Whendissolved in DGEBA resin, the MAM block copolymerself-assemble into nanostructures. The PMMA block willassociate with the epoxy resin, forming an effective shellsurrounding an immiscible PBuA core. (Figure 1) TheBates group has shown using non-acrylic block copolymers polymers that the size and shape of the self-assembled structures can be varied from sphericalmicelles to worm-like micelles to vesicles by increasingthe ratio of epoxy immiscible block to epoxy miscibleblock.
A second family of block copolymer useful for tougheningof epoxies are styrene-b-butadiene-b-polymethylmethacrylate (SBM, such as grades E21 andE41) block copolymers. These polymers, made by